Elastomer S

MATERIALS SCIENCE AND TECHNOLOGY
ELASTOMERS
TYPES, PROPERTIES AND APPLICATIONS
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MATERIALS SCIENCE AND TECHNOLOGY
ELASTOMERS
TYPES, PROPERTIES AND APPLICATIONS
JOVAN BALCAZARA
AND
EDGARDO PAULES
EDITORS
Nova Science Publishers, Inc.

New York
Copyright 2012 by Nova Science Publishers, Inc.

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Library of Congress Cataloging-in-Publication Data

Elastomers : types, properties, and applications / [edited by] Jovan Balcazara and Edgardo Pauless.
p. cm.
Includes bibliographical references and index.
ISBN: 978-1-61470-272-6 (eBook)
Elastomers. I. Balcazara, Jovan. II. Pauless,
Edgardo.
TA455.E4E435 2011
620.1'94--dc23
2011020347
Published by Nova Science Publishers, Inc. New York
CONTENTS
Preface
Chapter 1
vii
-Nucleated ThermoplasticVulcanizates Based

on iPP/EPDM Blends: Preparation, Properties
and Application
Wei-Kang Wang, Xue-Gang Tang, Rui-Ying Bao,
Wei Yang, Bang-Hu Xie and Ming-Bo Yang
Chapter 2
Chapter 3
Chapter 4
Chapter 5
Chapter 6
Patternable Biomaterials; Elastomers for

Biomedical Applications
Marga C Lensen, Mar Diez and Vera A Schulte
Properties and Applications of Water Swelling
Materials in Civil Engineering Fields
Shinya Inazumi, Tadashi Wakatsuki
and Masakatsu Kobayashi
Elastomeric Diffractive Optics Fabricated
by Soft Lithography
Raphael A. Guerrero
Optical Spectra of Chiral Elastomers During
Segregation and Elastic Processes
J. Adrian Reyes, Laura O. Palomares
and Carlos G. Avendano
Properties of Elastomers Based
on Caprolactone Prepolymers
Rui Xie
37
59
79
97
151
vi
Chapter 7
Chapter 8
Index
Contents
The Effect of Brominated Fire Retardants
on the Properties of Thermoplstic Elastomers
Based on PP and EPDM
N. A. Khalturinskii, D. D. Novikov, L. A. Zhorina,
L. V. Kompaniets, T. A. Rudakova, L. A. Tkachenko
and E. V. Prut
Interfacial Interaction in Blends of Elastomers
with Different Polarities
N. M. Livanova
169
177
189
PREFACE
This book presents topical research in the study of the types, properties
and applications of elastomers. Topics discussed in this compilation include
elastomers for biomedical applications; elastomeric diffractive optics
fabricated by soft lithography; optical spectra of chiral elastomers during
segregation and elastic processes; the effect of brominated fire retardants on
the properties of thermoplastic elastomers and interfacial interaction in blends
of elastomers with different polarities.
Chapter 1 - Thermoplastic vulcanizates, or TPVs, are blends where the
elastomers are vulcanized in-situ during melt mixing with the thermoplastic
component at high shear and elevated temperature. -nucleating agent (-NA)
for polypropylene (PP), is introduced into the phenolic resin (PF) vulcanized
TPVs based on isotactic polypropylene (iPP)/ ethylene-propylene-dienerubber
(EPDM) blends (PP:EPDM=50:50 wt%) and -nucleated TPVs based on
iPP/EPDM blends are obtained.
The fracture behavior of the -nucleated TPVs, or -TPVs for short, was
characterized with the double edge notched tensile loaded specimens (DENT)
using the essential work of fracture (EWF) approach. The specific essential
work of fracture, we, increases with increasing content of phase of PP,
indicating that the presence of phase can effectively enhance the fracture
toughness of TPVs.
Some factors influencing the development of phase in the TPVs were
considered. The effect of temperature gradient was considered first. Different
temperature gradients were created by selecting different sample thickness,
and the strength of the temperature gradient increases with the sample
thickness increasing. It was found that the content of phase increases with
the increasing sample thickness, which may be due to the reduction of the
viii
Jovan Balcazara and Edgardo Paules
entropy in the temperature gradient field, resulting from a decrease of the

molecular chain conformation. Second, the effect of the crosslinking degree of
the EPDM phase was considered. With the -NA content unchanged, the
content of phase in the blends initially increases a little and then decreases
with increasing content of cross-linking agent, PF. Spatial confinement
provides an explanation for the development of phase in this case.
For the application aspect, the repetitive processing of the -TPVs based
on iPP/EPDM blends and the toughening effect on PP and PA 6 were
considered. The repetitive processing does not cause much loss in the
mechanical properties of TPVs, especially for the -TPVs. During the EWF
test, the value of we of TPVs without -NA shows a significant decrease while
that of -TPVs almost keeps constant after repetitive processing.
With respect to the toughening ability, for iPP matrix, the notched impact
strength of PP toughened by the -TPVs shows an almost linear increase with
increasing -NA content. Especially when the content of -NA is 0.5 wt%, the
value of impact strength is ten times more than that of pure PP. For PA 6
matrix, we used maleic anhydride grafted EPDM to replace EPDM in the
preparation of the -TPVs and adopted another high-efficiency -NA, TMB
(amide compound) aiming at improving the compatibility between the
components. Also the value of notched impact strength of PA 6 toughened
with -nucleated TPVs is about 3 times that of pure PA6.
Chapter 2 - We have investigated two elastomers with contrasting
properties in terms of surface chemistry, and with similar applications as
a biomaterial. The first elastomer is prepared from a star-shaped poly(ethylene
glycol) (PEG) macromolecule with acrylate end groups. The second
elastomer is formed from linear perfluorinated polyether (PFPE)
dimethacrylatemacromonomers. Both precursor polymers can be transformed
into elastomeric materials by means of UV-curing, i.e. photoinitiated, radical
crosslinking reactions in the presence of a photoinitiator and eventually a
crosslinking agent by illumination with ultraviolet (UV-) light. Since both
macromonomers are viscous liquids before crosslinking, the precursor
mixtures can be molded in any shape and result in topographically patterned
elastomers. We have investigated both elastomers in cell culture studies to
elucidate cellular responses to the material depending on the surface
topography.
Elastomers prepared from the PEG-precursor form gels that are insoluble
in water, but have the propensity to take up large quantities of water, hence
hydrogels. These materials are very hydrophilic and their hydrated nature
results in effective prevention of non-specific protein adsorption and cell
Preface
ix
adhesion. PFPE-elastomers were also expected to be anti-adhesive to cells,

since the material after crosslinking of the precursors is both very hydrophobic
and oleophobic; it has properties comparable to those of teflon, which is
renown for its inertness and non-wettability by both water and oils.
Both elastomers have been investigated in cell culture, using fibroblasts
and human macrophages. The following, striking results have been observed:
1) whereas smooth PEG hydrogels are anti-adhesive to cells as expected, a
significant number of cells do adhere to the PEG surface when it is decorated
with micrometer topographic patterns; 2) PFPE elastomers were found to be
non-cytotoxic and to support cell adhesion in a comparable, albeit delayed,
manner as does tissue culture polystyrene (TCPS); 3) macrophages are not
activated by the PFPE biomaterial per se, but do show a pro- or antiinflammatory phenotype depending on the geometry, size and periodicity of
the topographic micropatterns.
In conclusion, the authors have prepared two distinctly different
elastomers and investigated them as novel biomaterials. Both elastomers
showed excellent cytocompatibility and patternability. These patternable
elastomers are a versatile platform for fundamental cell studies and the results
are very useful for biomedical applications, e.g. for the design of implant
materials with specific functions due to their surface characteristics and for
biosensor applications where the non-specific protein adsorption should be
suppressed, while at the same time complex 2D and 3D geometries are
required.
Chapter 3 - Water-swelling material is a fluid sealant obtained by blending
high absorbency polymer, a filler and a solvent by using a synthetic resin
elastomer as the base material. In this research, the authors have studied the
composition of water-swelling material, the extent of swelling, strength of the
water swelling-material and the long-term performance of swelling material
used as jointed water cut-off treatment material at waste landfill sites, by
conducting various experiments. One of the examples of the results is that the
adjustment of the degree of etherification of high absorbency polymer which is
a component of the water-swelling material and the resin content of the
synthetic elastomer contribute to the improvement of swelling of the sealant
and strength of the swelling material. Further, as time passes, the strength of
the water-swelling material shows a tendency to become stabilized and it was
confirmed that it had sufficient pressure-resistance in coastal landfill sites,
where its application as water cut-off treatment material is being considered.
Chapter 4 - Soft lithographic techniques allow the convenient preparation
of deformable elastomeric optical elements. Elastomers, due to their low cost
and versatile fabrication protocols, have proven to be ideal materials for

developing flexible optics for diverse systems. Specific applications in
multiplexed volume holography and variable diffraction with a silicone grating
are discussed in this chapter. Replication of diffractive surfaces by soft
lithography is described for both holographic phase masks and planar gratings.
A theoretical framework is established for storing multiple holograms with an
elastomer mask based on the modification of path length by the application of
strain. Dynamic diffraction with a stretchable grating is accounted for by a
simple modification of the grating equation that accommodates a change in
groove periodicity due to elongation. Experimental results for volume
holography include the storage and reconstruction of two-dimensional images
and notes on phase selectivity. Angular scanning as a function of strain is
demonstrated for elastomeric gratings. Included in this chapter are recent
developments in biomimetic optics afforded by soft lithography. Diffraction
effects from grating structures on an elastomer cast of an insect carapace are
presented. The chapter concludes with a discourse on beam deflection and
color displays with an elastomer grating actuated by a shape memory alloy.
Chapter 5 - Chiral elastomers (CEs) are rubbers formed by monomers of
liquid crystals weakly cross-linked to polymeric chains, this union produces a
flexible material whose molecular order is similar to cholesteric liquid crystals
with the advantage that in this new material the responses to external stimuli
are exceptionally large [1]. These stimuli could be mechanical, thermal, and
electromagnetical with elastic and optical responses, giving rise to a wide
range of applications such as artificial muscles, optical fibers, resonators and
optical filters. In this chapter we focus in optical responses due to changes
induced into the material by means of macroscopic deformations and chemical
segregation processes due to their interesting applications. CEs, just like
cholesteric liquid crystals [3] and chiral sculptured thin films [4], are
structurally chiral materials that display the circular Bragg phenomenon (CBP)
whereby a normally incident, circularly polarized plane wave of a specific
handedness is highly reflected in a certain wavelength regime, whereas a
similar plane wave but of the reverse handedness is transmitted. This
polarization-discriminatory filtering characteristic of structurally chiral
materials is very attractive in optical technology [5]. Additionally, materials
with helical symmetry are unique periodic structures whose optical properties
can be defined by equations which, for axial light propagation are exact and
very simple, this analytical expressions give remarkable insight on the
phenomena. Another outstanding property of CEs is segregation, which in fact
is the ability to absorb and retain preferably left- or right-chiral molecules
Preface
xi
from a racemic solvent. Mechanical stress in CEs make feasible to control the
optical properties for tunning the CBP and switching applications with the
potential additional application of optical monitoring the chiral pump when the
chemical segregation process is considered. Here, the authors revised in detail
the most widely used general formalisms, as the Berremans method and the
representation of Marcuvitz-Schwinger with the transformation of Oseen, to
calculate the band structure, transmittance and reflectance co-polarized and
cross-polarized spectra of chiral-elastomer slabs. The authors study the
modifications on optical spectra and band structure due to the action of some
external agents. When an externally induced mechanical strain is applied
parallel to the helical axis, the analysis of remittances shows the possibility of
mechanically control the CBP for which the bandwidth and the central
wavelength are significantly modified. Thus, the reflection band blue-shifts
versus the incidence angles, as happens in absence of strain [6]. On the other
hand, if an uniaxial transverse stress is applied on the slab, there exists a leftcircularly polarized thin reflection band immersed in a wider right-circularly
polarized band reflection when the elastomer is under a stress near to the
critical value. These band gap features suggest to design a finely tuning
polarization-universal optical filter [7]. Moreover, when a CE is immersed in a
racemic solvent, there is a significant width reduction of the reflection band
for certain values of nematic penetration depth, which depends on the volume
fraction of molecules from the solvent, whose handedness is preferably
absorbed. The appearance of nested band gaps of both handednesses during
the sorting mixed chiral process is also obtained. This suggests the design of
chemically controlled optical filters and optically monitored chiral pumps [8].
Chapter 6 In recent years, caprolactone based prepolymers have gained
more and more acceptance in the market place because of their balanced
properties. In some applications where high temperature performance,
dynamic properties, abrasion and flex fatigue resistance are desired, the
caprolactone-based prepolymers have become the primary choice. In this
chapter, properties of elastomers based on ether, ester and caprolactone
polyols were studied side-by-side. Preliminary results demonstrated that the
caprolactone-based elastomers possessed excellent dynamic properties,
improved heat resistance, excellent gasoline resistance, superior abrasion
resistance, and better cutting growth resistance and weatherability. These
characteristics make the elastomers suitable for various applications. Some
commercial applications of such elastomers in pipeline pigs, conveyor belts,
and industrial wheels and tires were discussed in the chapter.
xii
Chapter 7 - The effect of fire retardants on the combustion and mechanical

properties of thermoplastic vulcanizates based on PP and EPDM was studied.
A modified mixture of decabromodiphenyl oxide and antimony trioxide was
used as a fire retardant. It was shown that the addition of fire retardants results
in a considerable increase of the oxygen index from 17.2 to 27.9% and the
thermoplastic vulcanizate passes into the category of low-combustible
materials according to V0. The mechanical properties of the blends containing
up to 20 wt % fire retardant change insignificantly and their rheological
properties are deteriorated. The mechanism of combustion of thermoplastic
vulcanizates is proposed.
Chapter 8 - The effects of isomers of butadiene units, the ratio of
comonomers in ethylene-propylene-diene terpolymers, and the degree of
isotacticity of propylene units in the layer on the intensity of interfacial
interaction in covulcanizates of butadiene-acrylonitrile rubbers of different
polarities and ethylene-propylene-diene terpolymers have been analyzed.
In: Elastomers: Types, Properties and Applications ISBN 978-1-61470-198-9

2012 Nova Science Publishers, Inc.
Editors: J. Balcazara et al.
Chapter 1
-NUCLEATED THERMOPLASTIC
VULCANIZATES BASED
ON IPP/EPDM BLENDS: PREPARATION,
PROPERTIES AND APPLICATION
Wei-Kang Wang, Xue-Gang Tang, Rui-Ying Bao,
Wei Yang*, Bang-Hu Xie and Ming-Bo Yang
College of Polymer Science and Engineering, Sichuan University, State
Key Laboratory of Polymer Materials Engineering, Chengdu, 610065,
Sichuan, Peoples Republic of China
Abstract
Thermoplastic vulcanizates, or TPVs, are blends where the
elastomers are vulcanized in-situ during melt mixing with the
thermoplastic component at high shear and elevated temperature. nucleating agent (-NA) for polypropylene (PP), is introduced into the
phenolic resin (PF) vulcanized TPVs based on isotactic polypropylene
(iPP)/ ethylene-propylene-dienerubber (EPDM) blends (PP:EPDM=50:50
wt%) and -nucleated TPVs based on iPP/EPDM blends are obtained.
The fracture behavior of the -nucleated TPVs, or -TPVs for short,
was characterized with the double edge notched tensile loaded specimens
*
Corresponding authors. Tel.:/fax: + 86 28 8546 0130. E-mail address: ysjsanjin@163.com.
Wei-Kang Wang, Xue-Gang Tang, Rui-Ying Bao et al.

(DENT) using the essential work of fracture (EWF) approach. The
specific essential work of fracture, we, increases with increasing content
of phase of PP, indicating that the presence of phase can effectively
enhance the fracture toughness of TPVs.
Some factors influencing the development of phase in the TPVs
were considered. The effect of temperature gradient was considered first.
Different temperature gradients were created by selecting different
sample thickness, and the strength of the temperature gradient increases
with the sample thickness increasing. It was found that the content of
phase increases with the increasing sample thickness, which may be due
to the reduction of the entropy in the temperature gradient field, resulting
from a decrease of the molecular chain conformation. Second, the effect
of the crosslinking degree of the EPDM phase was considered. With the
-NA content unchanged, the content of phase in the blends initially
increases a little and then decreases with increasing content of crosslinking agent, PF. Spatial confinement provides an explanation for the
development of phase in this case.
For the application aspect, the repetitive processing of the -TPVs
based on iPP/EPDM blends and the toughening effect on PP and PA 6
were considered. The repetitive processing does not cause much loss in
the mechanical properties of TPVs, especially for the -TPVs. During the
EWF test, the value of we of TPVs without -NA shows a significant
decrease while that of -TPVs almost keeps constant after repetitive
processing.
With respect to the toughening ability, for iPP matrix, the notched
impact strength of PP toughened by the -TPVs shows an almost linear
increase with increasing -NA content. Especially when the content of NA is 0.5 wt%, the value of impact strength is ten times more than that of
pure PP. For PA 6 matrix, we used maleic anhydride grafted EPDM to
replace EPDM in the preparation of the -TPVs and adopted another
high-efficiency -NA, TMB (amide compound) aiming at improving the
compatibility between the components. Also the value of notched impact
strength of PA 6 toughened with -nucleated TPVs is about 3 times that
of pure PA6.
1. INTRODUCTION
Isotactic polypropylene (iPP) is a semicrystalline, polymorphic material
with several crystal modifications including monoclinic (), hexagonal (),
-Nucleated Thermoplastic Vulcanizates Based
and orthorhombic (). Generally, iPP crystallizes into -phase (-iPP) under
normal processing conditions used in the industrial practice, while -phase (iPP) can be prepared with the aid of selective -nucleating agent (-NA) and
results in peculiar crystal morphology, thermal and mechanical properties such
as lower crystal density, melting temperature and fusion enthalpy, but higher
heat distortion temperature, and especially higher impact strength in
comparison with the -iPP [1-7].
iPP is a general purpose resin with extensive usage and promising market
prospect, but its low-temperature brittleness restricts its application. Various
elastomers such as ethylene-propylene rubber (EPR), styrene-butadienestyrene (SBS) copolymer, butyl rubber, and ethylene-propylene-diene rubber
(EPDM), have been introduced into iPP to improve its impact toughness. The
materials prepared by blending a thermoplastic with an elastomer, such as
iPP/EPDM blends, are usually called thermoplastic elastomers (TPE). As TPE
combines the elastic properties of rubber and melt processability of
thermoplastics, it has many important applications including cable and wire,
especially in mineral, electronic equipment, constructions and automotives
industries [8-11].
Further improvement in performances of TPE can be gained by the
dynamic vulcanization process. Thermoplastic vulcanizates, or TPVs, are
blends where the elastomeric component is vulcanized in-situ during melt
mixing with the thermoplastic component at high shear and elevated
temperature. Compared with unvulcanized iPP/EPDM blends, the properties
such as the oil resistance, permanent set, ultimate mechanical properties,
fatigue resistance, heat deformation, and melt strength among others, of
iPP/EPDM TPVs are improved. It has been shown that dynamic crosslinking
of EPDM during its melt mixing with iPP can improve certain properties of
the blend, which even results in high impact PP based materials. These
enhanced properties of TPVs are attributed to the unique morphology that
small and uniform crosslinked rubber particles finely distribute in the PP
matrix [12-14].
2. PREPARATION OF -NUCLEATEDTPVS
In our work, we introduced -NA into the dynamically vulcanized TPVs
based on iPP/EPDM blends (iPP:EPDM=50:50wt%). 0.1~0.5wt% (to the
weight of the blends) WBG-II, a rare earth-containing -NA with high
selectivity and thermal stability was used. 1~6wt% (to the weight of the
blends) phenolic resin (PF), which just reacts with EPDM and does not induce
the degradation of iPP because of the absence of unsaturation [15], was
adopted as the curing agent. The melt reactive blending process for preparing
TPV samples was carried out in an SHJ-20 co-rotating twin-screw extruder
with a screw diameter of 25 mm, a length/diameter ratio of 23, and a
temperature profile of 170, 180, 190, and 185C from the feeding zone to the
die. iPP, EPDM, phenolic resin, and -NA were simply mixed first, and then
added to the twin-screw extruder. The obtained extrudate, -nucleated TPVs
based on iPP/EPDM blends, or -TPVs for short, were pelletized. The pellets
were then dried and injection molded into dumb-bell tensile test samples and
impact test samples on a PS40E5ASE precise injection-molding machine, with
a temperature profile of 170, 190, 200, and 195C from the feeding zone to the
nozzle. Both the injection pressure and the holding pressure were 37.4 MPa.
The obtained samples were heat pressed for 10min in a compression mold
machine (XLB-D 4004002) into a 1mm thick sheet, with a temperature of
200 C and a pressure of 10MPa. The compression molded sheet was then
cooled to room temperature under pressure and used for test after 24 h storage
at room temperature.
3. PROPERTIESOF -TPVS
3.1.Effect of -Phase on the Fracture Behavior of -TPVs
The curiosity is whether or not the introduction of -phase induced by NA can further improve the toughness of TPVs based on the iPP/EPDM blend.
So far as we know, this topic receives little attention. We investigated the
effect of -phase on the fracture behavior of -TPVs by Essential Work of
Fracture (EWF) approach [15].
For the toughness characterization of polymers, the impact test is a simple
and direct method unless the samples can not be broken under impact. At
present, the evaluation of fracture behavior for sheets and films still faces
some problems using conventional methods. Tear tests do not provide
information about instrinsic material properties. Linear elastic fracture
mechanics is not applicable for ductile films due to the strong yielding and
large plastic deformation occurring in the fracture process. The application of
J-integral analysis, a popular elastic-plastic fracture mechanics method, which
has been used traditionally for fracture evaluation of materials with significant
crack tip plasticity, is also limited because the strict size requirements make it
impossible to characterize the fracture behavior of thin sheets and films.
Recently, the EWF approach has gained more and more attention due to
its obvious merits such as the simplicity of experiment and data manipulation
[16-21]. So EWF approach is a useful alternative to characterize the fracture
behavior of thin sheets and films. In the EWF test, the following are the
important correlations:
(1)
W f = We + W p
We = we BL
(2)
Wp = wp BL2
(3)
wf =
Wf
= we + wp L
LB
(4)
where L is the ligament length; B is the specimen thickness; Wf is the total

work of fracture; wf is the specific total work of fracture; We, the essential
work of fracture, is essentially a surface energy dissipated in the inner fracture
process zone (IFPZ) to generate new crack surface during the fracture and is
proportional to the ligament area (LB); we is the specific essential work of
fracture; Wp, the non-essential work of fracture, is a volume energy dissipated
in the outer plastic deformation zone (OPDZ) and is proportional to the
volume of the yield zone (BL2); wp is the specific non-essential work of
fracture and is a proportionality constant or shape factor associated with the
volume of the plastic deformation zone. For a given thickness, we is regarded
as a material constant and, provided the term wp remains independent of the
L, a linear relationship is expected between wf and L as suggested by Eq. (4).
By extrapolating the curve of wf versus L to zero ligament length, the value of
we can be obtained from the intercept and the value of wp can be obtained
from the slope of the regression lines.
For the sake of brevity, the prepared TPVs with different -NA dosage
were denoted as TPV1 (0 wt %-NA), TPV2 (0.1 wt %-NA), TPV3 (0.2 wt
%-NA), TPV4 (0.3 wt %-NA), TPV5 (0.4wt%-NA), TPV6 (0.5wt%-NA)
respectively. The double-edged notch tension (DENT) specimens
(lengthwidth=10035 mm) seen in Fig. 1 for the EWF tests were die cut
from the compression molded sheets of TPVs. Deep blunt notches were
induced on both sides of the specimens by a sharp knife. The notches were cut
perpendicularly to the tensile direction by a fresh razor blade to produce the
sharp pre-crack that was required. Thus, at least 17 specimens for each set
were obtained. The ligament lengths and thicknesses were measured before
testing using a reading microscope and a Vernier caliper. Static tensile tests on
DENT specimens were performed on an Instron universal testing machine
(model 5567) test machine at 25C and the crosshead speed was 5mm/min.
Figure 1.The double-edged notch tension sample used in the EWF test; IFPZ: inner
fracture process zone; OPDZ: outer plastic deformation zone. (From Reference 15 with
permission from Elsevier Ltd.)
Wide-angle X-ray diffraction (WAXD) measurement was carried out to

investigate the crystalline structures of samples. The WAXD curves of the
TPVs containing different content of -NA are shown in Fig. 2(a). In the
diffraction pattern of TPV1, there are five distinct peaks appearing at 2 of
about 14.1, 17.0, 18.6, 21.2, and 21.9 respectively, which correspond to the
(110), (040), (130),(131), and (111) reflections of -iPP, indicating that the phase dominates TPV1. For TPV3, there is a very tiny peak at about 16,
which corresponds to the (300) reflection of -phase of iPP, indicating a few
crystals existed in TPV3 [3-6]. The intensity of the characteristic peak of phase, i.e. the (300) reflection, increases with the -NA content increasing, and
meanwhile, characteristic peaks of the -phase are weakened. When 0.5wt%
-NA is added, it is hard to find the characteristic peaks of -phase. The
relative content of -form ( K ) from the WAXD patterns can be calculated
by the well known Turner-Jones equation [22]:

K =
I1
(5)
I 1 + I 1 + I 2 + I 3
where I 1 is the intensity of the (300) reflection of the phase and I 1 , I 2

and I 3 are the intensities of the (110), (040) and (130) reflections of the
phase, respectively. All the diffraction data were corrected for background (air
and instrument) scattering before analysis. The K values obtained for the
blends are illustrated in Fig. 2(b). It is clear that the K value increases with
the -NA content increasing.
1.0
0.8
Intensity
TPV6
0.6
TPV4
TPV3
TPV5
0.4
0.2
TPV2
TPV1
10
20
(a)
30
0.0
0.0
0.1
0.2
0.3
0.4
0.5
nucleating agent content (%)
(b)
Figure 2.WAXD patterns (a) and corresponding K value (b) of TPVs with different NA content. (From Reference 15 with permission from Elsevier Ltd.)
The load-displacement curves of DENT specimens of TPV1 and TPV6 are

shown in Fig. 3. The load increases quickly with a slight increase of the
displacement before the upper point in the initial stage. After the peak, a
smooth and slow drop in load occurred with further increase of displacement
and suddenly a rapid load drop at the end stage of the curves signaling the
fracture of the specimens. A precondition for EWF method is that the curves
of the load-displacement should be fully yielded prior to crack growth.
According to the load-displacement curves in Fig. 3, no full ligament yielding
occurs prior to crack growth while yielding occurs simultaneously with crack
growth, which make using the EWF approach tolerable when all other
prerequisite of the EWF are met [23]. At the same time, the curves were
obtained for DENT specimens with different ligament length; good selfsimilarity of the curves was shown in each group. The maximum load and the
displacement to failure all increased regularly with increasing ligament length

indicating the mode of fracture is independent of ligament length and the
cracks propagate under similar stress conditions. This is another crucial
criterion for the application of EWF method, which ensures the cracks
propagated under similar stress conditions, unchanged with the ligament
length. The two requirements for validity are satisfied and the EWF
measurements are therefore valid at this deformation rate for the TPVs studied
[23-25].As a result, the linear regression of the specific work of fracture versus
ligament length gives a high relative coefficient.
70
60
60
50
Ligment length increasing
40
30
Load (N)
Load (N)
50
30
20
20
10
10
0
0
10
Displacement (mm)
(a)
12
14
16
Ligment length increasing
40
0
0
10
Displacement (mm)
12
14
16
18
(b)
Figure 3.Plot of load versus displacement of different TPVs: a) TPV1, b) TPV6. (From
Reference 15 with permission from Elsevier Ltd.)
The plot of wf versus L in different TPVs is shown in Fig. 4. It indicates

that the wf~L diagrams show very good linear relationships for all the samples,
proved by the linear regression coefficient (R2), most of which are higher than
0.97. The values of we and wp extracted from Fig. 4 are collected in Tab. 1. It
is obvious that the we for TPVs strongly depends on the -NA content. The
higher the -NA content, the higher the value of we and the higher the crack
resistance, which is believed to result from the presence of -phase with the
addition of -NA.

150
140
130
120
110
100
wf (kJ/m )
90
80
70
60
TPV1
TPV2
TPV3
TPV4
TPV5
TPV6
50
40
30
20
10
0
10
12
Ligment length (mm)
Figure 4.Specific total work of fracture plotted against ligament length for: () TPV1
(curve a), () TPV2 (curve b), () TPV3 (curve c), () TPV4 (curve d), () TPV5
(curve e), () TPV6 (curve f). (From Reference 15 with permission from Elsevier
Ltd.)
Table 1. Fracture parameters for the TPVs with varied content of -NA. (From
Reference 15 with permission from Elsevier Ltd.)
Sample
TPV1( 0%-NA )
TPV2( 1%-NA )
TPV3( 2%-NA )
TPV4( 3%-NA )
TPV5( 4%-NA )
TPV6( 5%-NA )
we(kJ/m2)
16.61
16.78
17.61
19.12
24.03
24.94
wp(MJ/m3)
9.26
11.12
9.48
11.18
9.04
8.61
It has been widely reported that -PP exhibits a superior impact

performance compared to their non-nucleated or -nucleated homologues [36]. The mechanism of toughness improvement is still a controversial topic.
However, there are no doubts that both the microstructure (lamellar
assignment) and loading-induced polymorphic transition play an
important role in the toughening effect. It is demonstrated by several
researchers that lamellae structure of phase are not organized in a crosshatched but in a bundled structure with no clear boundaries between them [2629]. The sheaf-like lamellar structure results in a substantial improvement in
ductility. It is worth noting that though the distinct structure of lamellae is
10
very complex (branching on screw dislocations, three dimensional

curvatures)[30], lamellae bundles, held together by the tie molecules that run
through the amorphous phase of -PP can easily separate from one another
upon loading. The micro-drawing of -PP proceeds mainly by inter lamellar
slippage and chain slip. Furthermore, the tie molecules are also aligned into
tie-fibrils during the inter lamellar slippage. This lamellae separation is
accompanied by massive voiding with the simultaneous onset of a craze-like
microporous structure [27-29]. It is also worth mentioning that the production
of films with such a microporous structure is one of the preferred applications
of -PP. The lamellae involved in these microcacks network deform and break
up by homogeneous (tilting) and heterogeneous slippages (break-up). Those
lamellae which are oriented along the loading direction may defold. This
failure, viz. break-up and defolding of the lamellae, is likely to lead the
polymorphic transition which also represents energy absorption for
toughening. This occurs via a recrystallization process as the handedness of
the helices in the related elementary cells should change during this transition.
So in TPVs, the introduction of -phase indeed further enhances the
toughness, especially when the content of -phase is 42.21% (TPV5,
calculated from DSC results, not shown here), there is an increase of about
52% in the value of we. The value of wp just fluctuates around 10 MJ/m3,
which means that there is not significant change for the energy of plastic
deformation absorbed during the fracture process. The results discord with
some literatures [31-32], which show that the we is constant and wp increases
with the appearance of -phase. The probable cause of the results is that the
role of -phase in this system and pure PP is different. For pure PP, -phase
may have a significant effect on the plastic deformation owing to its special
lamellar morphology. While in this system, the -phase shows a stronger
effect on the crack growth than on the plastic deformation owing to the
introduction of EPDM and resulting phase morphology where the -phase was
induced.
In conclusion, the introduction of -NA can not only effectively induce
the -phase in the thermoplastic vulcanizates based on PP/EPDM blends but
also further improves the ductility of TPVs. The factors influencing the
development of phase in the TPVs need to be considered in the following
work because the information can lead to deeper understanding of the essence
of the development of -PP in polymer blends and guide us to design and
prepare PP-based high performance materials.
11
3.2. Effect of Temperature Gradient on the Development of iPP in TPVs
Heat flow
As suggested previously, the role of -phase in the blend system and pure
PP is different. It is well known that the temperature field has a profound
effect on the formation of polymer crystals, which may affect the rate of
crystallization and the thickness of crystal lamella, and the situation is more
distinct for PP. So, the effect of temperature gradient on the development of iPP in TPVs was discussed in detail [33]. Samples with different thicknesses
were prepared by gently grinding the compression molded sheet on abrasive
papers. Then, they were heat treated on a hot stage to ensure that they
experienced the same thermal history.
1mm
0.7mm
0.5mm
0.3mm
60
80
100
120
140
160
180
Temperature ( C)
Figure 5.The melting behaviors of the compression molded TPVs with different
thickness. (From Reference 33with permission from Springer.)
The melting behaviors of the heat-treated samples were studied by

differential scanning calorimetry (DSC). Fig. 5 shows the melting behavior of
the TPV samples with different thicknesses. Two distinct melting peaks can be
observed clearly for all the samples, the lower one corresponds to the
characteristic melting peak for -PP, and the higher one corresponds to the
characteristic melting peak for -PP [3-6]. With the increasing of sample
thickness, the height of melting peak for phase PP increases, indicating the
higher content of phase PP. The temperature of the melting peaks also
increases with the increase of sample thickness, which means the higher
12
degree of perfection of phase was presented in TPV samples with larger

thickness.
According to WAXD measurements (not given here), different K values
and the total crystallinity depending on the sample thickness are illustrated in
Fig. 6(a) and (b) respectively. These results show clearly that the K value
increases with the sample thickness increasing while the total crystallinity
almost keeps constant. This suggests that the sample thickness has a distinct
effect on the development of the crystals and there may be competition
between the growth of -PP and -PP.
60
0.5
50
0.4
Crystallinity (%)
40
0.3
0.2
30
20
0.1
10
0.0
0.2
0.4
0.6
0.8
The thickness of TPV sample (mm)
(a)
1.0
0
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
1.1
The thickness of TPV sample (mm)
(b)
Figure 6.Effect of sample thickness on the K value (a) and crystallinity (b) of the
compression molded TPVs. (From Reference 33 with permission from Springer.)
To clarify the influence of temperature field on the development of phase, Cao and Faghris enthalpy transformation method, which shows good
practicability in solving heat conduction problems with latent heat effects, is
used to simulate the one dimensional phase-change heat conduction behaviors
of the sample during the cooling stage [34-35]. Through the discretization and
iterative process of the control-volume /finite-difference method, the
development of temperature versus the cooling time at various locations in the
samples can be predicted. Five positions with the same distance across the
thickness direction, in accordance with those in WAXD measurement, have
been selected (seen in Fig. 7).
Fig. 8 (a) shows clearly the temperature distribution during the cooling of
a 1mm-thick sample. The temperature variation of each layer is not the same
and there is a temperature gradient along the direction of sample thickness
during the cooling process. The same phenomenon is also found in the other
13
samples, but the strength of the temperature gradient (the temperature

difference divided by the thickness) for samples of different thickness is not
the same. From Fig. 8(b), it can be seen that the strength of temperature
gradient increases with the increasing of sample thickness. The thicker the
sample, the more time needed to dissipate the heat, and then the stronger
temperature gradient existed.
Figure 7.The schematic presentation of the simulated positions in the TPV samples.
(From Reference 33 with permission from Springer).
0.5
220
Temperature gradient ( C/mm)
200
140
120
160.4
60
40
e
d
c
160.3
100
80
1.0mm
0.4
160
Temperature ( C)
Temperature ( C)
180
160.2
160.1
b
160.0
0.7mm
0.3
0.2
0.5mm
159.9
113.0
113.2
113.4
113.6
113.8
0.3mm
0.1
114.0
Time (second)
20
-100
100
200
300
400
500
600
Time (sec)
(a)
700
800
900 1000 1100
-100
100
200
300
400
500
600
700
800
900 1000 1100 1200
Time (Sec)
(b)
Figure 8.Simulated cooling temperature profiles at various locations for the TPV
sample with the thickness of 1mm (a) and the strength of the temperature gradient of
samples with different thickness (b). (From Reference 33 with permission from
Springer).
The relationship among the -PP content, sample thickness, and

temperature gradient field should be built, so the following discussion comes
14
along with the above results. Usually, the processes of crystallization and
crystal growth are controlled by thermodynamic and kinetic factors.
Thermodynamics will dictate the preferred, lowest energy form, but the rate at
which this state is achieved will depend on the processes involved in the
molecule alignment-kinetic factors [36]. The classical approach to the analysis
of crystal growth considers the thermodynamic changes that occur in
crystallization [37]. The overall free energy difference, G, can be expressed
as an equation as follows:
G = H T S
(6)
Based on a lot of related researches [38-41], we can safely draw the

conclusion that in the temperature gradient field, the molecules move along the
temperature gradient. For macromolecules, long-chain molecules, they are also
supposed to orient along the temperature gradient because the segments in
high temperature have larger mobility than those in low temperature. It is wellknown that S=klnW, in which W stands for the probable configuration. Once
the orientation of the macromolecules occurs, the probable configuration will
decrease resulting in the reduction of the entropy and the increment of the free
energy according to Eq. (6).
Generally, iPP crystallizes into the -phase (-iPP) under processing
conditions used in the industrial practice, because -phase has a lower energy
barrier for the crystal formation. However, there are some differences in the
temperature gradient field because of the reduction of the entropy or increase
in the G. Further improvement of energy will make the system easier to
overcome the energy barrier, and finally form crystal with higher energy level,
i.e. -phase here.
For the TPV sample with the thickness of 1mm, because of the strong
temperature gradient field, a large reduction of the S occurs. So, it is easier to
overcome the energy barrier to form -phase, and more crystals form.
However, for the TPV sample with the thickness of 0.3mm, the temperature
gradient field is so weak that the reduction of the S is limited and thus the
content of -phase PP formed is lower [33].
In a word, the temperature gradient field along the thickness of sample
greatly influences the configuration of macro-chains, and indirectly leads to
the differences of content of -phase viewing from the thermodynamic and
kinetic factors.
(a)
(b)
(c)
(d)
15
(e)
Figure 9. SEM micrographs of TPVs with different PF content: (a) TPV1, (b) TPV2,
(c) TPV3, (d) TPV4, (e) TPV5. (From Reference 42 with permission from Elsevier
Ltd).
16
3.3. Effect of Spatial Confinement on the Development of theiPPin TPVs

It is generally known that morphology is a determinant of the properties of
polymer blends, so it is interesting to know how the change of morphology
affects the development of -PP in dynamically vulcanized TPVs based on
PP/EPDM blends [42]. Enhanced crosslinking degree of EPDM enlarges the
viscous difference between PP and EPDM and then brings about the changes
of the phase structure. So TPVs with different PF dosageas the curing agent,
designated asTPV1 (0 wt %), TPV2 (1 wt %), TPV3 (2 wt %), TPV4 (4 wt %),
TPV5 (6wt %) respectively, were prepared and examined.
The phase morphology of TPVs with different PF content examined by
scanning electron microscope (SEM) is shown in Fig. 9. With increasing
content of curing agent, the EPDM phase changes from the dispersed phase to
a continuous one, and again to the dispersed phase, while the PP component
always presents in a continuous phase. For TPV1 with a small amount of
curing agent, both the viscosity difference between EPDM and PP and the
interaction between EPDM particles are increased. The dominant shear effect
results in the dispersion of EPDM phase in the PP matrix, in the shape of
deformed fiber or ellipsoid. With increasing PF content (TPV2, TPV3, and
TPV4), the interaction between EPDM particles is dominant, so EPDM
particles aggregate easily in the shape of deformed fiber-like structures and the
blends form a co-continuous morphology. With further increases of the PF
content (TPV5), viscosity difference between EPDM and PP plays the critical
role, so the less immobilized EPDM phase is easily broken down into small
droplets by intense shear [43].
Fig. 10(a) shows the WAXD patterns of samples with different PF
content. For TPV1, not only distinct characteristic peak of -phase, i.e. the
(300) reflection but also some weak peaks of -iPP exist in the pattern. For
TPV2, TPV3, TPV4, it is hard to identify the characteristic peaks of -phase,
indicating the -phase dominates the samples. For TPV5, no characteristic
reflections of -phase but only characteristic peaks of -phase exist. K values
from WAXD results of the TPVs are illustrated in Fig. 10(b), which
indicates that the K value increases with increasing PF content, and then,
sharply decreases when the PF content is 6wt%. Fig. 10(c) shows the effect
of PF content on the crystallization temperature from DSC results (not given
here). Interestingly, the changing trend is similar to that of K. For TPV1TPV4, the crystallization temperature is always above 120C, which
corresponds to the crystallization temperature of -PP, while for TPV5 when
17
the content of PF is up to 6wt%, the crystallization temperature is 114.07 C,

which is the crystallization temperature of -PP [15]. The incorporation of PF
changes the crystallization ability of phase, resulting in the change of
phase content in the samples. Moreover, the almost unchanged total
crystallinity (not shown here) suggests the competition between the
development of -PP and -PP.
TPV5
Intensity
TPV4
TPV3
TPV2
TPV1
10
20
30
40
(a)
1.0
126
124
0.8
122
120
Tp ( C)
0.6
0.4
118
116
0.2
114
0.0
0
PF content (wt%)
(b)
PF content (wt%)
(c)
Figure 10. Effect of PF content on the (a) WAXD pattens of TPVs, (b) K value of
TPVs, (c) Tc (crystallization temperature) at the cooling rate of 10 . (From Reference
42 with permission from Elsevier Ltd).
On the basis of the study of the lamellae structures of -PP and -PP,
Norton et al. [44] have pointed out that there are two possible growth
mechanisms leading to the spherical symmetry, i.e.: central multidirectional
growth (category 1) and sheaf-like unidirectional growth (category 2). The
spherulites in a bundled structure consisting of conventional smooth lamellae
(i.e. without cross-hatching) develop through the sheaving mechanism, and the
resulting spherulites are clearly of category 2. spherulites are organized in a
18
cross-hatched structure, even in the absence of nucleating foreign particle

and the growth is multidirectional. It is expected that the initial crystal will be
a trellis structure of mutually orthogonal lamellae (such as can be observed in
isolation from solution, the so called 'quadrites'). The continuing growth of the
lamellae constituting the trellis structure, combined with some fanning and
branching, will lead to a spherulite which conforms more closely to category l
[26-30].
It is known that confinement will lead to orientation. The orientation of
the polymer chains in polymer blends has been extensively studied in past
decades due to the possibility of producing unique orientation textures which
cannot be formed in single-component polymeric materials. The oriented
crystallization
has
also
been
examined
for
some
miscible
crystalline/amorphous polymer blends [45-48]. There are many ways to form
the confined domain, such as nano-rods or nano-tubes [49], block copolymer
[50-52], and blend [53]. All of these will form nano-scale confinement
structures, which will lead to the orientation of the molecular chains, and result
in oriented crystals. To better elucidate the morphologies of TPVs in this
work, according to the SEM micrographs in Fig. 9, a schematic diagram of the
structure of the TPVs with different PF content is given in Fig.11. The EPDM
phase in TPV1-TPV4 shows a fiber-like or elliptical shape with a large aspect
ratio, while the dispersed EPDM phase in TPV5 consists of spherical or nearspherical particles. There is a strong morphology confinement in the microscale to the lamellae structures because of these fiber-like structures, which
will result in the orientation of the lamellae.
Figure 11.The skeleton micrographs and analysis of TPVs with different PF content.
(From Reference 42 with permission from Elsevier Ltd).
19
It is well known that most polymer blends are often phase-separated and
thermodynamically unstable. For example, under quiescent conditions, the
domain size of the dispersed phase tends to increase with increasing time and
the deformed structure tends to shrink on account of a reduction of the
interfacial area or interfacial energy [54-57]. So for the EPDM phase in the
form of fiber or ellipsoid, the shrinkage trend during cooling, functioned as
another confinement and will change the local flow field between the
deformed structures. Fig. 12 shows the detailed analysis of this kind of
confinement.
Figure 12.The skeleton micrographs and detail analysis of TPVs with different PF
content. (From Reference 42 with permission from Elsevier Ltd).
Fig. 12 a and c are the initial stages of different shapes of the EPDM
phase. The second stage occurs as time goes by. There are two effects exerted
by EPDM phase, shrinkage (compression effect) and coarsening of EPDM.
For Fig. 12 b, in the region between the deformed structures, there is a
compression force on PP exerted by EPDM because of a dramatic synergy of
two effects, which will be helpful to the orientation of lamellae. For Fig. 12 d,
the coarsening effect is strong and the compression effect is very weak. During
the course of crystallization, these confinements facilitate the orientation of
lamellae. On a larger scale, the lamellae are organized in spherulites, densely
branched, isotropic, polycrystalline superstructures, which give the final
crystal structures.
As mentioned above, the growth mechanisms of -PP and -PP are
different. The mechanism for -PP is sheaf-like, unidirectional growth and the
lamellae will firstly grow along a particular direction and then form
spherulites; however, the mechanism for -PP is central, multidirectional
growth and the lamellae will grow multidirectionally. Obviously, the
20
orientation of lamellae will contribute a lot to the development of -PP rather

than -PP.
From TPV1 toTPV4, the strength of the spatial confinement increases a
little reflected in the morphology changes, accordingly, the -PP content also
increases a little; for TPV5, the strength of the spatial confinement becomes
very weak, so the the -PP content decreases greatly. The evolution of phase
morphology of the blends resulting from different dosages of PF leads to the
different crystallization ability of the matrix PP and different content of -PP
[42].
4.APPLICATIONS OF ETA-TPVS
4.1. Effect of Repetitive Processing on the Mechanical Properties
and Fracture Toughness of -TPVs
Recycling and utilization of waste plastics get more and more attention
nowadays due to the critical problems in environment. To evaluate the
recyclability and the effect of recycling on the performance variation of
polymer materials, repetitive processing method is commonly used [59-64].
We have revealed that -TPV itself exhibits excellent fracture toughness.
Whether the superior performance of -TPVs can keep unaffected by
repetitive processing is concerned now. So the effect of repetitive processing
on the mechanical properties and fracture toughness of -TPVs was studied
and TPVs without -NA were also prepared as a comparison [58]. The two
group of TPVs denoted as G1 (TPV) and G2 (-TPV) were of the same
compositions except that G2 contains 0.5%wt (to the weight of the blends) NA. Five times repetitive extrusion was conducted. After each extrusion, a
certain amount of the pellets were put aside as one sample for G1 or G2 and
the remainder was extruded again. Five samples for G1 or G2 were prepared,
referred to as G1-1, G1-2, G1-3, G1-4, G1-5 for G1 group and G2-1, G2-2,
G2-3, G2-4, G2-5 for G2 group, respectively. For example, G2-3 refers to the
sample of G2 (-TPV) experienced thrice extrusion.
The WAXD patterns of TPVs samples of TPV and -TPV are shown in
Fig. 13. Effect of repetitive processing on the total crystallinity of TPVs, crystallinity and the K value for -TPV are shown in Tab. 2. For samples of
TPV group, only five characteristic reflections of -PP exist. For samples of
G2 group, two main reflections are clearly observed at 2=16.0 and 21.0,
21
G1-5
G1-4
10
20
30
2()
40
Intensity
Intensity
which are the characteristic reflections of the (300) and (301) planes of -PP.
At the same time, the transformation of -form to -form owing to the addition
of -NA substantially weakened the diffraction peaks of -form [3-6]. From
Tab.2, it can be seen that the relative content of -phase of all the samples in
G2 group maintains above 97%.With processing cycles increasing, the total
crystallinity of TPVs from G1 group increases slightly while the total
crystallinity of -TPV group fluctuates between 55.92% and 60.64% while the
-crystallinity almost keeps constant. These results indicate that the repetitive
processing shows little influence on the crystalline structures of TPVs with
and without -NA. It is evident that -NA maintains high-nucleating
efficiency and thermal stability after repetitive processing [65].
G2-5
G2-4
G1-3
G2-3
G1-2
G2-2
G1-1
G2-1
10
50
20
(a)
30
2()
40
50
(b)
Figure 13.Effect of repetitive processing on the WAXD profiles of TPVs samples: (a)
TPV Group, (b) -TPV Group. (From Reference 58 with permission from John Wiley
& Sons, Inc.)
Table2. Total crystallinity of TPVs, -crystallinity and the K value of -TPV with
different processing cycles. (From Reference 58 with
permission from John Wiley & Sons, Inc.)
Processing
Cycle
1
2
3
4
5
TPV
-TPV
Total crystallinity
(%)
Total crystallinity
(%)
crystallinity(%)
36.26
39.16
40.33
41.64
43.42
55.92
56.20
59.66
60.64
58.77
47.24
47.04
49.25
49.04
48.58
97.29
97.30
97.75
97.90
97.54
22
The mechanical properties of samples from TPV and -TPV group are
collected in Tab.3. On the whole, the tensile and flexural strength and modulus
of samples with -NA (G2 group) are lower than those of samples without NA (G1 group), which is the reasonable result of the presence of a large
amount of phase in samples of -TPV group, owing to the better fracture
toughness but lower tensile modulus, yield strength, flexural modulus and
flexural strength of phase compared with phase [3-6].
With the processing cycle increasing, the tensile modulus and flexural
modulus of samples from G1 group show a declining trend; finally, the tensile
modulus has fallen from 366 MPa to 266 MPa and the flexural modulus has
fallen from 225 MPa to 188MPa. However, both the tensile modulus and
flexural modulus of samples from -TPV group were almost unchanged with
the increase of processing cycle. Additionally, the tensile yield strength and
flexural strength of samples from both groups are similar, and with repetitive
processing, the variations of tensile strength and flexural strength for both
groups, less than about 1MPa, are also neglectable, especially for the -TPV
group. Therefore, the -TPVs show more stable performance than those
without -NA.
Table 3. Tensile properties and flexural properties of TPVs with different processing
cycles. (From Reference 58 with permission from John Wiley & Sons, Inc.)
Processing
Cycle
1
2
3
4
5
TPV
E
366
335
311
309
266
-TPV
yb
Ef
10.1
11.2
10.4
10.9
10.9
225
201
196
190
188
8.54
8.47
8.30
8.22
8.20
212
196
204
203
193
yb
Efc
fd
10.2
10.2
9.76
9.54
9.49
158
143
145
147
154
8.05
8.05
8.06
8.06
8.05
a Tensile modulus(MPa); b Tensile yield strength (MPa); c Flexural modulus (MPa); d

Flexural strength (MPa).
The reasons that the repetitive processing does not cause much loss in the
mechanical properties of both groups, especially for -TPV group may have
something to do with the increasing total crystallinity, and the stable relative
content of phase crystals, although scission of macromolecular chains and
oxidative degradation are unavoidable.
23
110
120
G2-1
100
110
100
G2-4
90
G-1
90
G2-3
80
80
G-2
70
70
G-3
G-5
40
G2-2
50
G-4
50
G2-5
60
60
40
30
30
20
2
10
20
12
Ligment length (mm)
10
12
Ligment length (mm)
(a)
(b)
Figure 14. Specific work of fracture against ligament length for: (a) samples of TPV
group and (b) samples of -TPV group. (From Reference 58 with permission from
John Wiley & Sons, Inc).
EWF approach was again used to study the fracture behavior. The plots of
wf versus L of samples of G1 and G2 groups are shown in Fig. 14. The values
of we and wp are listed in Tab. 4. It is worthwhile noting that the diagrams
gave very good linear relationships for all the TPVs, as proved by the linear
regression coefficient (R2), being in most cases higher than 0.95.
Table 4. Effect of repetitive processing on the fracture parameters of TPVs and TPVs. (From Reference 58 with permission from John Wiley & Sons, Inc.)
Processing
cycle
1
2
3
4
5
we (kJ/m2)
12.0
12.1
12.0
7.8
7.1
TPV
wp(MJ/m3)
8.3
6.1
4.7
4.6
4.7
R2
0.92
0.96
0.93
0.98
0.93
we (kJ/m2)
14.9
14.8
14.8
14.9
13.2
-TPV
wp(MJ/m3)
7.3
4.3
6.0
6.9
5.0
R2
0.97
0.96
0.92
0.96
0.98
It is obvious that the we for TPV group declines with the increase of
processing cycle; particularly after the fourth cycle, the value of we is reduced
by about 40%. wp is also dropped by more than 40% after the third cycle,
indicating less plastic energy absorbed with further increase in the processing
cycle. However, all the values of we for samples of -TPV group are higher
than that of TPV group because of the presence of -phase which improve the
fracture toughness of TPVs obviously [3-6, 8, 10]. The value of we for samples
of -TPV group keep stable though it decreases slightly after the fifth
24
processing cycle. There is no significant change in the value of wp, which just
fluctuates between 4.34 and 7.33 MJ/m3. Different from the case in pure PP,
the -phase shows stronger effect on the crack growth than on the plastic
deformation owing to the introduction of EPDM. So no significant changes for
the energy for plastic deformation absorbed during the fracture process [3132].
From what has been discussed above, we may safely draw a conclusion
that the introduction of -NA into TPVs based EPDM/PP can effectively
preserve toughness of TPVs after repetitive processing.
4.2. Study on the Toughening of PP and PA6with -TPVs

TPVs can be used as a toughening agent for PP or polyamide 6 (PA6).
How about the -TPVs developed in this work? Usually, the common
toughening agents such as EPDM, ethylene-octene copolymer (POE) [8-11,
66-75] are resource-limited, more expensive than general plastics while the TPVs includes partial rubbers, which can reduce the cost drastically. In
addition, for PP/-TPV systems, PP component in TPVs can improve the
interfacial compatibility between the EPDM phase and PP matrix and
therefore improve some mechanical properties of the corresponding blends.
But poor compatibility between PP and EPDM or POE will bring an adverse
effect to the PP/EPDM or PP/POE toughening systems. Also, using only
elastomers to toughen PP or PA6 often causes loss in strength, modulus and
heat deformation temperature to some extent. But the PP phase in -TPV,
considered as a hard component can make up for these losses.
For toughening of PP, six different TPVs with different -NA dosage
(0.0wt%, 0.1wt%, 0.2wt%, 0.3wt%, 0.4wt% and 0.5wt% to the weight
of TPVs) were prepared firstly. Correspondingly, six different toughening
systems (PP: TPV=4:1 wt) were produced through extrusion, denoted as P0,
P1, P2, P3, P4 and P5. Samples of pure PP and EPDM- toughened PP (PP:
EPDM=4:1 wt) were also prepared for comparison, referred as PP, P/E. For
toughening of PA6, we used maleic anhydride (MAH) grafted EPDM (MAHg-EPDM) to replace EPDM in the preparation of -nucleated TPVs. Because
of the possible reaction of anhydride group in modified EPDM phase with the
amine end of PA6, the compatibility between the PA6 and TPV may be
improved [74-75]. TMB (amide compound), also a high-efficiency -NA, is
used to induce the -phase here. Due to the interactions between the amino
group in TMB and hydroxyl group in PA6, the compatibility between the PA6
25
and PP in TPV will be further improved. Similarly, five different TPVs with
different -NA dosage (0.0wt%, 0.1wt%, 0.3wt%, 0.5wt% and 1.0wt% to the
weight of TPVs) were prepared first and then the corresponding toughening
systems (PA6: TPV=4:1 wt) were prepared, named PA0, PA1, PA3, PA5,
PA10 for short. Samples of pure PA6 and MAH-g-EPDM- toughened PP (PP:
MAH-g-EPDM=4:1 wt) were also prepared for comparison, denoted as PA6
and PA6/E.
Tab.5 illustrates the notched impact strength and some other mechanical
properties of pure PP and the toughened blends. With -NA content or the
content of -phase increasing, impact strength of the toughened blends almost
increases linearly, all superior to pure PP. The sample P5 with an impact
strength 11-12 times higher than that of pure PP and 1-2 times higher than that
of P/E blend has been achieved. From P0 to P5, both of the tensile yield
strength and flexural modulus show a decreasing trend, opposite to the
changing trend of toughness. What is gratifying is that tensile yield strength
and flexural modulus of -TPV toughened blends are higher than those of
EPDM toughened blend, though still lower than pure PP. The less loss in the
strength for -TPVs toughened blends compared to EPDM toughened blend
can be attributed to PP phase in the -TPVs functioning as hard component,
which can make up the loss in the strength of the corresponding toughened
blends while the single dispersed rubber phase greatly weakens the strength of
P/E sample. Additionally, PP phase in TPVs can improve the interfacial
compatibility between the EPDM phase and PP matrix of -TPVs toughened
blends while the poor interfacial adhesion in P/E sample causes much loss in
the strength. It is worth noting that all the samples of PP/-TPV system could
not be broken during the tensile test, which is also attributed to the improved
interfacial compatibility.
Tab.6 shows the notched impact strength, other mechanical properties and
thermal properties of pure PA6 and the toughened blends. Obviously, the
introduction of -TPVs enhances the impact strength of PA6. There is no
doubt that the -phase in TPVs increases with increasing the -NA content.
The larger content of -phase TPVs includes the higher impact strength of the
toughed blends. Sample PA10 shows an impact strength 3.3 times higher than
pure PA6 and 1.2 times higher than PA6/E blend. Moreover, the impact
strength of sample PA10 with 1wt% -NA in TPVs is nearly equal to that of
sample PA5 with 0.5wt% -NA in TPVs, showing that a better toughening
effect can be achieved by using less EPDM and -NA than using more EPDM
only, which is helpful for lowering the cost. Elastic modulus, yield strength of
-TPVs toughened PA6 blends are higher than these of TPVs toughening PA6
26
blends without -NA, and much higher than those of sample PA6/E. Flexural
modulus, flexural strength of -TPVs toughened PA6 blends are higher than
MAH-g-EPDM toughening PA6 blends. Besides, -TPVs toughened PA6
blends exhibit better thermal properties compared to PA6/E samples, TPVs
toughening PA6 blends without -NA, which can also be attributed to the PP
phase in TPVs functioning as a hard component.
Table 5. Notched impact strength and other mechanical properties of
pure PP and the toughed blends
Sample
Ia
y b
Efc
PP
P/E
P0
P1
P2
P3
P4
P5
1.94
15.4
10.7
11.8
13.1
14.6
17.1
22.2
32.9
23.5
27.5
27.0
26.6
26.1
24.8
25.1
1250
625
978
928
894
887
832
808
a Notched impact strength (kJ/m2); b Tensile yield strength (MPa); c Flexural

modulus (MPa).
Table 6. Mechanical and thermal properties of pure PA6 and the toughed blends
Sample
Ia
Eb
y c
EBd
Efe
f f
HDT g
PA6
PA6/E
PA0
PA1
PA3
PA5
PA10
5.5
15.1
15.2
16.2
16.5
17.7
18.0
3546
1936
1971
2025
2106
2311
2307
77.5
52.9
52.9
55.3
55.2
55.9
55.0
56.0
63.0
60.6
49.7
43.3
45.5
47.4
1061
749
842
840
843
873
881
42.4
31.4
33.9
33.9
33.8
35.6
35.2
48.4
46.2
46.7
47.4
47.8
47.4
47.1
a Notched impact strength (kJ/m2); b Tensile modulus(MPa); c Tensile yield strength

(MPa); d Elongation at break (%); e Flexural modulus (MPa); f Flexural strength
(MPa); g Heat deformation temperature (oC).
27
As for toughening mechanism, rubber particle cavitation, multiple crazing

and shear yielding are three broadly acceptable toughening mechanisms.
Based on quantitative analysis, Wu established the percolation model of
brittle-ductile transition and put forward the criterion of critical matrix
ligament thickness. The framework of Wus theory promoted the transfer from
qualitative analysis to quantitative analysis. For polymer/rubber binary blends,
a sharp brittle-ductile transition occurred at a critical surface-to-surface
interparticle distance, or the critical matrix ligament thickness c [76-77].
c = dc ( / 6r ) 1
1/3
where dc was the critical rubber particle diameter,
(7)
r the rubber volume
fraction, the average surface-to-surface interparticle distance (i.e., the

average matrix-ligament thickness), depending on the rubber volume fraction.
If < c , the continuum percolation of stress volume around rubber particles
would occur; the matrix yielding would propagate and pervade over the entire
matrix, and the blend would be tough. On the contrary, if > c , the matrix
yielding can not propagate, and the blend will fail in a brittle manner.
Here, we will try to elucidate the special toughening mechanism for the
toughening systems given previously by the example of -TPV toughened PP
blends. Usually, the use of soft particles as toughening agent is based on the
concept that the particles must cavitate and release the high plastic constraint
in the matrix.
From the SEM photos of impact fractured surfaces for different toughened
blends shown in Fig. 15, we can see that for P/E samples, the interface
between two phases is visible and there are many holes that are left by the
rubble particles extracted from the matrix during the impact test. From another
point of view, compatibility to a certain extent (not very bad or very good)
between PP and EPDM is beneficial to cavitation and energy absorption. For
sample P0, a few holes can be observed and most rubber particles are covered
by a layer of PP matrix, showing the improved interphase compatibility due to
the PP component in TPV. For sample P5 that exhibits the best toughness,
hardly any holes can be observed and almost all the dispersed phase is
immersed in PP matrix. So the cavitation theory is not suitable for our
toughening system.
The SEM photographs were also used to analyze the particle size and
particle size distribution using a computer image analyzer. The number of
28
particles for each sample was 300-600. The weight average diameter dw of
rubber particles can be determined as [78-79]
d w = ni di2 / ni di
(8)
From sample P0 to P5, the particle size does not change greatly, just
fluctuating around 0.75m. With the same rubber volume fraction, the surfaceto-surface interparticle distances for all the samples are similar. In other
words, the variation of the toughness does not depend on the matrix ligament
thickness. So Wus theory is not applicable here, either.
(a)
(b)
(c)
Figure 15.SEM photos of impact fractured surfaces for different toughened blends: (a)
P/E samples; (b) P0 samples; (c) P5 samples.
29
Fig. 16 gives SEM photos of impact fractured surfaces after etching the
rubber phase and amorphous region of PP for sample P0, P3, P5. As has been
revealed in many literatures, -spherulite is formed from one crystal via an
unidirectional growth mechanism. It develops initially as rod-like structures
and then by continuous branching and fanning via the intermediate stage of
sheaves, which finally evolves into a bundled structure. The parallel-stacked
lamellae tend to cluster into bundles that are separated from one another by the
amorphous regions. The -spherulite, consisting of aggregates of chain folded
lamellae growing from a central nucleus, conforms more closely to central
multidirectional growth with cross-hatching. Different crystals nucleate
separately during crystallization and the spherulites that are thus developed
have distinct boundaries and these boundaries are weak sites in the polymer as
failure of the PP is often initiated at these places [26-30].
(a)
(b)
(c)
Figure 16.SEM photos of impact fractured surfaces after etching the rubber phase and
the amorphous region of PP for three toughened blends: (a) sample P0; (b) sample P3;
(c) sample P5.
30
For sample P0 containing no -NA, only the lamellae structure of -phase

can be observed in the SEM photo. The lamellae grow radially from a centre
nucleus. For sample P3 containing some -NA, a few spherulites disperse in
the matrix. In some regions, complete -crystals can be observed and a typical
spherulite is shown in Fig. 16(b). The fine spherulite exhibits a sheaf-like
or butterfly tie-like structure and the bundled, lamellae are arranged
unidirectionally. When the content of -NA reaches 0.5 wt% (to the weight of
TPVs), mainly spherulites are observed, as seen in Fig. 16(c). Boundaries
between the spherulites are hardly distinguishable. Moreover, it can be seen
that bundles of lamellae of neighboring spherulites tend to cross each other
and some of these bundles tend to grow spirally. Hardly a whole structure of
-crystal can be identified. From sample P0 to P5, the toughness increases
gradually and we may safely come to the conclusion that the toughening
mechanism is considered to be linked with the -iPP in TPVs. In this work,
there is no evidence for the occurrence of a - transition.
The mechanism of superior toughness of -iPP has been attributed to: a)
the to phase transition induced by mechanical force, accompanying the
densification of the crystal transformation, which will result in fine cavities
and absorb more energy, b) superior mechanical damping of -iPP and c) the
peculiar crystalline structure of -iPP [80]. Since -iPP exhibits a sheaf-like
structure of lamellae growing in bundles from a central nucleus without any
epitaxial growth of tangential lamellae, the plastic deformation will not be
disturbed by the physical network created by cross-hatched crystallites.
Concretely, the deformation of the amorphous chains (and therefore the
lamella separating process) will be facilitated in the early stages of a
dilatational deformation for the -form since no interlocking structure
blocks their mobility, which allows an efficient stress transfer [26-30, 80].
As for our toughened systems, the toughening mechanisms of the rubber
phase and the phase should be considered together, and a schematic
representation is shown in Fig. 17. From Fig. 16, we discover that an amount
of rubber particles are inlaid between the crystal plates. Fig. 17(a) and (b)
also illustrate this well. Lamellae bundles, held together by the tie molecules,
can easily separate from one another upon loading. Those lamellae which are
oriented along the loading direction may slip and those which are oriented
perpendicular to the loading direction may bend or tilt [26-30, 80]. When the
samples are under impact, most of the rubber particles are forced to deform
greatly as shown in the SEM results. During this course, deformed rubber
particles and lamellae bundles squeeze mutually, and the lamellae are much
easier to slip or bend. The interaction between the rubbers and lamellae is
-Nuccleated Therm
moplastic Vulcaanizates Basedd
31
helpful for the yieldding initiationn and expanssion in the matrix

m
leadingg to
greater energy dissipaation.
Figure 17.The schemattic representatioon of synergic toughening effe

fect of -phase and
rubber phase
p
on -TPV
Vs toughening PP blends: (a)) toughened syystems with few
w
crystals in TPVs; (b) tooughened systeems with manyy crystals in TPVs;
T
(c) synergic
tougheniing mechanism..
CONCLUSION
N
t preparationn of dynamicaally-cured iPP
P/ EPDM TPV
Vs, we introduuced
In the
-NA of iPP into the TPVs, and thhe resulting maaterials were -TPVs.
A serries
of -TP
PVs with diffferent morphhology and prroperties can be obtained by
changin
ng the contentt of the curinng agent or -NA.
EWF evaluation
e
of the
fracturee properties off TPVs showeed that in TPV
Vs, the presencce of -phase PP
indeed enhanced thee toughness, especially when
w
the conntent of -TP
PVs
reached
d a maximum
m, there was about
a
52% inncreasing of the
t value of the
specificc essential worrk of fracture. The content of
o -phase in TPVs is affeccted
by the sample
s
thicknness. With inccreasing sample thickness, the
t content off phase increased,
i
whhile the totall crystallinityy almost keppt constant. The
T
32
simulation of temperature field showed that there was a temperature gradient

along the direction of sample thickness, and the strength of temperature
gradient increased with the sample thickness increasing. The reduction of the
entropy during the temperature gradient resulting from a decrease of the
molecular chain conformation leads to the variation of the content of -phase.
The formation of -phase in TPVs is also affected by PF content. The phase
morphology experiences a series of changes with increasing PF content: the
EPDM phase undergoes a change from the dispersed phase to a continuous
one, and again to dispersed phase, and the PP component always shows itself
in a continuous phase. With increasing PF content, the content of -PP
increased a little at first, and then decreased; When PF content was 6wt%, the
formation of -phase was completely restrained. This evolution of phase
morphology results in the change of spatial confinement which significantly
affects the development and final content of -PP in the blends.
The repetitive processing does not alter the crystalline structures and
crystallinity of TPVs with and without -NA. The repetitive processing did not
cause much loss of mechanical properties of the TPVs with and without -NA,
especially for -TPVs, which showed more stable performance than TPVs
without -NA. The -NA induced -phase indeed enhances the fracture
toughness of the TPVs. With the processing cycle increasing, the value of we
of TPVs without -NA showed a significant drop while the value of we of TPVs almost kept constant. -TPVs can also be considered as a new type of
toughening agent to improve the toughness of PP or PA6. As the content of phase induced by -NA increased, the toughness of corresponding toughened
PP blends increases; the value of notched impact strength of -TPVs with
0.5wt% -NA (to the weight of TPVs) is ten times more than that of pure PP,
higher than that of 20wt% EPDM-toughed PP systems. The results showed
that -TPVs could not only toughen PP, but also cause less loss in mechanical
properties. In like manner, with the -phase content increasing, the toughness
of toughened PA6 blends increases. The value of impact strength of -TPVs
with 0.5wt% -NA (to the weight of TPVs) is 3.3 times than that of pure PA6,
higher than those of 20wt%EPDM-toughened PA6 systems and TPVstoughened PA6 systems without -NA. Compared to EPDM-toughened PA6
blends, -TPVs bring less negative effect on mechanical properties and
thermal properties of toughened PA6 blends.
33
ACKNOWLEDGMENTS
The authors gratefully acknowledge the financial support of National
Natural Science Foundation of China (Grant No.50973074, 51073110 and
50873068), the Special Funds for Major Basic Research (Grant no.
2011CB606006) and the Program for Sichuan Provincial Science Fund for
Distinguished Young Scholars(2010JQ0014).
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Silvestre, C. Polym Eng Sci 1982, 22, 536-544.
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1993, 34, 1684-1694.
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1998, 39, 6781-6787.
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731-742.

Chapter 2
PATTERNABLE BIOMATERIALS;
ELASTOMERS FOR BIOMEDICAL
APPLICATIONS
Marga C Lensen1,21, Mar Diez2and Vera A Schulte2
1
Technische Universitt Berlin, Institut fr Chemie, Nanostrukturierte

Biomaterialien, D-10623 Berlin, Germany
2
DWI e.V. and Institute of Technical and Macromolecular Chemistry,
RWTH Aachen, D-52056 Aachen, Germany
Abstract
We have investigated two elastomers with contrasting properties in
terms of surface chemistry, and with similar applications as a biomaterial.
The first elastomer is prepared from a star-shaped poly(ethylene glycol)
(PEG) macromolecule with acrylate end groups. The second elastomer is
formed from linear perfluorinated polyether (PFPE) dimethacrylate
macromonomers. Both precursor polymers can be transformed into
elastomeric materials by means of UV-curing, i.e. photoinitiated, radical
crosslinking reactions in the presence of a photoinitiator and eventually a
crosslinking agent by illumination with ultraviolet (UV-) light. Since both
macromonomers are viscous liquids before crosslinking, the precursor
1
Correcponding author.
38

mixtures can be molded in any shape and result in topographically
patterned elastomers. We have investigated both elastomers in cell culture
studies to elucidate cellular responses to the material depending on the
surface topography.
Elastomers prepared from the PEG-precursor form gels that are
insoluble in water, but have the propensity to take up large quantities of
water, hence hydrogels. These materials are very hydrophilic and their
hydrated nature results in effective prevention of non-specific protein
adsorption and cell adhesion.PFPE-elastomers were also expected to be
anti-adhesive to cells, since the material after crosslinking of the
precursors is both very hydrophobic and oleophobic; it has properties
comparable to those of teflon, which is renown for its inertness and nonwettability by both water and oils.
Both elastomers have been investigated in cell culture, using
fibroblasts and human macrophages. The following, striking results have
been observed: 1) whereas smooth PEG hydrogels are anti-adhesive to
cells as expected, a significant number of cells do adhere to the PEG
surface when it is decorated with micrometer topographic patterns; 2)
PFPE elastomers were found to be non-cytotoxic and to support cell
adhesion in a comparable, albeit delayed, manner as does tissue culture
polystyrene (TCPS); 3) macrophages are not activated by the PFPE
biomaterial per se, but do show a pro- or anti-inflammatory phenotype
depending on the geometry, size and periodicity of the topographic
micropatterns.
In conclusion, we have prepared two distinctly different elastomers
and investigated them as novel biomaterials. Both elastomers showed
excellent cytocompatibility and patternability. These patternable
elastomers are a versatile platform for fundamental cell studies and the
results are very useful for biomedical applications, e.g. for the design of
implant materials with specific functions due to their surface
characteristics and for biosensor applications where the non-specific
protein adsorption should be suppressed, while at the same time complex
2D and 3D geometries are required.
INTRODUCTION
Polymers have become indispensible in our daily life; our life standard
wouldnt be the same if we had to waive many products ranging from cheap or
dispensable items made out of commodity plastics, via durable and tough
Patternable Biomaterials; Elastomers for Biomedical Applications
39
materials used for instance in cars and aircrafts to highly sophisticated

products made from functional polymeric materials. The latter are important in
state of the art applications such as microfabrication (chip technology),
therapeutics (e.g. targeted drug delivery) and nano(bio)technology (e.g.
miniaturized diagnostic devices and biosensors). In this chapter, the usefulness
of elastomers in micro- and nanofabrication will be highlighted and
subsequently, two classes of elastomers will be investigated as novel,
patternable biomaterials.
The development of materials for biomedical applications such as tissue
engineering, diagnostics, prosthetics, and regenerative medicine is a
contemporary research field in which many important challenges are faced and
many questions continue to rise. In principle, already much is known about the
processes that take place when (bio) materials are brought into contact with
biological fluids, e.g. blood or serum. It is generally agreed upon that upon the
first contact of a (bio) material with a biological system, proteins from the
medium adsorb to the foreign interface [1].Consequently, the cells do actually
not react to the surface itself, but to the proteins adsorbed. The composition of
the protein layer is a key mediator of cell behaviour, because cell anchorage is
dependent on the interaction with specific proteins. This non-specific protein
adsorption (NSPA), e.g. protein adsorption on contact lenses or cell growth on
implants, is mostly undesired, since it can lead to unwanted cell growth,
biofilm formation and inflammation [2].Furthermore, selectivity and
sensitivity of biosensors are severely hampered by NSPA. Therefore, one of
the largest challenges in biomaterials research concerns the development of
inert, protein resistant materials and coatings [3]. Once the background protein
adsorption and consequent cell adhesion are effectively suppressed, one can
introduce binding sites for specific biointeraction, for example the adhesion of
desired cell types in a controlled density at a predetermined location and with
spatio-temporal control of cells responses.
Generally the in vivo biocompatibility and in vitro cytocompatibility of a
material is dependent on the amount, type and accessibility of adsorbed
proteins, the so called adsorption profile. Protein adsorption is a highly
complex process which is determined by the properties of the biointerface
such as the surface wettability, roughness and stiffness. Numerous, systematic
studies have been carried out to understand the role of hydrophobicity on
protein adsorption and consequent cellular reactions, and a certain optimal
wettability has been outlined [4]. Also the effect of topography, i.e. the microor nano-sized surface structure, on cell adhesion has been recognized [5, 6].
40
Finally, recent studies have revealed that cells sense the substrates stiffness
[7] and usually adhere on and migrate towards stiffer substrates [8, 9].
In our research we aim at controlling cell adhesion and migration on
biomaterials surfaces by employing micropatterns of chemistry, topography
and elasticity; separately and in combination. To that end, we have employed
the strategy to synthesize novel biomaterials from liquid precursors. The
prepolymers can be crosslinked to form elastomers with desired chemical
properties; exhibiting surfaces that are either smooth or that bear a defined
topography and with tunable mechanical properties.
More specifically, we have investigated two classes of such patternable
elastomers that are diametrically opposed in terms of chemistry; a hydrophilic
hydrogel crosslinked from star-shaped polyethylene glycol (PEG) prepolymers
and a very hydrophobic elastomer from perfluoropolyether (PFPE)
prepolymers. The use of photocurable polymers allows straightforward
topographic patterning of the surface by the soft nanolithography techniques
(nano)imprinting or replica molding [10]. We have found that the transfer of
patterns from structured silicon masters to star PEG and PFPE samples can be
reproduced down to nm range sizes [11, 12]. The dry PFPE- and PEG-based
elastomers exhibit elastic moduli of a few MPa, while the PEG gels become
softer upon swelling in aqueous solution, such as cell culture medium, which
is also important to take into account when introducing synthetic polymers
into cell culture.
SYNTHESISAND CHARACTERISATIONOF THE ELASTOMERS

Synthesis of elastomersfrommacromolecularprecursors
PFPE and star PEG elastomers have been prepared by UV-initiated
(wavelength of 365 nm) radical cross-linking via (meth) acrylate-endgroups.
Figure 1 depicts the precursor macromolecules, i.e. a linear perfluorinated
polyether dimethacrylate (PFPE DMA) and a 6-armed, star-shaped poly
(ethylene glycol) derivate with acrylate end-groups (Acr-star PEG). The arms
of the PEG derivative consist of a statistical mixture of ethylene oxide (EO)
and propylene oxide (PO) rather than of pure PEG chains, by virtue of which
this molecule is liquid at room temperature and not crystalline as would be
expected for high molecular weight PEG. The precursor of the fluoropolymer
with teflon-like properties is also liquid before crosslinking and has therefore
been coined liquid teflon by Joseph DeSimone[13].
41
Figure 1. Schematic representation of the synthesis of patternable elastomers from

liquid prepolymers by UV-curing. Compiled from material originally published in Pure
Appl.Chem.2008 [14] and in Biomaterials 2010 [15] with permission of the original
copyright holders; the International Union of Pure and Applied Chemistry (IUPAC)
and Elsevier, respectively.
The crosslinked PEG gel is insoluble in water but able to take up a large
amount of water (depending on the crosslinking density), hence is called a
hydrogel [16].It is interesting to note that not all 6 telechelic acrylate groups
are needed in order to synthesize crosslinked gels; especially when using an
additional crosslinker (CL, e.g. pentaerythritoltriacrylate) only two reactive
groups of the star-shaped PEG prepolymer are essential. We can exploit this
aspect of multivalency in that we make use of the post-curing reactivity of
unreacted acrylates; we have adhered micrometer-sized patterns of a second
hydrogel precursor mixture to the crosslinked hydrogel surface (unpublished
results). Besides, we have prepared precursor macromonomers in which not all
6 end groups are converted into acrylates and intend to make use of the
remaining functional (-OH) groups for further (bio) functionalization of the
hydrogels; either of the surface reactive groups or throughout the bulk.
Chemical composition and mechanical properties

The crosslinking density can be easily tuned by varying the concentration
of the photoinitiator (PI) and/or of an eventual, low-molecular weight
crosslinker (CL, e.g. pentaerythritoltriacrylate, PETA). Several series of
hydrogels and PFPE elastomers with variable physicochemical and mechanical
properties (i.e. elasticity, porosity and swelling behavior) have thus been
prepared. Table 1 shows the properties we have determined for a series of
42
PEG-hydrogels, highlighting the fact that the modulus increases with increased
concentration of PI and/or CL, while the correlating swelling degree,
equilibrium water content (EWC) and mesh size decrease with increasing
crosslinking density.
Table 1. Different hydrogel formulations with
corresponding mechanical properties
dry
E (Mpa)
swollen
E (Mpa)
Mesh size
()
PI and CL
SD (%)
EWC
0.25% 0%
185
65
0.5% 0%
160
61
0.22
8.7
1% 0%
149
60
0.56
0.5% 5%
144
59
0.18
0.09
7.7
1% 5%
140
58
0.75
0.35
7.3
2% 5%
135
57
1.1
1% 10%
110
52
2.7
9.9
7.4
1.1
5.9
1.5% 10%
1% 15%
43
15
1% 30%
30
30
Although no standard deviations are given in Table 1, the values are

averaged from multiple measurements. Yet variations up to 10 % between
different measurements are not unusual. Also the calculated values for the
mesh size can vary depending on the assumptions made in the network model
that is applied to estimate the porosity [17]. Nevertheless, the experimental
data underline the trend of decreasing pore size with increased crosslinking
density.
The three hydrogel formulations that we have studied most extensively for
patterning and cell culture applications are highlighted in Table 1. For those 3
selected gels, which we notate standard (boldface), soft and stiff,
respectively, the elastic moduli as measured by rheometry and dynamic
P
Patternable
Bioomaterials; Elaastomers for Biomedical
B
Appplications
43
mechan
nical analysis are also depiccted for the swollen state; it becomes cllear
that the hydrogels sofften upon hydrration (Figure 2).
Figure 2.
2 Three diffeerent hydrogel formulations with correspoonding mechannical
propertiees, in dry andd swollen statte. Data reuseed from Diez et al. Advannced
Engineerring Materials, n/a. doi: 10.10002/adem.201080122 [18]. Coppyright Wiley-V
VCH
Verlag GmbH
G
& Co. KGaA.Reproduced with permisssion.
As far as the fluuoropolymer is

i concerned, we have usuually employeed a
standard
d formulationn of the precuursor with onnly 1% PI annd no additioonal
crosslin
nker (highlightted in Table 2)).
P
elastom
mers as synthesized from
Taable 2. Youngs moduli of PFPE
different preepolymer mixxtures. Data originally
o
pub
blished in
Nanotechnology (2010,
(
21, 2455307-13) [19]..
Copyrright IOP. Reeproduced wiith permission
n)
PFPE 1:0
PFPE 4:0
4
PFPE 4:1
PFPE 5:0
Percen
ntage
photoin
nitiator
Percen
ntage crosslink
ker
Youngs modulus [M
MPa]
1.8 0.3
0
4.3 0.1
4.55 0.04
6.2 0.22
Desspite the factt that the PF

FPE elastomer has outstannding replicattion
abilitiess down to a feew nanometerrs as shown byy us [12] and by DeSimonee et
al.[20] already
a
in its standard compposition, the increased stiffn
fness of the PF
FPE
44
has proved to be advantageous for its nanotechnological application, namely in

nanoimprint lithography (NIL), vide infra.
Both for surface patterning and for the eventual application in cell culture,
the surface chemistry is a very important parameter. As will be shown in the
following, the initial protein adsorption that occurs when a (bio) material
contacts a biological fluid is strongly depending on the wettability of the
biointerface. Table 3 depicts the water contact angles and the surface energy of
the PEG-based hydrogel and the PFPE elastomer and of 3 other polymeric
materials that we have investigated. TCPS is the abbreviation of tissue
culture polystyrene, a routinely used, standard material that supports cell
adhesion and growth. PVDF stands for poly vinylidene fluoride, an established
biomaterialthat is also a (partially) fluorinated polymer, but not as
hydrophobic as PFPE. Finally, the very popular elastomer PDMS (poly
(dimethyl siloxane)) that is used in soft lithography and nanobiotechnology
applications, was also included in the investigations.
Table 3. Static and dynamic contact angles () and surface energies of
different materials. Data originally published in Pure Appl.Chem. (2008)
11, 24792487 [14] is used with permission of the original copyright
holder, the International Union of Pure and Applied Chemistry (IUPAC)
PEG
TCPS
PVDF
PDMS
PFPE
77 1,5
81 1,6
110 1,9
110 2,0
Advancing n.d.
96 1
94 1
122 2,4
120 1,5
Receding
n.d.
74 1,8
63 1,8
63 3,5
52 2,5
Hysteresis
n.d.
22
32
59
68
Surface energy (mN/m)
40.1
38.8
31.0
22.4
17.3
Static contact angle ()
Dynamic
contact
anglea ()
43 1.3
Wilhelmy plate method; b captive bubble method; n.d. not determined
The liquid precursors of the PFPE elastomer, PFPEs, are characterized by

very low glass transition temperatures (about -120 C), chemical inertness,
solvent and high temperature resistance, barrier properties, low friction
coefficient, hydrophobicity and lipophobicity and in particular very low
surface energy [21](Table 3).In the crosslinked gel many of the precursors
properties are preserved and notably the very low surface energy of the PFPE
P
Patternable
B
Appplications
45
elastom
mer is very beeneficial for itts applicationn in nano impprint lithograpphy,
which will
w be elaboraated in the folllowing.
TOPOGRAPHICPATTE
ERNINGOF THE ELAST
TOMERS
Soft UV-basednano
U
oimprintlithoggraphy (softt UV-based NIL)
N
using the
PFPE elastomer
e
Wee have fabricated soft andd flexible, seecondary moldds of the PF
FPE
elastom
mers by replication from naano patternedd, hard masterrs and employyed
them inn soft UV-baased NIL (rooom temperatture embossinng) to resultt in
eventuaal, positive reeplicas of thhe original design
d
consistting of anothher,
polymerric material (thhe resist). Although
A
the PF
FPE elastomeers yield accurrate,
negativee replicas of the primary master the final
f
replicas were not exact,
positivee copies of thee original [19] (Figure 3).
Figure 3.Application
3
of the PFPE elaastomer as soft, secondary moold in nanoimpprint
lithograp
phy. Compiled from material originally published in Nanootechnology (20010,
21, 2453307-13) [19]. Coopyright IOP. Reproduced
R
withh permission.
App
parently, the pressure appplied duringg the NIL process led to
deformaation of the flexible
f
structuures on the secondary PFP
PE molds, andd it
46
Marga C Lensen, Mar

M Diez and Vera
V A Schultte
und that the stiiffer molds coould better witthstand such deformations
d
thhan
was fou
those faabricated from
m the standard formulation (ssee Table 2 annd Figure 4).
Figure 4.Feature
4
sizess on original master and onn final replicaa after using soft,
s
secondarry molds made from the PFPE elastomer withh different elastiic moduli. Mateerial
originallly published in Nanotechnologgy (2010, 21, 245307-13)
2
[199]. Copyright IOP.
I
Reproduuced with permiission.
Thee deformations were system

matically quanttified and it was
w found that the
deformaation does noot only depennd on the feaature size (255 nm to seveeral
hundred
ds of nm), butt also on the relative
r
spacinng between thhe protrusionss on
the mold [19].
Replicaamoldingusin
ng the PFPE elastomer an
nd the PEG-bbased hydrogeel
Toppographic pattterning of thee PEG-based hydrogel
h
wass also carried out
by embo
ossing using micro-patterne
m
ed silicon masters. We havee started off ussing
a secondary mold appproach; the orriginal, siliconn master was first
f
replicatedd by
the PFP
PE elastomer yielding
y
a softt and transpareent, secondaryy mold with antia
47
adhesive properties similar to those known for the inert material teflon, and
this secondary mold was then used to imprint the surface topography into the
PEG gel [11]. This strategy ensures excellent mold release in both steps; first
from the silicon master and then from the soft, secondary mold. Consequently,
no mold release agents are required in the process.
Figure 5.Replica molding using the PFPE elastomer to fabricate a soft and transparent,
secondary mold to imprint the original topographic pattern of the original master into
the PEG gel. Reproduced from a previous publication in Langmuir in 2007 [11] with
permission of the American Chemical Society.
Notwithstanding the usefulness of fabricating positive replicas from the

PEG-based elastomer, it should be noted that the hydrogel canbe imprinted
directly by an untreated silicon master as well to yield a negative copy of the
original master (Figure 6).
Figure 6 highlights the scope of features that can be replicated by the
PEG-based hydrogel, ranging from micrometer-sized patterns down to
ultrafine structures. In Figure 6c the mold consisted of a silicon wafer
decorated with gold nanoparticles (NPs) of only around 8 nm in size; the
atomic force microscopy (AFM) image reveals a hexagonal pattern of
nanoindents and demonstrates the accurate replication of the sub-10 nm
topography [12].It was even found that the PEG-replica can also serve as a
secondary mold itself, to imprint for example the PFPE elastomer as the
eventual substrate (Figure 7).
48
Marga C Lensen, Mar

M Diez and Vera
V A Schultte
Figure 6.Scope
6
of imprrinting into thee PEG-based hyydrogel; a) optiical micrographh of
micropattterned hydrogeel; b) and c) AFM
A
images of nanopatterned PEG gels, usinng a
silicon master
m
and a unnique master connsisting of goldd nanoparticles (NPs) on a siliicon
wafer. Compiled
C
from material origiinally publishedd in Langmuir (2007, 23: 788417846) [1
11] and in Diezz et al. Small,22009, 5, 275622760 [12] withh permission off the
original copyright holdders; the Ameriican Chemical Society and Wiley-VCH
W
Verlag
GmbH & Co. KGaA., respectively.
APPLIICATION OF
O THE PAT
TTERNEDBIOMATERIIALSIN CEL
LL
CULTURE
Expecta
ation of cellaadhesionbased on surface chemistry
To start with thee PEG-based hydrogel,
h
PEG
G is a biomatterial that is very
v
a cells. In fact,
f
well-knnown for its ouutstanding antti-adhesivenesss to proteins and
among the possible (macro)moleccules that can make surfaces non-foulinng,
PEG (or PEO) derivaatives can be considered thhe most populaar and have been
routinelly used in biootechnologicall applications to make anyy surface proteeinrepellen
nt [22]. Thus, part of the reeason why cellls dont adheere to PEG-baased
hydrogeel surfaces is that
t they preveent NSPA andd this in turn iss because of thheir
hydratio
on and hydropphilicity, whicch make hydroogels such uniique and versaatile
biomateerials. Other biomaterials
b
thhat are on thee other hand supportive
s
to cell
c
adhesion and growtth, for instannce TCPS, typically
t
havee (much) low
wer
e
taken upp by
wettabillity. Whereas water spreads on PEG surrfaces and is even
the hydrogel, finite water
w
contact angles
a
can be determined on those materrials
a depicted inn Figure 8).
(as listeed in Table 4 and
49
Figure 7.Imprinting sub-10 nm features by the two very different elastomers. The
primary master consists of a regular array of gold nanoparticles on silicon (1), which is
replicated by the PFPE elastomer or the PEG-based hydrogel to result in a secondary
master with nanoindents on the surface (2). This secondary master in turn is replicated
by either of the elastomers to yield positive copies of the original master, bearing
nanoprotrusions on the surface (3). Adapted from Diez et al. Small,2009, 5, 27562760
[12].Copyright Wiley-VCH Verlag GmbH & Co. KGaA. Reproduced with permission.
In fact, from several systematic investigations of the effect of surface

chemistry a correlation was found between the cell adherence and the surface
wettability: most cells have been found to adhere to surfaces with intermediate
wettability; too hydrophilic or too hydrophobic surfaces are less cell adhesive,
probably because of a diminished protein adsorption [23].
In contrast to the very hydrophilic PEG-material the PFPE elastomer has a
large water contact angle of 110 and based on this hydrophobicity, cell
adhesion was expected to be minimal as well. In addition to being
hydrophobic, this perfluorinated polymer is oleophobic, which means that it
can be considered repellent to anything. Unlike the protein resistance of
(hydrophilic and hydrated) hydrogels the lower cell adherence of cells on very
hydrophobic materials is probably not due to decreased protein adsorption but
should rather be attributed to protein denaturation, that is, due to the
50
Marga C Lensen, Mar

M Diez and Vera
V A Schultte
hobic interacction (betweeen the surfacce and hydrrophobic prottein

hydroph
residuess) the protein may lose its active conformation and potential
p
bindding
affinity to cells [24].
Figure 8.
8 Sketch of celll adhesion vs. water contact angle (based on
o literature vallues
[23] and
d exemplified byy our own findinngs) and depicttion of the wateer contact angless on
the mateerials. Material originally publlished in Pure Appl.Chem.
A
20008, 11, 247922487
[14] is used
u
with permiission of the orriginal copyrighht holder, the Innternational Unnion
of Pure and
a Applied Chhemistry (IUPA
AC).
hesion on PE
EG-based hyddrogels
Celladh
In order to veriffy that the buulk, PEG-baseed hydrogels are indeed antia
adhesivve in cell cultture we have prepared sevveral hydrogeels with differrent
crosslin
nking density and seeded fibroblast ceells on top of the (smoooth)
sampless. As expectedd, the PEG-gells were found to be inert; ceells do not adhhere
to any of
o the hydrogeels - regardless of their stifffness - and this is probably due
to the minimal
m
proteein adsorptionn. Besides thee lack of cell adhesion it was
w
observeed that the cells stayed com
mpletely rounnd and formedd clusters on the
substratte. Neverthelless, cytotoxiicity tests showed that the PEG-baased
hydrogeels are not cytootoxic and thee cells were viable.
How
wever, on miccropatterned suurfaces of the same materiaal it was observved
that quite
q
unexpecttedly - fibroblasts WERE able
a
to adheree and even soome
spreadin
ng was obserrved, especially inside of the
t micrometter-sized groooves
(Figure 9) [25].
P
Patternable
B
Appplications
51
Figure 9.
9 Fibroblast adhesion
a
on micropatterned
m
P
PEG
hydrogelss. Left panel: cell
adhere preferentially
p
innside of the miccrometer groovees; right panel: cell adhere onn the
side walls of large postts (20 m) or ffloat on top off a number of small
s
posts (3 m).
Compileed from materiaal originally puublished in Purre Appl.Chem. (2008, 11, 24479
2487) [114], in Biomacromolecules (22009, 10, 2795-2801 and 2010, 11, 3375-33383)
[25, 26] with permissioon of the originnal copyright hoolders; the International Unionn of
d Applied Chem
mistry (IUPAC) and the Americcan Chemical Society.
S
Pure and
o the enabledd cell adhesionn to

Wee have also stuudied the effecct of stiffness on
PEG-baased hydrogells and observved some inttriguing trendds. First, on the
topograaphically patteerned surfacess such as show
wn in Figure 9,
9 a significanntly
larger number
n
of cellls adhered to the
t softer rather than to the stiffer gels (w
with
the sam
me pattern geometry). Thosee adherent cellls were notabbly located insside
of the grooves and displayed a clearly moree spread shappe [26]. On the
y, on smoothh PEG-hydroggel surfaces exhibiting a binary elasticcity
contrary
pattern consisting of alternating soofter and stiffeer stripes (e.g.. 10 m 20 m
wide), we
w observed the
t more expeected behaviorr that the cellss accumulatedd on
the stifffer lanes [18].
Celladh
hesion on PF
FPE elastomeer
Bassed on its hydrrophobic and oleophobic naature, the PFP
PE fluoropolym
mer
was preedicted to bee anti-adhesivve to practicaally anything.. Thus, minim
mal
protein adsorption annd consequenttly very little cell
c adhesion was expectedd on
this matterial. Much too our surprise however, the cells (cell linne L929 of moouse
52
Marga C Lensen, Mar

M Diez and Vera
V A Schultte
i a
connecttive tissue fibrroblasts) adheered and spreaad on the smoooth material in
very sim
milar way as to the standardd cell culture plastic
p
TCPS, differing onlyy in
the timee frame; on PF
FPE the cell adhesion,
a
spreeading and forrmation of staable
adhesion complexes took
t
place wiith a delay of about 5 hourss when compaared
CPS [15]. Thee other, polym
meric materiall with a high fluorine conteent,
with TC
which is an already accepted
a
and often
o
used bioomaterial, wass also includedd in
mparative studdies and it wass found that cell
c adhesion and
a spreadingg on
the com
PVDF was
w not as goood as on PFPE
E (Figure 10).
Figure 10.
1 Adhesion and
a
spreading of fibroblasts on three diffeerent biomateriials;
PFPE, TCPS
T
and PVD
DF. Fluorescennce micrographhs of the fibrooblasts after 244 h,
stained with
w phalloidin (red) and DAP
PI (blue) and thhe average size of L929 cells after
a
24 h, as derived from fluorescence miccroscopy, are shhown.Reproducced from a previious
publicatiion in Biomaterrials in 2010 [155]with permissiion of Elsevier.
Thee cytotoxicityy tests of the PFPE elastomer demonnstrated that the

material is not cytotoxic. It should be noted heree that the elastoomer as prepaared
by UV-curing was sliightly cytotoxxic when appliied in cell culture immediattely
after cu
uring and this explains inn hindsight - the poor cell adhesion on the
PFPE material
m
that we
w reported in a previous puublication [14]]. From our more
m
extensiv
ve and system
matic studies peerformed everr since, we havve found out that
t
the maaterial as preepared mightt still containn some tracees of unreaccted
photoinnitiator, which can effectiveely be extracteed by organic solvents suchh as
hexane, acetone or ethanol. Thhis washing procedure leeads to a grreat
improveement in cytoccompatibility [15].
Wee have also invvestigated thee response of human macroophages (isolaated
from blood) to the paatterned, noveel biomaterial.. As can be seeen in Figure 11,
ular response to topographhic micropatterrns in terms of
o morphologyy is
the cellu
quite comparable
c
fo the cell line fibroblassts and the primary hum
for
man
53
macrophages. On the microline-pattern, the macrophages also spread and align

along the grooves (images not shown) [27].
Figure 11.Cell adhesion on smooth and micropatterned PFPE elastomers; top:

fibroblast cell line; bottom: human macrophages. Compiled from material published in
2010in Biomaterials[15] and ActaBiomaterialia [27]with permission of Elsevier.
Nevertheless, we have investigated the inflammatory response of the

macrophages on the substrate with different micropatterns of topography, i.e.
lines, big posts (20 m posts spaced 50 m; Figure 11 bottom right), small
posts small distance (3 m posts spaced 3 m; Figure 11 bottom middle),
small posts large distance (3 m posts spaced 20 m; not shown) and
discovered remarkable and significant differences in the cytokine expression
profile of the macrophages, based on which a pro- or an anti-inflammatory
phenotype can be assigned. For example, the line pattern induced a proinflammatory phenotype (M1), while interestingly, the big posts resulted in a
more anti-inflammatory response (M2-type). The responses to small posts with
large or small distance were also significantly different, implying that not only
the geometry and size of the features determine the cellular response, but also
the periodicity is important [27]. These results are very useful to predict
whether unwanted inflammatory responses will occur to for example implant
surfaces in tissue engineering applications.
54
CONCLUSION
We have shown the successful application of elastomers in biomedical
applications in that we fabricated biomaterials from prepolymers and
demonstrated that the cellular response to those materials can be manipulated
by tuning the chemical, physical and mechanical properties of the surface.
Both materials, the poly (ethylene glycol)-based hydrogels and the
perfluorinated polyether elastomers, are transparent and thus optimally suited
for life science investigations by inverted optical and fluorescence microscopy.
It cannot be stressed sufficiently that the patternability of the elastomers is a
great advantage, since many cell types, including stem cells, have been
observed to respond very sensitively to surface topography.
Our results have revealed that PEG-based hydrogels are not protein- and
cell-repellent perse; contrary to expectation we have discovered that as soon as
the PEG-surface is not smooth and homogeneous anymore, but patterned with
topography or elasticity, cell adhesion is enabled and cell spreading was
observed as well. Considering that the surface patterning should not change
the chemical and mechanical properties of the PEG-gels, these results are
highly unexpected and intriguing. This loss of anti-adhesiveness of PEG is
very important to take into consideration when designing for example
scaffolds or devices for applications in tissue engineering or diagnostics,
which rely on the bio-inertness of PEG. On the other hand it also opens new
opportunities for biomimetic material design which does not depend on
(difficult and expensive) biochemical surface functionalization for
manipulating cellular responses.
ACKNOWLEDGEMENTS
The authors greatly acknowledge financial support in the form of a Sofja
Kovalevskaja Award granted to M. C. Lensen by the Alexander von Humboldt
Foundation and funded the Federal Ministry for Education and Research
(BMBF). Financial support by the Deutsche Forschungsgemeinschaft (DFG) is
also gratefully acknowledged; within the frameworks of a) the German
Initiative for Excellence the Cluster of Excellence "Unifying Concepts in
Catalysis" (EXC 314)coordinated by the Technische Universitt Berlin, and b)
the Graduate School Biointerface (GRK 1035).
55
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C. M.; Chen, J.; Mller, M.; Netti, P. A.; Ventre, M. and Lensen, M. C.
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biosynthesis of collagen. J Biomed Mater Res, 28, 783789.
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3864-3872.

Chapter 3
PROPERTIES AND APPLICATIONS OF

WATER SWELLING MATERIALS
IN CIVIL ENGINEERING FIELDS
Shinya Inazumi11, Tadashi Wakatsuki2
and Masakatsu Kobayashi2
1
Graduate School of Engineering, Kyoto University, Japan

2
Nihon Chemical Paints Co., Ltd. Ayase, Japan
Abstract
Water-swelling material is a fluid sealant obtained by blending high

absorbency polymer, a filler and a solvent by using a synthetic resin
elastomer as the base material. In this research, we have studied the
composition of water-swelling material, the extent of swelling, strength
of the water swelling-material and the long-term performance of swelling
material used as jointed water cut-off treatment material at waste landfill
sites, by conducting various experiments. One of the examples of the
results is that the adjustment of the degree of etherification of high
absorbency polymer which is a component of the water-swelling material
and the resin content of the synthetic elastomer contribute to the
improvement of swelling of the sealant and strength of the swelling
material. Further, as time passes, the strength of the water-swelling
1
Corresponding author
60
Shinya Inazumi, Tadashi Wakatsuki and Masakatsu Kobayashi

material shows a tendency to become stabilized and it was confirmed that
it had sufficient pressure-resistance in coastal landfill sites, where its
application as water cut-off treatment material is being considered.
INTRODUCTION
Water-swelling material is a fluid sealant obtained by blending high
absorbency polymer, a filler and a solvent by using a synthetic resin elastomer
as the base material. In the field of civil engineering, water-swelling materials
are widely used as water cut-off treatment material for increasing water cut-off
properties at the joint section of steel sheet piles or steel pipe sheet piles (see
Fig. 1). 1, 2, 3 Further, the water-swelling material coated or pasted to the joint
section swells on contact with ground water, blocks the water passage gaps
and allows water cut off at the joint section.
Figure 1. Water cut-off treatment on joint section of steel sheet piles or steel pipe
sheet using water-swelling materials.
Recently, the H-jointed steel pipe sheet piles with an H-H joint, which is
one of the newly developed methods for high water cut off, is being tried for
application of water-swelling material for water cut-off treatment of the joints
Properties and Applications of Water Swelling Materials
61
section. In a series of research projects, one can see a number of reports

regarding the performance of water cut-off steel pipe sheet piles making use of
an H-H joint, using water-swelling material for adhesion. 3, 4 For example in
plain water or artificial sea water (3% saline), low hydraulic conductivity of
the order of 110-8 cm/s has been clearly confirmed. Peeling off or the ability
of water cut off of the water-swelling material at the field has been studied and
good results have been reported in general.
In this paper, we have carried out studies on the composition of waterswelling material and the strength of the swelling membrane, which is used for
water cut-off treatment of the joint section of steel sheet piles or steel pipe
sheet piles, by conducting various experiments for the purpose of improving
the swelling ability and making it stronger. Further, the long-term performance
of water-swelling material used at the joint section of jointed sheet piles as
water cut-off treatment material was also considered regarding the relation
between the change of the strength of the swelling material with the elapsed
time and pressure resistance.
HISTORICAL BACKGROUND OF
WATER-SWELLING MATERIAL
The water extracted from a dried film of water-swelling material fulfills
the Food Sanitation Law Standards and is not harmful to the environment. At
present, the composition of frequently used water-swelling materials (hereafter
referred to as current water-swelling material) is such that when it is soaked
in plain water or sea water for 24 hours, it swells up to 15 - 30 times and 5 - 7
times, respectively, in terms of weight ratio. Thus, the current water- swelling
material has extremely high swelling ability in plain water, nevertheless, the
swelling percentage in sea water is 1/6 - 1/3 of that in plain water. Further,
there is a tendency for the strength of the swelling material film (strength of
water-swelling material after swelling) to be lower in plain water due to the
effect of the water temperature. Because of this type of swelling and the
strength properties of the swelling-type material, water-swelling material has,
thus far, been used mainly as temporary water cut-off material. Here, the
improvement in the swelling properties of the water-swelling material and the
strength of the swelling material are not restricted only to increases in the
water cut off at the joint section of the steel pipe sheet pile or steel sheet pile,
62
but they may be contributing to several other applications of water-swelling

material.
Representative examples of the application of water-swelling material
includes vertical water cut off wall (barrier) built from steel sheets pile or steel
pipe sheet pile in costal landfill sites. The vertical water cut-off property of
steel sheets pile or steel pipe sheet piles is manifested by the swelling effect of
water swelling material previously coated or pasted at the joints before setting
up (see Fig. 1). 1, 2, 3 While employing the water swelling material for water
cut-off treatment of joints, it may be used in the form of a sheet pasted inside
the joint (swelling-type sheet) or it may be used as a coated sealant. Depending
upon the situation, it is possible to select the appropriate form of the material.
Further, it is possible to prevent peeling off by synthesizing a swelling-type
paint that adheres strongly to the steel. On the other hand, the water
permeability factor of swelling-type material itself and that of the steel or paint
are not different and both are of the order of 110-9 cm/s. 3
SWELLING PROPERTIES OF THE WATER-SWELLING

MATERIAL
Swelling test
Here, the swelling properties of the water-swelling material were studied
for various compositions, with water of different properties, different
temperature and different pH, by designing individual tests.
The procedure for swelling tests was as follows:
(i) A definite quantity of water-swelling material was dried, it was converted
into a 2 mm thick sheet and a test piece sized 2 cm2 cm was prepared.
(ii) The initial weight of the test piece was measured and it was soaked in a
water tank having various qualities of water at various temperatures.
(iii) After soaking for 48 hours, it was taken out and the weight was measured.
(iv) Swelling ratio (= weight after soaking / initial weight) was calculated.
The swelling ratio has been calculated by weight due to difficult in
measuring volume of the water-swelling material after swelling. The swelling
ratio by volume almost equaled 70% of it by weight, as a result of a
preliminary test on swelling ratio of water-swelling material.
63
Composition and swelling ratio

Swelling mechanism of the water-swelling material depends mainly on the
expansion of the high absorbency polymer (polymeric material designed to
hold a large quantity of water). We focused on the etherification (degree of
substitution; DS value) of the polymer that is blended, and swelling
experiments were conducted in the case of water-swelling material blended
with polymers having different DS values. The DS value is an index showing
the strength of bonds in the polymer structure. It is the molar quantity (number
of mols) of sodium (Na) etherified (conversion into Na compound)
corresponding to 1 unit (6 carbon atoms) of glucose (C6H12O6) from the high
absorbency polymer.
Figure 2 shows the swelling ratio of the water-swelling material soaked in
plain water and artificial sea water (3% saline) and the DS value of the high
absorbency polymer). Moreover, the DS value of the high absorbency polymer
used at present in water-swelling material is 0.6 M/c6. According to Fig. 2,
when a polymer with a high DS value is used for blending, the swelling ratio
in artificial sea water greatly increases. Especially by reforming the DS value
of the high absorbency polymer to 0.9 M/c6, the swelling ratio increases 2
times of that of the current water-swelling material (High absorbency polymer
DS value = 0.6 M/c6). This is because the insolubility of the high absorbency
polymer is enhanced due to the large number of ions present in the artificial
sea water. Nevertheless, the enhancement of insolubility is moderated by the
use of high absorbency polymer with a high DS value, to a certain extent. On
the other hand, in plain water (which does not enhance the insolubility of the
water-swelling material) it is possible to maintain the swelling ratio of the
same order (27 - 29 times) even if the DS value of high absorbency polymer is
increased.
Figure 3 shows the relation between the addition ratio of the high
absorbency polymer (having its DS value reformed to 0.9 M/c6 in waterswelling material) and its swelling ratio. From this it is understood that the
increase in the addition ratio of high absorbency polymer contributes to the
increase in swelling of water-swelling material in an environment comprising
plain water and artificial sea water. Further, in general, the addition ratio of the
high absorbency polymer currently used for blending with water-swelling
material (high absorbency polymer with a DS value = 0.6 M/c6) is 32.5% by
weight.
64

35
Soak in plain water
Swelling ratio
30
25
20
Soak in artificial sea water (3% saline)
15
10
5
Current value
Water temperature: 20 degrees

Addition ratio of
high absorbency polymer: 32.5%
0
0.6
0.8
1.0
1.2
1.4
DS value of high absorbency polymer (M/c6)

Figure 2. Relationship between swelling ratio and DS value of high absorbency
polymer for water-swelling material.
35
Soak in plain water
Swelling ratio
30
25
20
15
10
5
0
20.0
Current value
25.0
30.0

DS value of
high absorbency polymer: 0.9 M/c6
35.0
40.0
45.0
50.0
Addition ratio of high absorbency polymer (%)

Figure 3. Relationship between swelling ratio and addition ration of high absorbency
polymer for water-swelling material.
65
Thus, for further improvement of the swelling ratio of the water-swelling

material, it is proposed to ensure blending of high absorbency polymer having
a DS value in excess of DS = 0.6 M/c6 and with more than 32.5% by weight.
Salinity of soaking water, its temperature, pH and the swelling ratio

The properties of the soaked water (salinity, plain water or sea water),
water temperature and pH are supposed to greatly influence the swelling
property of the water-swelling material. For this, swelling experiments were
carried out by varying the conditions like the quality of soaked water, its
temperature and pH.
Depending upon whether the soaking water is plain water or artificial sea
water (3% saline) there is a large difference in the swelling ratio of the waterswelling material. On the other hand, in the case of a high absorbency polymer
with a reformed DS value of around 0.9M/c6, the swelling ratio increases a lot,
especially in the case of artificial sea water (3% saline) as stated in above, and
it is possible to get a swelling ratio twice that of the value found in a case
utilizing the currently used high absorbency polymer with a DS value = 0.6
M/c6. As a result, the difference between the swelling ratio in an environment
of plain water and artificial sea water declines (see Fig. 2).
As shown in Fig. 4, the temperature of the soaking water influences the
swelling ratio of the water-swelling material and, especially in the case of the
plain water environment, the swelling ratio shows a tendency to increase as the
water temperature increases. On the other hand, increasing the temperature of
artificial sea water does not improve the swelling ratio of the water-swelling
material. The high absorbency polymer blended with water-swelling material
is a high polymer electrolyte and, when it is soaked in an aqueous
environment, water gets absorbed in the mesh of the high absorbency polymer
and it is gelatinized (swollen condition). Further, the gelatinized high
absorbency polymer dissolves in water, giving ride to a uniform polymer
solution. However, the high absorbency polymer has the property of bonding
with polyvalent metal ions and if polyvalent metal ions exist in the water, it
forms insoluble metal salts. The formation of insoluble metal salts restricts the
free movement of the molecules, and as a result, only gel formation (swelling)
unidirectional water absorption into the high absorbency polymer occurs.
Moreover, increasing the water temperature enhances the quantity of water
absorbed into the high absorbency polymer (swelling is enhanced) more. On
the other hand, in an artificial sea water environment, as the ionic
concentration is high, the water content that the high absorbency polymer can
66
absorb may reduce (insolubility is enhanced and swelling becomes less). Thus,
the insolubility of high absorbency polymer is enhanced and, when the
swelling ratio of the water-swelling material itself is small (under the artificial
sea water environment), the increase in the swelling ratio may also be
prevented as the temperature goes up.
60
DS value of
Addition ratio of
Swelling ratio
50
40
Soak in plain water
30
20
10
0
0
10
15
20
25
30
35
Temperature of soaking water (degrees)

Figure 4. Relationship between swelling ratio and temperature of soaking water for
water-swelling material.
Figure 5 shows the relation between pH of the soaking water and of the
swelling ratio of the water-swelling material. From this, it is understood that
the water- swelling material has a tendency to have a lower swelling ratio in a
strongly acidic or strongly alkaline area. However, if the pH is in the area of 4
- 12, the influence of pH on the swelling ratio is less and thus in the actual use
of water-swelling material, pH of soaked water does not have a great
influence.
Swelling ratio and concentration of chemical substances of the soaking

water
Assuming that the water-swelling material is going to be used as water
cut-off material for coastal waste-disposal sites; the swelling properties of the
water-swelling material were studied in various harmful chemical substances
that are supposed to be present in reclaimed landfills. Further, as it is not
67
possible to identify all the chemical substances that are found in reclaimed
landfills, the study was conducted in water containing chemical substances
shown in Table 1.
35
Swelling ratio
30
25
20
15

DS value of
Addition ratio of
10
5
0
0
10
15
pH of soaking water
Figure 5. Relationship between swelling ratio and pH of soaking water for waterswelling material.
Table 1 also shows the swelling ratio of water-swelling material obtained

in the water containing chemical substances. From this, it could be confirmed
that even in soaking water containing heavy metals, the water-swelling
material shows swelling of the same order as that in the case of plain water
(see Table 1(a)) and the deterioration of the swelling material could not be
confirmed. Thus, it can be concluded that heavy metals contained in the
soaking water do not have a large influence on the swelling ratio of the waterswelling material.
On the other hand, when organic solvents are contained in the soaking
water, the synthetic resin elastomer (which is the base material for the waterswelling material), gets soaked in the solvent, when the organic solvent is in a
saturated concentration. Due to this, the water-swelling material collapses and
this disables the application of the water-swelling material when the organic
solvent is in a saturated concentration. Further, swelling is also not possible in
a saturated concentration of organic solvents. On the other hand, the influence
of organic solvents on swelling of the water-swelling material is not at all seen
in soaking water containing organic solvents to the extent of 2.0 g/L, and
68
sufficient swelling takes place (see Table 1(b)). Moreover, deterioration of the
water-swelling material was also not seen in the condition of a concentration
around 2.0 g/L.
Table 1. Swelling ratio of water-swelling material obtained in water

containing chemical substances
(a) Water containing heavy metals
Chemicals
Chrome oxide IV
Cadmium sulfate
Selenious acid
Lead chloride II
Mercury nitrate II
Potassium ferrocyanide
Arsenic trioxide
Thiram
Thiobencarb
Simazine
0.2 g/L solution

Swelling ratio
27.3
27.1
25.8
28.7
27.3
27.5
28.0
26.5
28.6
27.0
(Swelling ratio under plain water: 28.0)
(b) Water containing Organic solvents

Chemicals
Benzene
Trichlorethylene
Tetrachloroethylene
Dichloromethane
Carbon tetrachloride
Dichloroethane
Trichloroethane
Saturated
2.0 g/L
solution
solution
Swelling ratio Swelling ratio
decay
27.3
decay
28.6
decay
29.3
decay
28.1
decay
27.4
decay
28.7
decay
27.1
(Swelling ratio under plain water: 28.0)
69
STRENGTH CHARACTERISTICS OF
WATER-SWELLING MATERIAL
Water-swelling material strength test
Water-swelling material strength means the strength of the material when
the water swelling-material is in a swollen condition. Swelling material
strength of the water-swelling material greatly influences the resistance to
water (hydraulic) pressure and long-term endurance. Thus, a study was
conducted from various viewpoints for improving the strength of swelling
material, and it was concluded that the composition of water-swelling material
is the factor behind this. Here, the swelling strength of the water-swelling
material was measured by using a small desk testing machine (EZTEST-500N,
SHIMADZU Corporation) and penetrating elastic tool (diameter 3 mm) (see
Fig. 6) and, the relation of the composition of the water-swelling material with
the swelling strength was studied. The swelling material strength was defined
as the strength required (by the penetration elastic tool with a 3 mm diameter),
for penetration and breaking of the water-swelling material.
Water-swelling material
Figure 6. Simple overview of water-swelling material strength test.
The procedure for the swelling film strength test was as follows:
(i) A definite quantity by weight of water-swelling material was dried, it was
converted into a 2 mm thick sheet and a test piece sized 2 cm 2 cm was
prepared.
70
(ii) The test piece was submerged in a water tank filled with plain water and
artificial sea water at a set temperature.
(iii) After submerging for 48 hours, the penetration tool (3 mm diameter) was
slowly allowed to penetrate into the water-swelling material as shown in
Fig. 6 and the swelling material strength (penetration elasticity value) was
measured.
Composition and swelling material strength

Synthetic resin elastomer, which is the base material for the waterswelling material, is one of the materials that influences the swelling film
strength. Here, attention was paid to the resin content (vinyl acetate) of the
synthetic resin elastomer, and swelling material strength tests were carried out
in the case of water-swelling material blended with elastomer B and elastomer
C (having a resin content 1.3 times and 1.5 times that in the synthetic resin
elastomer A, which is used for blending with the current water-swelling
material).
Table 2. Swelling ratio and the swelling material strength of waterswelling material soaked in plain water and artificial sea water at 20 C
water temperature
Elastomer
Elastomer A
Elastomer B
Elastomer C
Swelling ratio
Plain
Artificial
water
sea water
31
15
28
14
24
11
Strength (N)
Plain
Artificial
water
sea water
0.3
1.0
0.6
1.3
1.0
1.8
Table 2 shows the swelling ratio and the swelling material strength of the
water-swelling material soaked in plain water and artificial sea water at 20C
water temperature. Further, Fig. 7 shows swelling material strength with the
variation of the temperature of the soaking plain water or artificial sea water.
Table 2 shows that the swelling ratio of the water-swelling material decreases
according to the synthetic resin elastomer content blended with it. However,
when blended with elastomers B or C, which have a higher resin content, the
swelling material strength increases in plain water and artificial sea water.
Especially water-swelling material blended with a higher quantity of synthetic
resin elastomer B can increase the swelling film strength to about 2 times and
1.5 times that of the currently used water-swelling material in plain water and
71
artificial sea water, respectively. The increase in the swelling material strength
by blending with elastomer B and C is manifested in the case of both a plain
water and artificial sea water environment under a water temperature of 5 30C (see Fig. 7). On the other hand, the swelling material strength blending
with each elastomer shows the tendency to decrease with the increase of water
temperature in the case of both a plain water and artificial sea water.
Furthermore, the decrease in the strength under the artificial sea water
environment may be confirmed to be larger than that under the plain water
environment. However, it is thought that the strength decreasing rate of the sea
water environment and that under the plain water environment are the almost
the same levels. Also, no much difference in the decreasing tendency in both
swelling ratio and swelling material strength was seen between two cases of
plain and artificial sea water (see Figs. 4 and 7).
LONG-TERM ENDURANCE OF WATER

CUT-OFF TREATED JOINTS
Outline of the test
A swelling material strength test and endurance test were carried out in the
case of water-swelling material, supposing its application at the joints of steel
sheet piles or steel pipe sheet piles, for understanding the relation between the
changes of the swelling material strength and its resistance to water pressure
with elapsed time. Here, water-swelling materials used for the tests simulate
the condition of being pasted on the joints of steel sheet piles and steel pipe
sheet piles as shown in Fig. 1, and swelling of the water-swelling material was
imitated to some extent in the joint gaps. The swelling film strength test
conducted here is called a restraint-type swelling material strength test for
differentiating it from the swelling material strength test mentioned above. The
difference between the two is whether the swelling is restrained or not,
during soaking of the water-swelling material. In the restraint-type swelling
material strength test, a test piece holder was prepared by pasting the waterswelling material in the form of a 2 mm thick sheet on two acrylic plates as
shown in Fig. 8 and it was submerged in a water tank filled with plain water or
artificial sea water (3% saline). Further, swelling of the water-swelling
material was restrained between the two acrylic plates. After being submerged
for a set period of time, the water-swelling material was taken out from the
acrylic plates and it was slowly allowed to be penetrated by the penetration
72
elasticity tool shown in Fig. 6 (3 mm diameter) to measure the swelling film

strength.
Swelling material strength (N)
2.0
DS value of
Addition ratio of
1.5
1.0
Blending with elastomer C

Blending with elastomer B
0.5
Blending with elastomer A

(curent elastomer)
0.0
0
10
15
20
25
30
35
30
35
(a) Soaking in plain water
2.0
Blending with elastomer C
1.5
Blending with elastomer B

Blending with elastomer A
(curent elastomer)
1.0
DS value of
Addition ratio of
0.5
0.0
0
10
15
20
25
(b) Soaking in artificial sea water

Figure 7. Relationship between swelling material strength and temperature of soaking
water for water-swelling material.
73
Figure 8. Swelling of water-swelling material under restraint-type swelling.
On the other hand, in the test for evaluating the relation between pressure
resistance of water-swelling material and the swelling material strength (see
Fig. 9), water-swelling material of thickness 1, 1.2, 1.4 and 2 mm was pasted
on both sides of the flange tool of the pressure resistance container (gap: 10
mm) and the pressure resistance container was submerged in a water tank
filled with plain water and after 15 - 30 days have passed, pressure was
applied on the pressure resistance container in a step-wise manner and the
pressure required for a leakage of air was measured. The pressure of the
previous step was considered to be the pressure resistance. At the same time,
by measuring the swelling material strength by using a penetration elasticity
tool for a test piece after the pressure resistance test, the relation between the
pressure resistance of water-swelling material and the swelling material
strength under the condition of restricted swelling in the flange tool was
worked out. Now the use of water-swelling material of various thicknesses in
the tests and tests conducted for arbitrary submerging periods are for working
out the relation between restricted swelling film strength at various levels and
pressure resistance of the water-swelling material.
74
Flange tool
Flange tool
Figure 9. Evaluation chart of relation between pressure resistance of water-swelling

material and swelling material strength.
Variation of swelling material strength with elapsed time

Figure 10 shows the elapsed time of the film strength under the restricted
swelling condition of water-swelling material of 2 mm thickness obtained
from a restraint-type swelling film strength test. In the initial period of water
submerging, the water-swelling material maintains its swelling film strength
which it had prior to submerging. As time passes, the water content penetrates
the entire water-swelling material and the swelling film strength shows a
decreasing tendency. A reduction in the restricted swelling film strength can
be attributed to the reduction of density (cross linking density) of the waterswelling material due to a swelling of the high absorbency polymer in the
water-swelling material in the stage where the water spreads into the waterswelling material. On the other hand, water-swelling material submerged into
artificial sea water has a higher value of swelling material strength as
compared to that in plain water. This may be because the quantity of swelling
in water-swelling material is less in a sea water environment, which contains
electrolytes, than in a plain water environment. Therefore, the density of
water-swelling material is higher than in a plain water environment. In other
words, although water-swelling material exposed to a sea water environment
has a lesser quantity of swelling as compared to that exposed to plain water,
the density of water swelling sealant material exposed to sea water is
comparatively high and the swelling material strength of water-swelling
material is higher than that of the material submerged for the same time in a
plain water environment.
Further, as explained earlier, by varying the composition ratio of the high
absorbency polymer, filler and solvent, and water-swelling material, it is
possible to increase the swelling material strength (improvement of waterswelling material) of water -swelling material.
75
7.0
DS value of high absorbency polymer: 0.6 M/c6
6.0
Addition ratio of high absorbency polymer: 32.5%

Blending with elastomer A (curent elastomer)
5.0
4.0
Soak in plain water

3.0
2.0
1.0
1.6
0.95
0.0
400
800
1200
1600
2000
Elapsed time (days)

Figure 10. Change in film strength under the restricted swelling condition of waterswelling material.
Relation between swelling material strength and pressure resistance

Figure 11 shows the relation between the swelling film strength and
pressure resistance under the restricted swelling condition for water-swelling
material submerged in plain water for 15 - 30 days. From this, it is understood
that as the swelling film strength increases, the pressure resistance of waterswelling material also increases and when the swelling film strength of waterswelling material under a restricted swelling condition is more than 1.0 N, the
pressure resistance is 0.5 MPa or more and when the swelling film strength
under a restricted swelling condition becomes 0.2 N or less the pressure
resistance reduces to 0.1 MPa. Here, in case of a coastal landfill with 2 m
managed water level 5 (difference of water level on inside and outside of the
landfill); the pressure resistance required for water-swelling material at the
joint for water cut off is about 0.05 MPa, even after considering the dangerous
level (water level difference of 5 m). Thus, if the swelling film strength is
maintained at or above 0.2 N, the water-swelling material can maintain a
sufficient water cut-off effect for a pressure of 0.05 MPa. Further, in the
restraint swelling-type elasticity experiments in the case of water-swelling
material, in a period of 5 years, the restricted swelling film strength of waterswelling material shows an asymptotic tendency near 1.6 and 0.95 N in sea
water and plain water (see Fig. 10) and thus a swelling film with a stable
76
strength and pressure resistance even for a long period is expected. However,
for evaluation of the endurance of the water-swelling material in more detail, it
is necessary to continue these experiments.
Pressure resistance (MPa)
0.6
0.5
> 0.5 MPa
> 0.5 MPa
0.4
0.3
0.2
0.1
0.0
0.0
1.0 mm thick sheet

1.2 mm thick sheet
1.4 mm thick sheet
2.0 mm thick sheet
Submerged periods: 15 - 30 days

0.5
1.0
1.5
2.0
2.5

Figure 11. Relationship between swelling film strength and pressure resistance.
CONCLUSION
In this paper, experimental studies were carried out in the case of the
composition of water-swelling material, its swelling and swelling material
strength. Further long-term performance of water-swelling material used for
water cut-off treatment of H-jointed steel pipe sheet piles with an H-H joint
was discussed from the point of the variation of the swelling film strength and
pressure resistance with elapsed time.
The results obtained were as follows:
(i) In case of water-swelling material blended with high absorbency polymer
with higher etherification value (DS value), the swelling ratio is very high
in artificial sea water. Especially, by reforming the DS value of the high
absorbency polymer to 0.9 M/c6, swelling ratio that is 2 times the value of
that of the currently used water-swelling material (with a DS value of the
high absorbency polymer = 0.6 M/c6) can be obtained in an artificial sea
water environment.
77
(ii) An increase in the water temperature of plain water influences the increase
in the swelling ratio of the water-swelling material. On the other hand, the
temperature of sea water does not influence the swelling ratio of the
water-swelling material. Further, water-swelling material shows a
tendency of lowering the swelling ratio in strongly acidic or strongly
alkaline areas, but the influence of pH on the swelling ratio of the waterswelling material is less in the area of pH 4 - 12.
(iii) The quantity of synthetic resin elastomer, which is a component of the
water-swelling material, contributes to the improvement of the swelling
film strength of the water-swelling material. Especially water-swelling
material blended with a higher quantity of synthetic resin elastomer B can
increase the swelling film strength to about 2 times and 1.5 times that of
the currently used water-swelling material in plain water and artificial sea
water, respectively.
(iv) The swelling film strength of water-swelling material is higher when
exposed to a sea water environment as compared to that exposed to a plain
water environment. Further, with elapsed time, the swelling film strength
shows a tendency to stabilize. Moreover, the swelling film strength
showing some stability has sufficient pressure resistance at coastal
landfills.
REFERENCES
1. Kamon M, Inui T (2002) Geotechnical problems and solutions of
controlled waste disposal sites (in Japanese). JSCE Journal of
Geotechnical Engineering 701/III-58:1-15
2. Oki T, Torizaki K, Kita H, Yoshida M, Sakaguchi Y, Yoshino H (2003)
Evaluation of impermeability performance of the vertical impermeable
walls by using steel sheet piles and steel pipe sheet piles (in Japanese).
Proceedings of the 5th Japan National Symposium on Environmental
Geotechnology 53-58
3. Inazumi S, Kimura M, Too A.J.K, Kamon M (2005) Performance of Hjointed steel pipe sheet piles with H-H joint in vertical hydraulic cutoff
walls. Proceedings of the 16th International Conference on Soil
Mechanics and Geotechnical Engineering 4:2269-2272
78
4. Inazumi S, Kimura M (2009) On-site verification for installation and

permeability of H-jointed SPSPs with H-H joints. Proceedings of the 17th
International Conference on Soil Mechanics and Geotechnical
Engineering (Accepted for Publication)
5. Waterfront Vitalization and Environment Research Center (2002) Design,
Construction and Management Manual for Managed Type Waste
Reclamation (in Japanese). Waterfront Vitalization and Environment
Research Center

Chapter 4
ELASTOMERIC DIFFRACTIVE OPTICS

FABRICATED BY SOFT LITHOGRAPHY
Raphael A. Guerrero
Department of Physics, Ateneo de Manila University
Loyola Heights, Quezon City, Philippines
Abstract
Soft lithographic techniques allow the convenient preparation of
deformable elastomeric optical elements. Elastomers, due to their low
cost and versatile fabrication protocols, have proven to be ideal materials
for developing flexible optics for diverse systems. Specific applications in
multiplexed volume holography and variable diffraction with a silicone
grating are discussed in this chapter. Replication of diffractive surfaces
by soft lithography is described for both holographic phase masks and
planar gratings. A theoretical framework is established for storing
multiple holograms with an elastomer mask based on the modification of
path length by the application of strain. Dynamic diffraction with a
stretchable grating is accounted for by a simple modification of the
grating equation that accommodates a change in groove periodicity due to
elongation. Experimental results for volume holography include the
storage and reconstruction of two-dimensional images and notes on phase
selectivity. Angular scanning as a function of strain is demonstrated for
elastomeric gratings. Included in this chapter are recent developments in
biomimetic optics afforded by soft lithography. Diffraction effects from
grating structures on an elastomer cast of an insect carapace are
80
Raphael A. Guerrero
presented. The chapter concludes with a discourse on beam deflection
and color displays with an elastomer grating actuated by a shape memory
alloy.
INTRODUCTION
Dielectric elastomers such as silicone are emerging as ideal materials for
optical applications due to their low cost, design versatility and convenient
fabrication techniques. Diffractive elements based on silicone include
interference gratings [1], high-speed beam deflectors [2], and thermal
detectors [3]. Numerous options are available for the preparation of grating
structures on elastomer substrates, ranging from contact printing [4] to laser
scanning [5]. Soft lithography is a replication process designed to copy
surface relief structures by casting a liquid prepolymer against a master mold
[4]. In addition to its relative simplicity, soft lithography also produces
replicas that are highly faithful to the original, even on the nanoscale [6].
Soft lithography is employed to create the elastomeric optics for
diffractive applications discussed in this chapter. Through a straightforward
elastomer casting protocol, tunable diffraction gratings and deformable phase
masks for holography are fabricated. Each optical element is described in
detail below.
MULTIPLEXED HOLOGRAPHIC STORAGE WITH AN

ELASTOMER PHASE MASK
Polydimethylsiloxane (PDMS) is an ideal material for phase masks due to
its transparency and the relative ease with which phase information can be
tailored for a specific use. This section deals with how phase-multiplexed
volume holographic storage can be performed with an elastomer mask [7].
Images can be stored at different phase addresses determined by the
displacement of the elastomer from an unstretched configuration.
Multiple holograms may be stored through volume holography with a
photorefractive crystal by assigning a unique phase distribution to the
reference beam used in recording individual data pages. Figure 1 is a
schematic diagram of the phase-encoding process employed in the holographic
system [7]. Two-dimensional intensity information O(x,y) is recorded by a
Elastomeric Diffractive Optics Fabricated by Soft Lithography
81
plane wave R(x1,y1) = Roexp[i1(x1,y1)]exp(ikr1). Phase information 1(x1,y1),

encoded on the reference beam by the elastomer, is given by:
1 ( x1 , y1 ) =
2
n t1 ( x1 , y1 ) ,
(1)
Ro
Elastomer mask
t1(x1,y1)
L1
R(x1,y1)
t2(x2,y2)
O(x,y)
L2
Photorefractive
crystal
Figure 1. Multiplexed volume holographic storage with an elastomer phase mask.

Random phase addresses for individual data pages are generated by stretching the
elastomer. Original dimensions length L1 and thickness t1 are related to deformed
values L2 and t2 by the conservation of volume.
where t1(x1,y1) is the thickness at each point on the mask, n is the refractive
index of the elastomer and is the recording wavelength. Via the
photorefractive effect, O(x,y) is recorded as a hologram in the form of a
refractive index modulation proportional to the resultant intensity of the two
interfering beams [8]. Succeeding holograms are stored by stretching the
elastomer in one dimension, introducing a different phase address 2(x2,y2):
2 (x 2 , y 2 ) =
2
n t 2 (x 2 , y2 ) .
(2)
Assuming that the elastomer is incompressible and, for small

displacements the stretching is uniform, the new thickness t2(x2,y2) is related
to t1(x1,y1) by the conservation of volume:
82
Raphael A. Guerrero
L1 / 2
W1 / 2
L 1 / 2 W1 / 2
t1 ( x1 , y1 )dx1dy1 =
L2 / 2
W2 / 2
L 2 / 2 W2 / 2
t 2 ( x 2 , y 2 )dx 2dy 2
(3)
In the relaxed state, the elastomer mask is taken to have length L1 and
width W1. Stretching is confined along L1, leading to a displaced length L2 =
(1 + )L1, where is a strain factor. The new width W2 and a modified
thickness function result from contractions of the elastomer in the directions
perpendicular to the elongation [9]. The change in width is negligible
compared to the extension from L1 to L2. By further displacements from the
elastomers equilibrium state, the thickness may be easily changed to provide
different phase addresses for additional data pages. For a random thickness
distribution, high selectivity among recorded holograms is achieved since
reconstruction with a reference beam carrying a phase code different from the
original beam retrieves an amplitude Or(x,y), such that
O r ( x, y) O( x, y) exp[i( 2 ( x 2 , y 2 ) 1 ( x1 , y1 ))]
(4)
A more detailed expression for Or(x,y), along with additional comments
regarding phase selectivity, is provided elsewhere [7, 10]. Intensity
components of the reconstructed image tend to interfere destructively because
of the random phase factor. O(x,y) is completely recovered only if the correct
phase distribution is used during reconstruction with 1(x1,y1) = 2(x2,y2). The
selectivity possible with the phase mask depends on both the original phase
distribution and the elastic modulus of the elastomer [9].
Random phase masks for holographic multiplexing are prepared via soft
lithography. The basic surface replication process is illustrated in Figure 2. For
a mask with arbitrary phase distributions, a thin layer of quick-drying adhesive
is first applied nonuniformly on the bottom of a water-tight mold. PDMS is
then poured into the mold up to the desired thickness, where the elastomer
flows into all available gaps on the hardened adhesive. After a sufficient
amount of curing time, the elastomer becomes solid, with one surface taking
exactly the same three-dimensional profile as the randomly applied adhesive.
The resulting mask is carefully peeled off from the mold. A similarly simple
method may be applied to fabricate replicas of diffraction gratings and
biological surfaces. Replicated surface structures discussed in this chapter are
much smaller than the feature size limitation for accurate elastomeric casting
[6]. Representative elastomer phase masks made using the above technique are
shown in Figure 3. Thickness distribution for one side of the solid elastomer,
83
directly related to the phase generated by the mask, may be varied according to
the specific manner of applying the original adhesive.
(a)
(b)
(c)
Figure 2. Basic soft lithographic replication process for elastomer phase masks: (a) a
random thickness distribution serves as a master template for casting; (b) PDMS is
poured into the mold, completely covering the surface; (c) after curing, a flexible
complementary copy of the surface may be extracted. For fabricating other types of
diffractive optics discussed in this chapter, the template in (a) is simply replaced with a
planar grating or a beetle carapace.
Figure 3. Elastomer phase masks for volume holography. A single mold may be used
to make several masks with different random surface features.
84
Raphael A. Guerrero
Holographic recording and readout are performed with a HeNe laser

operating at 4 mW with = 543.5 nm. The photorefractive medium is a
LiNbO3 crystal, doped with 0.05% Fe. The reference beam is encoded with
phase information after passing through the elastomer mask. A special holder
is constructed to allow stretching of the elastomer phase mask in one directon.
Images may be recorded in less than a minute. Figure 4 shows a pair of images
reconstructed from multiplexed holograms recorded with the elastomer phase
mask. Stretching the mask by 0.1 to 0.4 % produces enough phase mismatch to
prevent a previously stored hologram from being reconstructed. Another
hologram may then be stored at this modified phase address. Minimum applied
strain to produce sufficient phase mismatch varies for successive holograms
because of the randomness of the surface of the phase mask.
Figure 4. Reconstructed images from holograms recorded with an elastomer phase

mask. E is stored at a particular elastomer strain level. Stretching the phase mask
introduces a phase mismatch that allows the recording of O. No cross-talk between
images is observed.
Phase selectivity for the elastomer mask is described in terms of the

amount of strain required to sufficiently reduce the reconstructed intensity
from a previously recorded hologram. Ideally, only a minimal amount of
elongation is needed in order to record an additional data page. Figure 5 is a
plot of reconstructed intensity as a function of % elongation of the phase mask.
A sharp drop in intensity is observed when the mask is stretched by 0.06%,
corresponding to an elastomer displacement of only 0.07 mm. Selectivity
depends on the degree of non-uniformity of the surface profile of the mask.
For this particular phase mask, more than 50 holograms may be multiplexed
with 3% elongation of the elastomer.
Reconstructed Intensity
85
1
0.8
0.6
0.4
0.2
0
0
0.05
0.1
0.15
0.2
0.25
0.3
% strain
Figure 5. Plot of normalized reconstructed intensity vs. % strain applied to the

elastomer phase mask. Multiple holograms may be stored with minimal elongation of
the mask.
VARIABLE DIFFRACTION WITH A DEFORMABLE

ELASTOMER GRATING
Soft lithography may also be used to imprint grating grooves on an
elastomer substrate. The elasticity of the elastomer allows for the modification
of grating parameters through the application of strain. Viscoelastic silicone
gratings can act as high-speed laser scanning elements that exhibit large
angular deflection [2]. Stretching and relaxing an elastomer grating would
allow real-time control of diffraction characteristics. Tunable gratings find
utility in beam steering, optical communications and spectroscopy.
Elastomer gratings generate variable diffraction angles by the
modification of groove spacing through mechanical stretching. Given an
incident angle , an expression for the tunable diffraction angle is provided
by a modified version of the grating equation:
m = d s (sin + sin ) ,
(5)
where m is the diffraction order. The effect of grating elongation is included in

groove spacing ds, which is a linear function of strain:
d s = (1 + s )d o ,
(6)
86
Raphael A. Guerrero
where s = L/Lo, with change in length L much smaller than initial length Lo,
and do is the groove pitch of the original grating template. is an elastomer
strain factor that describes the resilience of the material [11].
Replication of grating grooves on an elastomer is performed by soft
lithography using an aluminum-coated master with dimensions 25.4 mm x
12.7 mm. Groove density is 1200 lines/mm with a triangular groove profile.
The master grating is placed face-up in a custom mold designed so that the top
portion of the grating rises only 1 mm from the bottom of the mold. Liquid
PDMS with an appropriate amount of curing agent is poured into the mold,
filling the volume completely. Curing time is 5 days at 25 oC. Once fully
cured, the elastomer is carefully peeled off the mold, leaving a copy of the
grating surface imprinted on the substrate (Figure 6). White light dispersion is
easily observed with the replica and faithful reproduction of grating structures
is verified by optical microscopy [11]. The elastomer grating is lightweight,
robust and may be conveniently mounted for diffraction experiments.
Figure 6. Planar grating replica fabricated via soft lithography. Flexibility of the
grating leads to tunable diffraction angles.
Scanning capability of the stretchable grating in reflection mode is

demonstrated by measuring the angular deflection of the 1st-order diffraction
as the elastomer is subjected to strain levels ranging from 0 to 8%. Diffraction
is observed with a P-polarized beam at normal incidence on a point at the
center of the grating. Figure 7 illustrates the behavior of diffraction angle vs.
% strain. For this strain interval, a diffraction angle range = 2.3o is
87
achieved by a 2 mm elongation of the grating. Experimental results follow Eq.

(6) for = 632.8 nm and = 0 with = 0.62. For reflection geometries,
grating efficiency may be improved by coating the transparent elastomer
replica with a metal thin film such as Au. Improvement in diffraction
efficiency due to the metal coating, however, decreases with increasing strain.
Spontaneous buckling structures appear on the thin film surface in response to
elongation, leading to reflectivity loss and secondary diffraction effects [11].
Diffraction angle (deg)
50.5
50
49.5
49
48.5
48
47.5
47
46.5
0
% strain
Figure 7. Variable diffraction with an elastomer grating as a function of strain. At

normal incidence, the diffraction angle ranges from 49.8o to 47.5o within a strain
interval of 8%. The solid theoretical curve is based on a linear change in grating pitch
as strain increases.
DIFFRACTION FROM A BIOMIMETIC

ELASTOMER GRATING
Soft lithography has recently received much attention as a fabrication
method in the emerging field of biomimetic engineering. In biomimetics,
useful properties of biological systems serve as precursors to improved manmade designs [12]. Future applications involving advanced optical materials
may be based on the ingenuity of natural photonic structures [13]. As a means
of synthesizing biomimetic elements, soft lithography is a viable alternative to
cumbersome techniques such as electron-beam etching [14], and the use of
nanostructured templates [15].
88
Raphael A. Guerrero
(a)
(b)
Figure 8. Soft lithography of a beetle surface: (a) the ventral side of C. cobaltina is
employed as a biomimetic template; (b) surface features on the transparent elastomer
replica are inverted after the casting process. Elastomer casting cannot replicate the
iridescent coloration on the original beetle carapace.
Elastomeric casting of the ventral side of the beetle Chrysochroa

fulminans cobaltina, a member of the order Coleoptera native to the Philippine
89
archipelago, is carried out via soft lithography [16]. Figure 8a is a photograph

of the plexiglass mold custom-made to accommodate the shape of C.
cobaltina. The beetle is positioned with the ventral side exposed just slightly
above the bottom surface of the mold. Glue is applied to fix and seal the
specimen in place. PDMS is again used for the casting process. Liquid silicone
is poured into the mold so that the beetle is completely covered and curing
time is 6 days at 25 oC. Care is exercised in extracting the cured elastomer
layer due to the intricate nature of the beetle surface. The transparent
elastomer replica takes on the main features of the beetle specimen (Figure
8b). Replication with soft lithography is limited to surface features and the
elastomer cast does not have the iridescent coloration of the original surface
since silicone cannot penetrate the interior of the beetle scales [17]. In Figure
9, optical microscopy of the replicated surface reveals periodic microstructures
consisting of closely-packed hexagonal scales, perfectly copied off matching
features on the actual beetle carapace. The scales are arranged in a step-like
fashion, with elevation of approximately 1 m, following a rough periodicity
with an average spacing of 13.2 1.7 m [16]. As a result of the single-step
casting process, replicated features are three-dimensional complementary
structures with elevated regions on the beetle carapace copied as depressions.
Periodicity of the structures remains the same despite the surface inversion.
Figure 9. Periodic microstructures on the biomimetic elastomer cast. The hexagonal

features are faithful replicas of structures found on the original insect surface.
Horizontal direction in the image is along the beetle long axis.
90
Raphael A. Guerrero
Differences in elevation between steps provide a periodic refractive index

modulation at the air/elastomer interface. The repeating surface morphology
may be immediately exploited to observe diffraction effects. With the
elastomer cast mounted as a transmission grating, a far-field diffraction pattern
(Figure 10) may be generated with a laser beam at normal incidence to the
sample. Distribution of intensity among the diffraction orders is largely
dependent on the groove profile. The limited extent of diffraction orders is
attributed to low depth modulation of the step-like grooves. Inherent
limitations of the original biological template, including surface roughness and
uneven groove edges, contribute to significant scattering effects. Applying the
grating equation for normal incidence at = 488 nm, measurements of
diffraction angle for the 1st-order bands result in an average groove spacing of
13.6 m, consistent with pitch values determined through optical microscopy.
Diffracted intensity profiles may be approximated by the Fourier transforms of
aperture distributions based on the replicated microstructures [16].
Figure 10. Far-field diffraction pattern produced by the biomimetic elastomer cast with
a laser beam at normal incidence.
91
SHAPE MEMORY ACTUATION OF AN

ELASTOMER GRATING
The versatility of elastomeric optics depends on effective actuation
methods. Current technologies make use of artificial muscles [18],
piezoelectric actuators [19], and shape memory alloys (SMAs) [20]. SMAs
have the ability to recover their original shape upon heating after being
mechanically deformed at a lower temperature. The underlying mechanism is
a phase transformation between rigid high temperature austenite and compliant
low temperature martensite [21]. Soft lithographic fabrication of an elastomer
grating with an embedded SMA wire leads to a tunable grating that
cylindrically bends when heat is applied to the SMA. The change in curvature
may be used for beam deflection as well as color displays.
Body temperature nitinol wire is employed as the SMA actuator. The wire
has length = 100 mm with cross-sectional radius = 0.25 0.04 mm. Critical
actuation temperature for the SMA is rated by the manufacturer at an upper
limit of 40 oC. Initially, the wire is trained into a curved shape and annealed at
500 oC in a pre-heated furnace for 15 minutes. After heating, the wire is
quenched in water. Mechanical deformation is performed by straightening the
wire. The SMA is expected to return to the annealed curvature upon heating
above 40 oC. Previously discussed steps are followed in preparing the
elastomer grating via soft lithography, only with the additional stage of
immersing the SMA wire within the PDMS while the replica is curing.
Figure 11a is a photograph of the grating replica with an installed SMA
wire. The grating area is coated with a thin metal film to improve diffraction
efficiency. Actuation of the elastomer grating in response to resistive heating
by an applied current of 1.5 V is seen in Figure 11b. A DC power supply
operating at 10 V provides a fixed current to heat the nitinol wire until a
steady-state curvature is reached. Recovery of strain due to the shape memory
effect in response to increasing temperature causes the nitinol wire to curve
within the elastomer. Curvature of the grating is modified and dynamic
diffraction is enabled by a shift in the grating normal.
1st-order diffraction angle as a function of applied current is plotted in
Figure 12. Incident angle is approximately 3o. Within the current range of 0 to
2.5 A, the diffracted beam sweeps from a diffraction angle of 45o to 30o. The
angular range achieved with SMA actuation is larger than the deflection
reported for artificial muscles and at a much lower applied voltage [18].
Beyond 2.0 A, larger values of current no longer affect the wire as the SMA is
92
Raphael A. Guerrero
now primarily in the austenite phase. Response time of the SMA at 2.0 A is 5
seconds [20], suggesting viability of the deformable grating as a moderatespeed scanning element. Once heating is stopped and the SMA is allowed to
cool, the original diffraction angle is recovered after a few minutes.
Relaxation of the grating during cooling is assisted by the elastomer restoring
force.
(a)
(b)
Figure 11. A nitinol wire embedded within the grating replica provides shape memory
actuation: (a) 0 applied current; (b) 1.5 A creates sufficient resistive heating to change
the grating curvature.
Diffraction angle (deg)
48.00
44.00
40.00
36.00
32.00
28.00
24.00
0.0
0.5
1.0
1.5
2.0
2.5
3.0
Current (A)
Figure 12. Change in diffraction angle as a function of applied current. Steady-state

actuation for the SMA is achieved with 2.0 A.
93
Normaliz edreflec tanc e
Tunable diffraction gratings function as natural color display elements

with wavelength selectivity over the entire visible range [18]. The SMAactuated elastomer grating shares this capability. When a collimated white
light source is directed at a fixed angle of incidence onto the grating surface,
diffracted color spectra may be projected onto a screen. Figure 13 plots
reflectance of the elastomer grating for varying levels of current at fixed
incident and viewing angles. The entire visible spectrum is reproducible with
the elastomeric grating [22].
1
0.8
0.6
0A
0.4
1.0A
0.2
1.5A
0
350
450
550
650
750
Wav eleng th(nm)
Figure 13. Normalized reflectance of an SMA-actuated grating for different current

levels. Spectra are measured at a fixed viewing angle.
CONCLUSION
Soft lithography has served as the fabrication protocol of choice for
several applications involving diffractive optics.
Multiplexed volume
holographic storage may be implemented with an elastomer phase mask that
demonstrates high selectivity. Dynamic diffraction gratings imprinted on an
elastomer substrate show potential as real-time beam-scanning elements with
large angular deflections. Functional biomimetic diffractive elements may be
fabricated with a single-step soft lithographic process. White light dispersion
from an elastomer grating actuated by a shape memory alloy is applied as a
selective color display.
94
Raphael A. Guerrero
Continuing work on soft lithography of optical

the low production costs, versatility of design and
possible by elastomeric replication procedures.
numerous materials applicable to soft lithographic
elastomeric optics holds much promise for new
innovation.
elements is motivated by
ease of fabrication made
With the availability of
techniques, the future of
applications and further
REFERENCES
[1]
Calixto, S. Appl. Opt. 2002, 3, 3355-3361.
[2]
Simonov, A.N., Akhzar-Mehr, O., Vdovin, G. Opt. Lett. 2005, 30, 949951.
[3]
Rogers, J. Jackman, R., Schueller, O., Whitesides, G. Appl. Opt. 1996,

35, 6641-6647.
[4]
Liu, B. Wang, M., He, Y., Wang, X. Langmuir 2006, 22, 7405-7410.
[5]
Lyutakov, O., Huttel, I., Siegel, J., Svorcik, V. Appl. Phys. Lett. 2009,
95, 173103.
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Sun, M., Luo, C., Xu, L., Ji, H., Ouyang, Q., Yu, D., Chen, Y. Langmuir
2005, 21, 8978-8981.
[7]
Guerrero, R. Opt. Commun. 2005, 245, 75-83.
[8]
Yeh, P. Introduction to Photrefractive Nonlinear Optics; Wiley: New

York, NY, 1993.
[9]
Tschoegl, N. The Phenomenological Theory of Linear Viscoelastic

Behavior; Springer-Verlag: Berlin, 1989.
[10] Sun, C., Su, W. Appl. Opt. 2001, 40, 1253-1260.

[11] Guerrero, R., Barretto, J., Uy, J., Culaba, I., Chan, B. Opt. Commun.
2007, 270, 1-7.
[12] McPhedran, R., Nicorovici, N., McKenzie, D., Rouse, G., Botten, L.,
Welch, V., Parker, A., Wohlgennant, M., Vardeny, V. Physica B 2003,
338, 182-185.
[13] Galusha, J., Richey, L., Gardner, J., Cha, J., Bartl, M. Phys. Rev. E
2008, 77, 050904.
[14] Parker, A., Townley, H., Nature Nanotech. 2007, 2, 347-353.
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[15] Li, Y., Cunin, F., Link, J., Gao, T., Betts, R., Reiver, S., Chin, V.,
Bhatia, S., Sailor, M. Science 2003, 299, 2045-2047.
[16] Guerrero, R., Aranas, E. Mater. Sci. Eng. C 2010, 30, 1170-1174.
[17] Kang, S. Tai, T., Fang, T. Curr. Appl. Phys. 2010, 10, 625-630 .
[18] Aschwanden, M., Stemmer, A. Opt. Lett. 2006, 31, 2610-2612.
[19] Wong, C., Jeon, Y., Barbastathis, G., Kim, S. Appl. Opt. 2003, 42, 621626.
[20] Guerrero, R., Sze, M., Batiller, J. Appl. Opt. 2010, 49, 3634-3639.
[21] Otsuka, K., Wayman, C. Shape Memory Materials; Cambridge
University Press: Cambridge, 1998.
[22] Guerrero, R., Sze, M., Batiller, J. Proc. SPIE 2010, 7788, 77880B.

c 2012 Nova Science Publishers, Inc.
Editors: J. Balcazara, E. Paules

Chapter 5
O PTICAL S PECTRA OF C HIRAL

E LASTOMERS D URING S EGREGATION AND
E LASTIC P ROCESSES
J. Adrian Reyes1 , Laura O. Palomares2 and Carlos G. Avendan o3
1
Universidad Autonoma Metropolitana
Ixtapalapa, Apartado Postal 55 534 09340,
Mexico D. F., Mexico
2
Instituto de Fsica,
Universidad Nacional Autonoma de Mexico,
Apartado Postal 20 364 01000,
3
Universidad Autonoma de la Ciudad de Mexico,
Av. La Corona No. 320, Col. La Palma, C.P. 07160, G. A. Madero,
Abstract
Chiral elastomers (CEs) are rubbers formed by monomers of liquid
crystals weakly cross-linked to polymeric chains, this union produces a
flexible material whose molecular order is similar to cholesteric liquid
On leave from Instituto de Fsica, Universidad Nacional Autonoma de Mexico, E-mail address: adrian@fisica.unam.mx
98
J. Adrian Reyes, Laura O. Palomares and Carlos G. Avend

crystals with the advantage that in this new material the responses to external stimuli are exceptionally large [1]. These stimuli could be mechanical, thermal, and electromagnetical with elastic and optical responses,
giving rise to a wide range of applications such as artificial muscles, optical fibers, resonators and optical filters. In this chapter we focus in optical
responses due to changes induced into the material by means of macroscopic deformations and chemical segregation processes due to their interesting applications.
CEs, just like cholesteric liquid crystals [3] and chiral sculptured thin
films [4], are structurally chiral materials that display the circular Bragg
phenomenon (CBP) whereby a normally incident, circularly polarized
plane wave of a specific handedness is highly reflected in a certain wavelength regime, whereas a similar plane wave but of the reverse handedness
is transmitted. This polarization-discriminatory filtering characteristic of
structurally chiral materials is very attractive in optical technology [5].
Additionally, materials with helical symmetry are unique periodic structures whose optical properties can be defined by equations which, for
axial light propagation are exact and very simple, this analytical expressions give remarkable insight on the phenomena. Another outstanding
property of CEs is segregation, which in fact is the ability to absorb and
retain preferably left- or right-chiral molecules from a racemic solvent.
Mechanical stress in CEs make feasible to control the optical properties for tunning the CBP and switching applications with the potential additional application of optical monitoring the chiral pump when the
chemical segregation process is considered.
Here, we revised in detail the representation of Marcuvitz-Schwinger with the transformation of Oseen, to calculate the band structure,
transmittance and reflectance co-polarized and cross-polarized spectra of
chiral-elastomer slabs. We study the modifications on optical spectra and
band structure due to the action of some external agents. When an externally induced mechanical strain is applied parallel to the helical axis,
the analysis of remittances shows the possibility of mechanically control
the CBP for which the bandwidth and the central wavelength are significantly modified. Thus, the reflection band blue-shifts versus the incidence
angles, as happens in absence of strain [6]. On the other hand, if an uniaxial transverse stress is applied on the slab, there exists a left-circularly
polarized thin reflection band immersed in a wider right-circularly polarized band reflection when the elastomer is under a stress near to the
critical value. These band gap features suggest to design a finely tuning
polarization-universal optical filter [7]. Moreover, when a CE is immersed
Optical Spectra of Chiral Elastomers . . .
99
in a racemic solvent, there is a significant width reduction of the reflection

band for certain values of nematic penetration depth, which depends on
the volume fraction of molecules from the solvent, whose handedness is
preferably absorbed. The appearance of nested band gaps of both handednesses during the sorting mixed chiral process is also obtained. This
suggests the design of chemically controlled optical filters and optically
monitored chiral pumps [8].
1.
Elastomers with Liquid Crystal Structure
Elastomers are elastic systems which uniquely combines, three important properties: orientational order of large range in amorphous soft materials, macroscopic susceptibility to the molecular shape, and quenching to the topological constraints. Classical liquid crystals are fluids typically composed by rigid
molecules, which with a continuous model , are represented by bars and exhibit
an orientational order of large range. The simplest order displayed by these
systems is the nematic for which all the molecules are aligned in average. Complementary, the polymeric long chains embodying anisotropic rigid units can be
nematically aligned and may form polymeric liquid crystals (PLC).
However, the long chains are elongated when theirs rigid monomeric components are oriented giving rise to an anisotropic material. If additionally, the
polymeric chains are joint to a backbone in such way that their topology is
restrained, hence the melt condenses in a very elastic solid or rubber. It is convenient to mention that in general, within the rubbers, the nematic monomeric
molecules retain the same mobility as in a liquid phase.
Theses soft constrictions made the resulting material, which is then a solid
one, to be very extensible. Rubbers resist mechanic deformations since the
polymeric chains reach their maximum entropy when they stay in their natural state without deformation. The polymerization of these compounds creates
links between the chains which joint to the backbone formed collectively among
themselves.
It is to be expected that in this process the anisotropic rigid units of nematic
character, for instance, nematogens, which lie in the inner of the medium, form
spontaneously domains distributed in all the rubber, whose preferred orientation
is to be in different directions. This variety of domains causes light scattering
giving rise to a macroscopic turbid appearance to the material. One very im-
100
portant advance in the design of these materials was managed by Finkelman, by

developing a procedure for obtaining samples which form a single domain. The
basic idea consists in applied electric field to the melt substance in order to align
the anisotropic monomeric units while the polymerization is taking place and/or
the temperature is decreased to maintain the orientational order of the oriented
nematic elements and in turn attain a monodomain.
A material prepared in this way is called as a liquid crystal elastomer and
has the amazing property of being deformable, within certain interval of elongations, investing in this a practically negligible amount of energy. This is caused
essentially by the reorientation and accommodation of the anisotropic structure
formed by the rigid nematic monomers or other mesophases in the inner of long
polymeric chains while the material is distorted in such way that the energy
utilized is minimized when the mention structure turns.
Nowadays the liquid crystal elastomers are synthesized to generate phases
in the same variety obtained with classical liquid crystals. It can be created
nematics, smectic and chiral liquid crystals. Similarly to any polymeric rubber,
the materials are very deformable since their dimensions can be changed under
the influence of external stresses as much as 300% of their original sizes. They
can be easily oriented by electrical fields as the ordinary liquid crystals. Both
features make of these new materials excellent candidates to design artificial
muscles. On the other hand, their transparency in the monodomain phase and
the fact that as solids do not require a container to be used as electro optic
devices.
2.
2.1.
Polymers
Polymer configuration
A polymer is a very long chain formed by many repeated molecular units, as

much as thousands, called monomers. All polymeric chain posses a characteristic length l, at which the chain can be bent. This length can contain various
monomers when the total number of monomers in the chain N is much larger
than the number of monomers per length l and then we can affirm that there
exist various possible spatial configurations for the polymer. Thus, it is possible
to employ a Gaussian distribution to describe adequately the system. Here we
101
shall assume that this is the case.

A chain composed by N bar of length a freely joint like the one shown in
fig 1 is statistically equivalent to the path of a random walk with fixed step a.
The average mean square of the end to end vector ul formed after this walk of
N steps [1]
hR2x i = hR2y i = hR2z i =
1
1
1 2
hR i = a2 N aL,
3
3
3
(1)
where L = N a is the total length of the chain. In terms of the end to end
vector which joint the monomers ui of length a, the distance between the two
edges of the chain is given by the magnitude of the vector: R = i ui . This
quantity is very important since provides a notion of the spatial configuration of
the polymer chains and from the polymer chain distribution we can derive the
free energy characterizing the system. The vectors ui are not correlated each
other so that hui uj i = ij a2 which is consistent with Eq. (1)
Figure 1. A linear chain of polymer is similar to a random walk. R is the vector

joining the start and end of the chain.
A polymer is a thermodynamical system in equilibrium interacting with its
surrounding at volume and temperature constants. Hence, the total number of
102
possible conformations of one given chain ZN (or the number of possible random walk without restrictions) must be equal to the partition function of the
chain: ZN = conf ig eH/kT , where H is the energy of the configuration, k
is the Boltzman constant and T is the temperature. If we know take a random
walk for which the two ends of the walks are fixed, we expect that the number of
possible configurations is to be smaller than that of the system just mentioned.
us the number of configurations for fixed boundary conditions is given by
ZN (R) = pN (R)ZN ,
(2)
where pN (R) is the probability of having a configuration with an end to end

vector R Since ZN is the partition function of the system, the probability of
distribution must be Gaussian and as a consequence its explicit normalized expression is given by [9]:
3/2

2
2
3
e3R /2Ro ,
(3)
pN (R) =
2R2o
where Ro is the variance of the system and from Eq. (1) we get R2o = aL.
The fact that the polymer chain is kept at volume and temperature constants
allow us to use the Helmholtz free energy to describe the system which in agreement with the statistical physics is given by
F = kB T lnZN (R);
substitution of Eqs. (2) and Eq. (3) in the latter equation, yields
2
3R
F (R) = Fo + kB T
+ C,
2R2o
(4)
(5)
where Fo = kB T lnZN is the free energy of the polymeric chain without restrictions in their ends and C is the constant coming from the normalization of
the distribution pN . Fo and C are constants independent of R, which only determine the reference point, thus their values are irrelevant to find the minimum
of the free energy of the system. We remark that the energy given in Eq. (5)
is purely entropic since only depends on the number of possible configuration
of the systems. To obtain this expression we assume that all the possible configurations contribute with the same energy and we neglect the chemical energy
103
caused by the electromagnetic repulsion between the molecules. if we take into

account the internal energy associated with chemical processes, U (R), the free
energy of the system is given by F (R) = U (R) T S(R),where the entropy
per molecule is represented by S(R). Strictly speaking, this term should be
considered however it has been shown that the entropy [1] dominates the free
energy and then we can neglect it.
S(R) = kB
3R2
2R2o
(6)
A polymeric liquid crystal PLC combines the spontaneous orientation of

the liquid crystals with the elasticity governed by entropy discussed above. It is
necessary a delicate balance in these properties to create a PLC.
2.2.
Polymeric Liquid Crystals Shape
The average shape of the polymeric main chain is crucial since this is responsible of the equilibrium elastic response of the network it belongs. Some ordinary
polymers are isotropic or spheric so that only one dimension is enough to characterize these materials. In contrast, the nematic polymers may adopt diverse
shapes due to the fact that the average backbone is distorted by the reorientation
suffered by the molecular bars guided by the director n, that is the nematic order modifies the backbone form of the polymer. Hence, nematic polymers more
than one direction to describe their anisotropic form.
To characterize the chain form and its probability distribution the quadratic
mean square of shape is given by
1
hRi Rj i = lij L,
3
(7)
where we have defined lij as the effective length steps in distinct directions. For
uniaxial polymers hRiRj i, is the same for every perpendicular direction to n.
Thus, if n is along the zaxis, we have Rx = Ry = R , and the tensor l for
this case is
l 0 0
lo = 0 l 0
(8)
0 0 lk
104
where l and lk are the length steps sin the directions parallel and perpendicular
to n, respectively. For the general case for which n is not necessarily aligned
with with one of the axes of our reference system, the matrix l is not necessarily
diagonal but uniaxial and has the form:
lo = l + [lk l ]nn.
(9)
Let us define the radius r, as the ratio between the effective length steps
l
parallel and perpendicular as: r = lk . Using the latter equation, we can express
the tensor lo , Eq. (9) as:
lo = l ( + [r 1]nn)
and
l1
o

1
1 nn).
= l ( +
r

(10)
(11)
If r > 1, means that we have a prolate backbone, which is larger along the
direction n; Instead for r < 1, we have an oblate, whose backbone is larger in
perpendicular plane to n (see Fig. 2).
Figure 2. Nematic polymer backbones: oblate and prolate.
105
The probability of find a configuration with end to end vector: R, Eq. (3).
On the other hand the probability of find certain configuration for the anisotropic
case, is obtain by using Eq. (1) from which it can be derived, R2o = lij L and
R2 = Ri Rj . Substituting these expressions in Eq. (3), we get the probability
for the anisotropic case:
p(R) =
3.
"
3
2L
3
1
Det[l]
#1/2
1
3
e( 2L Ri lij Rj ) .
(12)
Rubbers Elasticity
Let us consider a long polymeric chain whose more common features are coming from its resistance to be distorted from certain average shape. The entropy
of only one thread Eq. (6) diminish as the distance between their ends increases.
In reducing the number of conformations the free energy of the rubber increases.
A simple rubber without cross-linking would be a melt polymer which eventually will flow under the action of a shear strain. Having relatively a few
number of monomers which are locally constrained by cross-linking,the chain
continue retaining a great mobility and can explore a large quantity of proper
conformations of such a fluid.
A rubber is a liquid in every sense except for the fact it cannot flow. similarly
as for the case of an individual thread discussed above, the whole rubber resists
to the changes in its average shape which implies that a given end to end vector
connecting a pair of chain will be deformed in geometrical proportion to the
body distortion (affine deformation approach).
If Rf represents the the end to end vector corresponding to certain chain,
hence the deformation defined as
R = Rf
(13)
where R is the new value of Rf after suffering a deformation. For instance, if a

rubber whose shape is a parallelepiped, is deformed by the factors xx , yy and
zz in the directions x, y and z respectively in such way that there are no shear
106
strains. Under circumstances is given by
xx 0
0
= 0
yy 0
0
0
zz
(14)
The energy of this particular thread is given by Eq. (5), thus upon substitution
of this expression we get
!
3Rf T Rf
,
(15)
F (R) = kB T
2R2o
where we have neglected the additive constants. In this way the actual energy
depends on the deformation and on the initial separation between end to end
Rf . The complete free energy of a rubber block joints all the contributions
of this type cause by every thread of the rubber. Each different thread has its
own vector and the proportion of threads with certain vector Rf is given by Eq.
(3). Thus, the sum of free energies of individual threads in the distorted body
is equivalent to averageF on their distributions and in turn, to multiply the free
average energy per resulting thread, by the total number of threads in the system
per unit of volume ns . Therefore the average free energy per thread is given by
F =
=

3kB T
Rf T Rf p(R )
2
f
2Ro
Z
2
2
3kB T
Rf T Rf e3R /2Ro d3 Rf ,
2
2Ro
(16)
where we have assumed that the average size of chain in formation is Ro which
is the same than the actual one of the distorted rubber and only can change by
varying the temperature. If we take into account the identity hRiRj i = R2o ij /3
then, F = ns F reduces to the expression
F
=
=
T r( T )
2
2
2
2
( + yy
+ zz
)
2 xx
(17)
where = ns kB T is the shear elastic modulus which of the order of 109

1010 J/m3 . Thus, the energy associated to the entropic effects of a rubber is
107
negligible in comparison with that of volume changes. For this reason we shall
assume that the rubber distortions occur by keeping the volume constant. If
we assume this and the deformation is described by Eq. (14) then the rubber
volume can be calculated from the determinant of given by
Det [] = xxyy zz = 1
(18)
which in this case we have assumed a unit volume of the sample. Thus, if
we enlarge the rubber in the zdirection by the factor = zz and allow the
dimension in the other dimensions to be simply determined by the restriction of
constant volume then we have xx = yy = 1/ (see Fig. 3). From this we

can deduce the free energy by inserting these expressions in Eq. (17) to obtain
F =
2 2
( + ).
2
(19)
where the upper order corrections are caused by changes in the volume and
can be neglected taking into account the constriction Eq. (18). The energy
density as function of the elongation determines the force per unit of area as the
deformation is imposed. The force fz acting on and the extreme located in the
positive z-axis of the body is obtained multiplying the change of the energy by
the transverse area in the zdirection:

F
1
fz = A
= 2 .
z
The polymeric structures forming the rubbers are systems complex. The
model considered here does not take into account the interaction among the
chains and the limited extensibility of each chain.
3.1.
Nematic rubbers elasticity
Nematic elastomer systems can be quite elastic, that is they can be extended or
compressed for large proportions. The difference between nematic and isotropic
rubbers is the molecular shape anisotropy induced by liquid crystal order. The
most simple description of nematic rubbers is arising from extension of the
molecular theory of rubbers just discussed in the foregoing section and is known
as the neoclassic theory.
108
Figure 3. Deformation of an isotropic rubber.
The number of configurations in one thread connecting two cross-linkings

separated by a distance R in one nematic rubber is proportional to the anisotropic Gaussian distribution given by Eq. (12). As before, let us consider that
a total deformation t affine leads from the formation state Rf to the actual
situation R = t Rf . The free energy, is obtained by averaging over a ensemble
of initial condition whose energy of formation are the same
F
= kB T hln p(R)i p0 (Rf )

=

3kB T
1 kB T
Det[l]
Rl R +
ln
2L
2
a3
(20)
the term in Det[l] is due to the normalization factor containing the information
of the nematic order by means of the step length tensor l. The free energy can
109
be rewritten as

3kB T
Rf T l1 Rf p + .
(21)
0
2L
The average over the set of formation states can be performed directly using
the relation hRf Rf i p0 (Rf ) = loL/3, so that the average energy per thread is
finally

kB T
kB T
Det[l]
T 1
F=
T r lo l +
ln
.
(22)
2
2
a3
This expression is a generalization of the classical free energy for the elasticity for a thread Eq. (17) for which is known as the neoclassic free energy.
To obtain the whole free energy of the rubber we need to count the number of
threads per volume ns , that is F = ns F and since the linear shear modulus of a
rubber is = ns kB T. The free energy density is given by
F = T r lo T l1
(23)
2
This expression is valid for all the deformation, including the larger ones,
but it cannot describe those deformations which can stretched totally the polymeric chains. This expression involves the orientational information about the
initial state n0 and actual state n of the elastomer by means of lo and l. By
contrary the free energy of ordinary nematic liquid crystal only depends on the
actual state of distortion. Eq. (23) exhibits a more complex structure than that
of the classical formula Eq. (17) since the distortions appear expressed in terms
of the combination T l1 suave.
F=
4.
Soft Elasticity
Elastomer have internal freedom degree which is the director rotation and give
rise to peculiar properties as spontaneous distortions, instabilities and deformations of low energy cost. The signature point is that the variation of the director
allow to obtain a meaningful reduction in the elastic energy invested to cause
certain distortions. This phenomenon has been originally discovered by Warner
[10], by using a direct minimization of Eq. (23) under constriction circumstances.
Let us consider first the director turns an angle with respect to the axis y
which can be managed by applying obliquely either an electric or magnetic field
110
n0 . The same can be obtained if the rubbers turns instead while the director is
clamped. the free energy density by taking = takes the form
1
T r(lol1 )
(24)
2
where, by neglecting the changes in the order tensor, we get the current step
length tensor l which is the result of the rotation of the initial tensor lo by an
angle , that is
l = UT loU
(25)
Fel =
Hence, we take l = l ( + (r 1)no no ) where r = lk is a measure of the

anisotropy of spheroidal shape chain. Similarly the inverse tensor is l1 =
( (1 1/r)nn)/l where (1 1/r) provides a negative deviation departing
from a sphere. Substituting in Eq. (24) we get
3
1 (r 1)2
Fel = +
sin2
2
2
r
where no n = cos which for small values of reduces to
(26)
1 (r 1)2 2 D1 2
=
.
2
r
2
The coefficient D1 gives the elastic cost to perform small rotations of the director with respect to the rubber. Notice that as the rubbers tends to be isotropic,
r 1 when the value of D1 vanishes, as should be expected. It should be
remarked that both, prolate (r > 1) and oblate (r < 1) elastomers increase their
energy by rotating their chain with respect to the rubber.
Fel '
4.1.
Coupling between pure shear deformations and rotations
We shall apply a pure shear deformation of amplitude to a nematic elastomer

in the plane where the director n lies. This deformation is represented by a local
combination of extension and compressions and as a result induces directors rotations in the diagonal direction. The pure shear deformation tensor preserving
the volume is given by

1 + 2
(27)
=
1 + 2
111
since Det = 1. If we substitute Eq. (23) where

l and lo are defined as above,
then we can write as a dyad, that is = 1 + 2 (xx + yy) + (xz + zx)

and we have therefore
Fel

r1
1
1 + r + 2(r + 1) 2
(r (r 1) sin2 )(1 + 2 )
=
2
r

p
+ 1 + (r 1) sin2 ) 2 + 2(1 + r) 1 + 2 sin cos . (28)
If we now expand this expression up to second order in and , we can identify

the coefficients as follows
1 (r + 1)2 2
= 4C5 2
2
r
1 (r 1)2 2
= 4D1 2 /2
2
r
1
(r ) = D2
r
(29)
(30)
(31)
The term D1 introduced above, refers to the energy associated to directors

rotations with respect to the rubber. There exists also a term corresponding
to symmetric shear deformations in the no plane which do not vanish for the
isotropic case r 1. finally, the coupling term between rotation and shear deformations is quantify by the constant D2 = (1 r 2 )/r which as expected,
is null in the isotropic limit. Even more, this term has different sign for prolate
and oblate chains by contrast with the behavior of D2 which is always positive.
This implies that the induced rotation direction of by certain must be opposite between prolate and oblate polymers. As a consequence the term D2
may assume a negative sign by adequately choosing the sign of . Thus, in despite of having positive contributions of C5 2 and D1 2 , the term D2 offers a
mechanism for diminishing the elastic energy employed in distortion (see Fig.
4). Indeed, as we shall see in next section, even for large deformations, this
contribution may cancel completely the other contributions to result in a null
total energy necessary to deform a nematic rubber.
112
4.2.
Goldstone mode
Let us consider the deformation represented by the following expression whose

justification for its explicit form is not evident so far,
= l1/2 W lo1/2 .
(32)
where W is one arbitrary rotation by the angle . The chain in their current and initial state are specified by their respective step length tensors l and
lo which in turn are characterized by their directors n, no and order parameters Q and Qo . If we take into account the rotations transforming no in n
and those described by W , this represents a great amount of potential distortions. By inserting this expression into Eq. (23) and its transpose matrix
1/2
T = lo WT l1/2 . we get, using the fact that l is symmetric:
Fel =
=
1
1/2
1/2
T r(lo l1/2
WT lo1/2 l1
)
o
o lo W lo
2
3
1
T r() = .
2
2
1/2
1/2
(33)
which is equivaNotice that the central part of this expression is lo l1

o lo
lent to the unit matrix by definition. Thus, W is multiplied by its transpose
matrix to be reduced to the identity matrix. Similar reductions are valid for
the terms involving the tensor lo which leads to the final result Fel = 3/2,
which is identical to the free energy of a rubber without distortions. We can
conclude that the energy does not differ from the undistorted energy, for set of
distortions involved in definition. An illustrative diagram of this situation is
displayed in Fig. 4) in which an extension is applied in the perpendicular direction to the initial director. This causes that the chains distribution rotates and
accommodates itself turning to the direction in which the elongation is applied.
Other features of this deformation are the following. i) All the distortions originated by the imposed extension zz remain in the rotation plane. That is, only
a transverse contraction is present xx and a shear deformation xz but distortions along y are not necessary. ii) Softness of the elastomer finishes when the
chain rotation
q is complete and the z dimension z has diminished in the proportion zz = l /lk , whereas the dimension x has been extended by the factor

xx =
lk /l . That is, the original dimensions of the rubber

p
were transformed in l and lk , respectively.
113
p
lk and
Figure 4. Schematic plot of the goldstone mode for which the necessary energy
for distortion is null.
Since the directors rotations occur by changing the shape of the rubber
there are no entropic expenses to deform the chain distribution of the rubber by
contrast to what occurs upon deformation of conventional elastomers. Observe
that in the isotropic limit (r = 1) both step length tensors l and lo turn out to be
the identity matrix, and as a consequence the soft deformation matrix Eq. (32)
is simply an arbitrary rotation. Of course, there is no energy expense when the
sample turns as a whole and thus the modes are relevant only when the material
is nematic.
5.
Chiral Elastomer under an Axial Deformation
Let us consider a cholesteric elastomer submitted to distortion along its chiral

axis, which in this case we chose to be the zaxis, as shown in Fig. 5.
The deformation tensor, in its simplest, can be expressed as [1]:
xz
0
1
(34)
= 0
yz ,
0
0
where we have simplified the notation by the convention zz = , as we discussed above, to keep the volume fixed , it is necessary to ask for Det= 1,
114
Figure 5. Cholesteric elastomer configuration axially distorted.

which is straightforwardly fulfil by this expression since Det= 1 1 = 1.
The terms xz and yz , are coming from the fact that we allow the director to
rotate in the plane xy which will be modified by expanding the elastomer along
the z-axis.
The initial elastomer vector without deformation is given by: no =
(cos qo z, sin qo z, 0), after the deformation, the director will be rotated by the
angle = 2 , in such way that it lies over the surface of a cone Fig. 5; the
new vector after deformation can be expressed as
n = (sin cos qz, sin sin qz, cos ),
(35)
where q = qo / is the new helix wave number scaled by the strain ; the initial
step length vector without deformation, lo, is defined in agreement with Eq. (10)
in terms of no and the inverse tensor is similar to Eq. (11) by interchanging the
vectors n and no we have introduced.
The Helmholtz free energy of the system is given by Eq. (23) in terms of lo ,
Eq. (10) and l1 , Eq. (11). Upon expansion of the Helmholtz free energy we
115
F = xT Ax + bx + c
(36)
can express this as

where
x = {xz , yz },
A=
1+3r+(r1) cos 22(r1) cos 2qz sin2

4r
(r1) sin 2qz sin2
2r
b = {
(r1) sin2r2qz sin
1+3r+(r1) cos 2+2(r1) cos 2qz sin2

4r
(r 1) cos qz sin 2 (r 1) sin qz sin 2

,
}
r
r
and
3 + r(3 + r + 3 ) + (r 1)(r 3 ) cos 2

.
2r
Eq. (36) represents the free energy of our system; it contains the information
of the deformation. To find the state of deformation after a relaxation it is necessary to find the minimum of the free energy. When we extend an elastomer,
first the strains are relaxed and after that the molecules will reorient. The minimum of energy is found by searching the values xz and yz which minimize
the energy and then the optimum value of .
To this purpose, we find the minimum with respect to xz and yz by diagonalizing the matrix A and translating to the principal axes system of the
0
0
deformation (where we have denoted the strains by: xz yz ). Using the fact
the the minimum of systems energy is the same in any frame. Once doing this
we find
c=
2
1
0
1
r
02
F = 2 + + yz2 ([r + 1 + (r 1) cos 2]( 2 xz
)
2r
0
+ 2(r 1)xz
sin 2 2 2 . (37)
0 = 0 and
minimizing this free energy with respect to the strains: yz
0
xz
=
(r 1) sin 2
.
(r + 1) + (r 1) cos 2
(38)
Substituting these optimum values of the strains in the free energy density Eq.
(37), we have:

1
2 2
3 + r + 1 + (r 1) cos 2
F =
+
. (39)
2
r + 1 + (r 1) cos 2
2
116
It remains to know the value of minimizes the latter expression. The director
vector n will incline towards the z direction with an angle (see Fig. 5) after
the deformation, to find the value of , we minimize the free energy Eq. (39)
we respect to , we get:
s
3/2 1
.
(40)
() = arcsin
r1
The latter equation indicates which is the degree of reorientation of the

cholesteric, the maximum deformation is reached when the director vector aligns
totally parallel to the z-axis, that is, when = 2 , we find that = r 2/3 ; when
there is no deformation = 1 and = 0.
5.1.
Imprinted cholesteric elastomers
Let us consider elastomers imprinted with chiral structure, but without chiral
molecules, in the complementary sense from intrinsic cholesteric elastomers.
Director rotations are now not submitted mechanically, but by the requirement
to diminish Frank elastic energy. A simplest approach, avoiding compatibility
problems generating expensive extra distortions, is not to allow any distortions
at all, that is = .
We can delimit then the process as follows. Let us crosslink nematic polymers in a chiral solvent to form a gel. Then, the solvent, which causes a natural twist q0 to the nematic, is then removed but nevertheless leaves behind
a cholesteric elastomer. There are two competing processes in the elastomer.
i)The twist 0 = qo of the gel, which gave the minimal energy at cross-linking,
is now unfavorable since without chiral material the lowest energy twist is
q = 0. The Frank energy density would be F = K2 02 /2 if no twist is lost. ii)
The director is anchored to the configuration in the matrix that pertained at the
moment of cross-linking. In the absence of any mechanical distortions being
allowed, this anchoring is given by the first de Gennes coupling. This nematic
elastomer contribution must be described in an exact way since the local rotation
can be very large. The clamped, large rotation form was derived by inserting
= into Eq. (23) which becomes Eq. (24) and then finally Eq. (26). The
rotation is the difference between the current angle (z) of the director and its
formation angle, 0 = q0 z. The effective pitch wave number q0 has the information of any possible changes in the pitch length due to any solvent loss since
117
gelation. The energy for an elastomer formed under a cholesteric solvent which
is afterwards replaced with an racemic one is then:

Z
1
1
02
2
(41)
f = A dz K2 + D1 sin ( q0 z)
2
2
where A is the sample area perpendicular to the helix. Let us consider two extreme cases (i) the perfect cholesteric state has an energy F = K2 q02 /2 where
the director is aligned with its formation direction. (ii) the untwisted state with
0 = 0 whose energy F = D1 /4 , where the extra factor of 1/2 comes from the
2
averaging. The
p director is kept twisted (strong imprinting) if K2 q0 < D1 /2.The
length = K2 /D1 is named the nematic penetration depth. The
p estimation
for retention or loss of the helical structure turns out to be q0 < 1/2. If the
effective director twist propagates against anchoring over a distance greater
than a period p0 of the helix, then the helix is unwind [11]. The product q0 determines stability. It is a non-dimensional measure of the nematic length relative
to the chiral pitch.
Practical procedures of tuning are perform by using light or a solvent. If
the chiral centres that induce twist are at or near photo isomerisable parts of a
molecule, then absorption of light could alter this crucial part of the molecular
structure. The bent molecule could have an entirely different twisting power. We
could speculate that such cholesterics could be radically altered by reversibly
pushing them over the imprinting threshold. If the new natural pitch wave number becomes q, then the resulting effective q then becomes:(q0 q).
5.2.
Chirality pumps
The process of reswelling of the imprinted elastomer is subtle and lead to chiral segregation of racemic mixtures (stereo-selection). Imagine an imprinted
network with qo > 2/ so that it has partially unwound from its originally
right-twisted state. The elastic energy has risen because the Frank energy of remaining twisted was high. The elastomer is now immersed in a racemic mixture,
that is, a solvent with equal number of right (R) and left (L) handed molecules.
If R-molecules swell the network, they would restore the natural twist towards
the imprinted value. The Frank energy is minimized, but now at a value of
twist that also satisfies the elastic anchoring requirements since n is restored
to n0 . The collective rewinding of the rubber towards its initially crosslinked
118
helical state is the benefit for selecting one handedness of the solvent preferentially to the other (provided the gel is not so swollen that nematic order is lost
altogether).
Given the critical character of unwinding, it is reasonable that the maximal
resolving power is obtained when the imprinting power of the resulting network
is near the transition point qo = 2/. We have taken this case in the illustration. We have also assumed for simplicity that the solvent is mesogenic in its
own right, indeed that its absorption into the cholesteric gel does not change the
underlying nematic order. The process can in principle then be reversed. Mechanical stretching of the swollen gel can remove all twisting. There being no
intrinsically chiral material actually part of the network, the network has neither
natural twist nor twist retained by nematic anchoring. Solvent expelled by the
stretch will then simply have the enriched concentration, that is its concentration is not unbiased on expulsion because it is leaving a now achiral host. The
process, we speculate, could be repeated cyclically leading to greater chiral enrichment. The first experiments [12] have demonstrated the chiral imprinting,
as well as the selective retention of one of the chiral enantiomers of a racemic
solvent.
6.
Electromagnetic Propagation in a Layered Medium
Optical propagation in layered media can be studied by conveniently writing

Maxwells equations and their corresponding constitutive equations in a 4 4
matrix form so that we can take advantage of the transversality of electromagnetic EM waves. First, we show that in this matrix representation the boundary
conditions of waves impinging on material can be imposed in a simpler way
in such a way the transfer and scattering matrix formalism can be used in a
natural way to obtain the transmittances and reflectances [13, 14]. Next, we
analytically solve the problem of axial propagation of an EM wave through a
cholesteric elastomer by solidly rotating the laboratory reference system along
the axial direction in the same way as the director n
.
6.1.
119
4 4 Matrix representation
Maxwells Equations in a free-source region can be written as (MKS unit system):

D = 0,
B = 0,
B
,
t
D
.
t
E =
H =
(42)
where the displacement vector D and the magnetic flux vector B, inside a bianisotropic medium, are related to electric field E and magnetic field H by the
following general constitutive relations [15, 16]:
D = 0 E + 0 0 H,
B =
0 0 mE + 0 H,
(43)
here, and are the dielectric permittivity and magnetic permeability tensors.
The inclusion of tensors and m emphasize the fact that inside a medium,
known as bianisotropic, the electric field E can also induce a magnetic polarization and a magnetic field H can induce an electric polarization. In addition
to this, the chirality of the medium is included through tensors and m which
satisfy the next relation
= mT ,
(44)
where T means the transpose, and they are equal to zero for non-chiral media. Here 0 and 0 are the dielectric permittivity and magnetic permeability
constants in vacuum.
It is well known that for systems where boundary conditions cannot be
avoided, Maxwells equations require the continuity of tangential components
of E and H fields at the boundary. Because of this, the symmetric form of relations (43) is convenient for systems where boundary conditions are imposed in
terms of these EM fields.
It is worth mentioning that we are interested on studying the optical properties of elastomers which are confined between parallel walls, so that, it is useful
120
to write the set of equations (42) in a representation where only appears the
transversal components of E and H.
As mentioned before, the transversality of EM waves suggest to rewrite
Maxwell equations (42) in a representation which permits to analyze, at the
same time, the behavior of the four transversal components of an EM wave (2
components for E and 2 components for H). This representation is frequently
referred as Marcuvitz-Schwinger representation [17].
If we define
1/2
e = Z0
h =
1/2
0 d = Z0
E,
1/2
Z0 H,
0 b =
D,
1/2
Z0 B,
(45)
with Z0 = 0 /0 the free-space impedance, the pair of constitutive relations

(43) can be written as
d = e + h,
b = me + h,
(46)
and Maxwells equations (42) as

5 d = 0,
5 b = 0,
1 b
,
c t
1 d
,
c t
5e =
5h =
(47)
where c = 1/ 0 0 is the light propagation speed in vacuum.

Now, we propose explicitly the components of e and h fields in a harmonic
time-dependent form as follows
ex
hx
e = ey eikt rt it ,
h = hy eikt rtit ,
(48)
ez
hz
where we have explicitly written the transversal incident wave vector kt =

(kx, ky ), with rt = (x, y) and the angular frequency of the propagating wave.
121
By substituting these electric and magnetic fields into (47) and after several algebraic manipulations we obtain the next differential equation
z = ik0 J4 L,
(49)
where is the four-vector defined as
ex
hx
=
ey ,
hy
(50)
J2 is the antisymmetric inversion matrix given by

0
1
J2 =
= J1
2 .
1 0
Also,
0 0
0 1
0 0 1 0
J4 = J2 J2 =
0 1 0 0 ,
1 0
0 0
(51)

1
L = tt (Dt + t + tz ) zz
Dt + t + zt ,
where
tt =
T
J4 = J1
4 = J4
xx xy
yx yy
tz =
Dt = (ik0 )1 ((J2 t ) J2 ) ,
xz
yz
zt =
t =
(52)
zx zy
x y
T
(53)
the upper symbol denotes Hermitian adjoint, the elements of tt, zt, tz are
square matrices of 2 2. The matrices ij have elements
ij =
ij ij
ij ij
(54)
122
with i, j = x, y, z and A B represents the Kronecker product with elements

aij B.1 Also,
t = (J2 t ) J2 ,
t =
x y
T
(55)
and = k/k0 is the normalized incident wave vector. Finally, k = (kx , ky , kz ),

k0 = 2/ and is the free-space wavelength.
Notice that, the differential equations (49) represent a set of equations which
only contains the transversal components of fields e and h and it is completely
equivalent to the set of Maxwells equations for a monochromatic EM wave
propagating through a bi-anisotropic medium with wave vector k. They can be
used for modeling several systems, including elastomer ones, provided that the
expressions for the tensors , , and m are explicitly given in every case.
Notice also that, the choice of the transversal components of fields e and h
in the four-vector (50) is actually arbitrary, and we can freely choose another
four-vector according to our convenience. For example, if we desire to write the
Maxwell equations by defining
ex
ey
=
hx ,
hy
(56)
instead of (50), then Eqs. (49) require to be transformed according to the following:
= 1 ,
L = 1 J4 L,
1
(57)
Let A a matrix of m n with elements aij and B a matrix of p q with elements bkl , the
Kronecker product C = A B is a matrix of (mp) (nq) with elements defined by
c = aij bkl ,
where
= p(i 1) + k
and
= q(j 1) + l,

where is the symmetric matrix given by
1 0 0
0 0 1
=
0 1 0
0 0 0
123
0
0
;
0
1
(58)
in such a way that we obtain the set of equivalent equations:

z = ik0 L .
(59)
In what follows, we will use the Marcuvitz-Schwinger representation to

solve the problem of axial propagation of an EM wave through an elastomer.
In the remaining sections of this chapter we will use the four-vector given by
(56) and the set of equations (59).
Particularly, inside a non-magnetic medium, the set of differential equations
(59) can be expressed in the following form:
z = iA,
(60)
where the 44 matrix A has the particular elements
k k
x y
zx
xzzzy
k0
kxzz
k0 zz
k k
ky zx ky zy
k0
k0xzzy
zz
zz
A =
kx yz
k0 yx k0 yy ky yz
zz
zz
ky xz
kx xz
k0 xx
k0 xy
zz
zz
0
0
0
0
+k0
yz zx

kx ky
kx2
+ yzzzzy
k2 + zz
k02
0
k2

kx ky
xzzzzy
ky2 xzzzzx
k2
0
ky2
2
k0 zz
k2
k2 xzz
0
(61)
As said above, ij , with i, j = x, y, z, represent the elements of dielectric permittivity tensor. In the following section, we proceed to implement the transfer
and scattering matrix approach by taking advantage of this more appropriate
representation of Maxwells equations.
124
6.2.
Boundary Condition
Let us consider a medium confined between two planes at z = 0 and z =

d where the optical properties continuously depend on z and the surrounding
medium is air. This implies that the elements of dielectric tensor ij depend only
on the zcoordinate. An incident EM wave, having wave vector kt impinges
from the left side of the medium. This EM wave propagates through the sample
and it is transmitted and reflected outside the medium having the structure
(x, y, z) = (z) exp[kxx + ky y],
(62)
because the phase matching condition implies the continuity of the tangential
components of k.
The general solution of the differential equation (60) for EM waves propagating in homogeneous media is the superposition of four waves planes, two
left-going and two right-going waves. With this in mind, we state the procedure
to find the amplitudes of the transmitted (at z = d) and reflected EM waves in
terms of incident waves at z = 0. This implies the definition of the following
quantities [18]:
i) The propagation matrix U(0, z), that is implicitly defined by the equations
(z) = U(0, z)(0),
U(0, 0) = 1I,
(63)
where 1I is the identity matrix and U(0, z) satisfies the same propagation equation (60) found for :
z U(0, z) = iAU(0, z);
(64)
the propagation matrix gives the right-side field amplitudes of the medium as
function of the left-side ones.
ii) For a specific value d, the transfer matrix is defined as U(0, d).
iii) The scattering matrix S, that gives the output field as function of the
incident one. The matrix S is defined as:
out = Sin
(65)
where in and out are the amplitudes of the in-going and out-going waves.
125
To find out S, we must express the field, in any one of the external media,
as a superposition of planes waves, by setting:
= T;
U (0, d) = T1 U(0, d)T,
(66)
where
+ T
= (a+
1 , a2 , a1 , a2 ) .
(67)
The relation = T can be interpreted as a basis change in the four dimensional space of the state vectors . The columns of T are the vectors representing the four plane waves generated by the incident waves in the two external
medium (here we assume as identical). The elements of vector are the amplitudes of the four plane wave. The choice of the new basis could be different
depending on the particular problem. By setting

Uf f Ubf
U() =
,
(68)
Uf b Ubb
the scattering matrix writes:

1
1
Uf f Ubf Ubb
Uf b Ubf Ubb
S=
.
1
1
Ubb
Uf b
Ubb
(69)
In equations (67) and (68) the symbols + and f ( and b) mean forward
(backward) propagating waves.
We point out that the methods of transfer and scattering matrices are very
useful in studying the plane wave transmission and reflection from surfaces or a
multilayered medium.
Eq. (60) can be formally integrated over a certain distance d of the cholesteric elastomers
Rd
0
0
(d) = ei 0 A(z )dz (0),
(70)
and, by straight comparison of Eqs. (63) and (70), the transfer matrix U(0, d)
is defined as:
Rd
0
0
(71)
U(0, d) = ei 0 A(z )dz ,
where plane waves are incident and reflected in the half-space z < 0 and a plane
waves are transmitted on the half-space z > d.
126
It can be seen immediately that the problem of finding U(0, d) is reduced to

find a method to integrate expression (71) on the whole sample. Because of the
non-homogeneity of the medium proposed here (an elastomer), we consider it
as broken up into many thin parallel layers and treating each as if it had homogeneous anisotropic optical parameters [19]. In this way, U(0, d) is obtained by
multiplying iteratively the matrix for each sublayer from z = 0 to z = d.
In next section, we will show that for axial propagation through a cholesteric elastomer, and by choosing appropriately a reference system, the system
(60) and the transfer matrix U have completely analytical solutions.
Now, we proceed to give the explicit form of the four-vector for the surrounding medium (free space). As said above, the general solution of the differential equation (60) for EM waves propagating in homogeneous media is the
superposition of forward and backward propagating waves. We consider a incident wave from left-half space with wave vector
k = (kx, ky , kz ) = k0 nd (sin cos , sin sin , cos ),
(72)
where, nd is the refractive index of surrounding medium, is the angle made

between k and z axis and is the angle made between k and x axis in
the xy plane. For an arbitrary polarization state the solutions of (60) can be
expressed as [20, 6]:

ib
u+b
v
b
v+
+ eikz z
a
aL ibu
R
2
2

ib
u
b
v
ib
u
+b
v
ik
z
z
e
,
+ rL 2 + rR 2

(z) =
ib
u
+b
v+
ib
u
b
v+
ikz z
+
a
e
in
a
R
d
L
2
2

ib
u
b
v
ib
u
+b
v
ikz z
+ind rL 2 + rR 2
e
for 0 z
(73)
where aL , aR represent the amplitude of incident propagating waves and rL , rR

denote the reflection amplitude of propagating waves. The subscript indexes R
and L correspond to right- and left-circularly polarized wave, respectively (see
Fig. 6).
b and v
b are defined as
The unit vectors u
b = b
b cos ,
u
x sin + y
b = (b
b sin ) cos + b
v
x cos + y
z sin ,
(74)
127
Figure 6. Schematic representation of a liquid crystal cholesteric elastomer. The

circular components of the obliquely incident beam as well as the components
of the transmitted an reflected parts are shown.
b, y
b, b
with x
z the unit vectors parallel to the x, y, z axis, respectively. In
the region z d, we write the transmitted field as

b
v+
ib
u+b
v+
ikz (zd) ,
tL ibu
t
e
R
2
2

(z) =
ib
ub
v+
+b
v+
ikz (zd)
ind tL 2 + tR ibu
e
2
for z d
(75)
As the tangential components of e and h must be continuous across the

planes z = 0 and z = d, the boundary values (0) and (d) can be fixed as:
aR
aL
1
,
(0) = Q
2 rR
rL
(76)
128
and
where
tR
tL
1
,
(d) = Q
2 0
0
cos cos
cos cos
cos sin
cos sin
Q=
ind cos cos ind cos cos
ind cos sin ind cos sin
i sin
i sin
i cos
i cos
+
nd sin nd sin
nd cos
nd cos
(77)
cos cos
cos cos
cos sin
cos sin
ind cos cos ind cos cos

ind cos sin ind cos sin
i sin
i sin
i cos
i cos
(78)
nd sin
nd sin
nd cos nd cos
If we restrict our analysis to the case when the electromagnetic wave is

incident parallel to z axis, the angles and equal zero and expression for
Q is reduced to
1
1
1
1
i
i
i
i
Q0 =
ind ind ind ind .
nd
nd
nd nd
(79)
Using Eqs. (70), (71), (76) and (77) the problem of reflection-transmission
can be established as follows
tR
aR
tL
= M aL .
(80)
0
rR
0
rL
where M = Q1 U(0, d)Q and U(0, d) is defined in (71). Notice that the
matrix equation (80) gives a set of coupled equations relating amplitudes aL ,
aR , rL and rR (from z 0) to transmitted amplitudes tL , tR (for z d).
129
The scattering matrix S relates amplitudes tL , tR , rL and rR with the incident amplitudes aL , aR . This relation can be expressed in terms of matrix M as
follows [21]
tR

tL
a
R
(81)
rR = S aL ,
rL
where
tRR tRL
tLR tLL
S = (P1 MP2 )1 (MP1 P2 ) =

rRR rRL ,
rLR rLL
and
1
0
P1 =
0
0
0
1
0
0
0
0
0
0
0
0
,
0
0
0
0
P2 =
0
0
0
0
0
0
0
0
1
0
0
0
.
0
1
(82)
(83)
Co-polarized coefficients have both subscripts identical, and cross-polarized

have different subscripts. The square of the amplitudes of t and r is the corresponding transmittance and reflectance; thus, TRR = |tRR |2 is the transmittance
corresponding to the transmission coefficient tRR , and so on. In the absence of
dissipation of energy inside the TPLC, the principle of conservation of energy
must be satisfied, this means that
TRR + TLR + RRR + RLR = 1
TRL + TLL + RRL + RLL = 1
(84)
Before ending this section, we mention that an alternative to find the transmission and reflection coefficients is using the expressions given by (68) and
(69). Also, the system of equations (80) can be solved numerically to find the
scattering matrix.
130
6.3.
The Oseen Transformation
Using a numerical procedure the set of coupled differential equations (60) can
be solved in a straight way. Nevertheless, the intrinsic helical symmetry, particularly of cholesteric elastomers, allows to suggest the possibility of finding a
reference system, for normally incident wave, for which the solution can be obtained analytically. For this aim, it is convenient to write the coupled equations
in a frame of reference in which the matrix A is diagonal and not dependent on
z propagation coordinate. This can be realized by rotating solidly and uniformly
the four-vector around zaxis, with the principal axes of ij making constant
angles with z. The required transformation can be realized by setting:
ex
ey
=
(85)
x = R(qz),
h
y
h
and
H = R(qz)A(z)R(qz),
(86)
with R(qz) the rotation matrix defined as

R(qz) = exp(Rqz) cos qz1I + sin qzR,
0 1 0
0
1
0 0
0
,
R=
0
0 0 1
0
0 1
0
(87)
q = qo / and 1I the 4 4 identity matrix. This transformation is known as

Oseens transformation [22].
For axial propagation and by considering the explicit form of dielectric tensor ij for cholesteric elastomers,
= ij + a nn,
(88)
= iH ,
dz 0
(89)
the Eqs. (60) are reduced to

the matrix H is given by
0
iq
H=
0
2k 1 ()
and
() =
iq
0
2 1
0
0
21
0
iq
21
0
,
iq
0

,
sin () + k cos2 ()
2
131
(90)
(91)
where ij is the identity tensor, a = k is the dielectric anisotropy of

medium, (k ) represent the principal values of dielectric permittivity tensor
in the rotating frame with axes x1 , x2 , z; again is the wavelength in free space.
In what follows, and to simplify notation, we omit the symbol () of four-vector

Unless we say the contrary, by writing , e and h, we will always
,
e and h.
mean the fields in the rotating frame and z the dimensionless variable.
Since the system matrix H is z-independent, the propagation equation (89)
admits four solutions having the form of plane waves
j (z) = tj exp(inj z),
(92)
where nj , tj are the eigenvalues and eigenvectors of H, respectively. They are

given by the equations:
n21,2 =
4 2 m 2u
+ q2 ,
2

2
2 2
t
1 = c1 n1 u1 , iq(4m + u1 ), 2iqmn1 , 2k ()u1 + 2m q ,

2
2 2
t
2 = c2 n2 u2 , iq(4m + u2 ), 2iqmn2 , 2k ()u2 + 2m q ,
(93)
where
p
u = 2 a2c 2 + m q 2 2 ; u1,2 = 2ac u;

1/2
ck = 4nk k ()u2k + 2m q 2 2 (2m + uk )
; (k = 1, 2)
ac =
k ()
k () +
; m =
.
2
2
(94)
132
As shows (92) the internal field can be represented as a superposition of the

four eigenwaves (amplitude representation), by setting
(z) = aj tj exp(inj z) T(z)
(95)
where T is the matrix whose j th column coincides with tj and (z) is the
4-vector with components aj exp(inj z). Obviously, and = T represent
the same state in two different sets of basis vectors. The metrization of the state
space is obtained by defining a metric tensor G and a scalar product 1 G 2
1 G 2 , where G and G = T G T are the matrixes representing G in the
two sets of basis vectors. Setting
0
0
0 1
0
0 1 0
G =
0 1
0 0
1
0
0 0
(96)
the norm of the state vector represents the time average of the z-component of
the Poynting vector, and the tensor G satisfies the relation
G G G1 .
(97)
In lossless media the z-derivative of the norm is identically zero and the matrix
G H is self-adjoint:
G H = (G H) H G.
(98)
The above property and the fact that the eigenvalue equation for H is biquadratic
imply that the eigenvalues are n1 , n2 , n3 = n1 , n4 = n2 , with nj real or
purely imaginary. It is worth mentioning that the normalization constants c1 ,
c2 were obtained using the metric tensor G ; this means that ck = |tk Gtk |1/2
with k = 1, 2, and tk is the conjugated complex of eigenvectors tk .
Only the modes n1 show a band gap for within the interval defined for the
positive roots of equation n1 = 0. The band edges are given by
q
1 = 2 /qo and2 = 2 k ()/qo .
(99)
133
Here, the modes n1 are pure imaginary and their corresponding eigenvectors
1 define evanescent and linearly polarized standing waves. The central wavelength of the bandgap is
s
p
1 + 2
q
1 +
,
=
(100)
c =
(3/2 1)
2
2
+ a r1
where Eqs. (40) and (91) were substituted in the last equation. This Eq. demonstrates clearly that for a positively anisotropic elastomer, the reflected wavelength c increases by stretching the sample along the helix axis. This behavior
is in qualitative agreement with the biaxial extension experiments performed by
Finkelmann et al. [23] in which c decreases due to an effective compression
along the helix axis. We finally observe that within the gap the polarization
of the propagating eigenwaves 2 is nearly circular and, in general, they are
elliptically polarized.
7.
Mechanical Control of Optical Spectra
In the last sections we have reviewed in detail a general mathematical formalism

to find the electromagnetic modes and the optical spectra of a chiral stratified
inhomogeneous media. The Maxwell equation are set up, and by means of the
representation of Marcuvitz-Schwinger and the transformation of Oseen the localized and propagating modes in the physical system are found. Then, the
dispersion matrix is calculated in order to determine the reflectances and transmittances and, thus, analyze the circular Bragg phenomenon. The Oseen transformation allows us to set up a rotating reference system along the helical axis of
the structural chiral material that rotates in the same way as the director. On the
other hand, with the Marcuvitz-Schwinger formalism, the Maxwell equations
become a set of differential equations in terms of the transversal components of
the electromagnetic fields. Hence, we obtain a set of first order differential equations that in a matrix representation have a very simplified notation and have
analytical exact solutions for axial propagation of the electromagnetic fields.
In this section, this mathematical formalism is applied to a slab of cholesteric
elastomer, where light impinges on the material, in order to analyze the optical
spectra and their dependence on macroscopic deformations.
134
It is a known fact that structural chiral materials presents the circular Bragg
phenomenon in a wavelength regime [24], where normal incident electromagnetic plane waves of left- and right-circular polarization (LCP and RCP) states
are reflected and transmitted differently, i. e., light of right handedness is highly
reflected in a right helical structure whereas a similar plane wave but of the reverse handedness is not. Thus, structural chiral material are circular-polarization
rejection filters in optics [3, 5, 21]. In addition cholesteric elastomers are very
sensitive to external stimuli as electric fields, temperature and mechanical stress.
Therefore, it is possible to control the Bragg regime with these sorts of stimuli.
cholesteric elastomers are formed by monomers of liquid crystals cross-linked
to polymeric chains that produces a flexible material whose molecular order is
similar to cholesteric liquid crystals with the advantage that in this new material
it is feasible to change the optical properties by means of macroscopic deformations. In this section we focus in the control of circular Bragg phenomenon
under the influence of an externally induced mechanical strains applied parallel
and transverse to the helical axis of a slab of cholesteric elastomer.
7.1.
Cholesteric elastomer slab subjected to an axial deformation
In this section we present and analyze the optical spectra obtained from the
remittances. The reflectances and transmittances obtained from the scattering
matrix or the transfer matrix are in terms of the elongation , the wavelength
and the incidence angles of light, (angle between the light direction and the
helical axis, z) and (angle between the light direction and the x-axis). By
numerically solving the set of equations (80) for oblique incidence we obtained
these optical spectra for a sample of siloxane backbone chain reacting with 90
mol % and 10% of the flexible difunctional cross-linking groups (di-11UB).
The rod like mesogenic groups are present in the proportion 4 : 1 between the
nematic 4-pentylphenyl-4-(4-buteneoxy) benoate (PBB) and the derivative of
chiral cholesterol penteonate (ChP) [36]. The behavior of the optical spectra
for another material is expected to be qualitatively similar to the presented here;
the material parameters are: r = 1.16, L = 10.7 m, p2 = 214 nm, = 1.91
q = 2.22, = 1.
The optical spectra show a circular Bragg regime in the RRR co-polarized
transmittances and reflectances, which depends on the axial elongation of the
cholesteric and the incidence angles of light. These spectra are consistent with
135
the circular Bragg phenomenon for which the right circularly polarized wave
impinging a right-handed elastomer, is highly reflected, while the left circularly
polarized wave is transmitted as we can see in Fig. 7 for reflectances. We see
in this Fig. that the center of the bandgap blue-shifts as the incidence angle increases, as it occurs in the absence of stress. We also observe that by increasing
the elongation, the band width decreases as can be seen by comparing the right
and the left hand columns of this Fig. , that correspond to = 1 (elastomer
under no deformation) and m = 1 + M21 = 1.052 (elastomer submitted to
half of its critical elongation).
Figure 7. Co-polarized teflectance RRR versus the wavelength and the incidence angle for the elongations = 1 and = m .
Moreover, when the strain is the critical M = 1.1622/3 = 1.1040, the
bandgap disappears due to the fact the cholesteric director is completely aligned
with the helical axis as can be observed in Fig. 8. This effect opens up the
door for proposing novel devices to mechanically control the light flow, since it
allows to switch off a bandgap by applying a mechanical stress to the elastomer.
This is clearly illustrated in Fig. 8 where the bandwidth diminishes as a function
of the deformation for normal incidence. Further results confirm the displacement of the band reflection for RRR for larger incidence angles as get larger
[6]. Therefore, these results show the possibility of mechanically control the
circular Bragg phenomenon for tuning and switching applications. On the other
136
hand, analytical results show that the reflected wavelength at normal incidence
red-shifts by stretching the elastomer along the helical axis.
Figure 8. Co-polarized transmittances TRR and reflectances RRR as a function

of the wavelength and the axial elongation for normal incidence.
7.2.
Cholesteric elastomer slab subjected to a transverse deformation
In this section the optical spectra of obliquely incident light on a cholesteric

elastomer slab immersed in vacuum, under the action of an externally applied
transverse mechanical stress are reviewed [7]. A structurally right-handed monodomain cholesteric elastomer initially making an angle 0 = q0 x with the
yaxis, subject to the action of a transverse elongation, is considered, where
the helix wave number is q0 = 2/p and the spatial periodicity or pitch is p
and the director n
= (0, cos , sin ). After imposing a stress perpendicular to
the pitch direction yy = , all the nondiagonal elements of vanish [1]. After
deformation, the material frame shrinks and the effective helical wave vector
becomes q = q0 /zz and thus 0 = qz.
In Fig. 9 we can observe vs z parametrized by for r = 1.16 and for
values of both, smaller and larger than the critical stress value c = 1.06.
Notice how, for < c , the configuration gets deformed from the undistorted
linear dependence on z in the absence of stress ( = 1); but keeping the same
137
value at points distanced from the origin by integer multiples of the pitch. On
the other hand, for > c. does not grow continuously but spatially oscillates
with the pitch period and its amplitude diminishes as enlarges.
Figure 9. Configuration angle for a transverse elongated cholesteric elastomer

for various values of .
Assuming monochromatic plane waves in Maxwell equations, following the
Marcuvitz-Schwinger representation and the Oseen transformation it is feasible
to find the optical modes in the slab. Likewise, the scattering matrix could be
obtained following the formalism in Sec. 6.2., in order to find the optical spectrums that depend on the incidence angle and as well as the wave number
k0 , in addition to the constitutive parameters of the elastomer cholesteric and its
thickness.
When the reflectance RRR is plotted as a function of both, the wavelength
and the incidence angle, in the absence ( = 1) and presence ( = 1.04) of an
external stress, we can observe than in both cases the center of the reflection
band blueshifts as increases, see Fig. 10. However, without an applied stress,
the bandwidth remains almost constant, whereas under stress, it narrows for
angles smaller than 450 and widens for larger angles. By looking carefully, it
138
can be noticed that the band gap splits into three peaks for shorter angles, which
joint up for an angle about 450 ; after of which stand together to finally separate
for larger angles. It is worth mentioning that transmittances show consistently
the complementary part of the band gap.
Figure 10. Circularly polarized reflectance RRR as function of the wavelength

and for a) = 1 and b) = 1.04. Other parameters are: = 3.0, k = 3.8,
h = 1, = 0 and L/ = 100.
It is shown, in Fig. 11, that the transmission bands distort, for circularly polarized transmittances for both incidence angles: = 0 and = 45. We can see
that there is a region for values of around c for which the transmittance TLL
presents a thin band gap in an inner region of a wider band gap of the transmittance TRR . Hence, a wide but partial reflection band for left-circularly polarized
waves contains a thinner total reflection band where the system behaves actually
as a polarization-universal filter.
Therefore, the elastomer under distortion exhibits a band reflection which
blueshifts for obliquely incidence, as in the absence of stress, but whose bandwidth lessen for shorter angles an get larger for angles near to 900 . The reflectances of both handedness are quite different opposed to periodical twisted
nematics for which a polarization-universal band gap was found and the reflectances of both handedness are very similar. Nevertheless, for values of
around c , there is a thin right-circularly polarized band reflection nested in a
139
TLL
TLR
TRR
=0
1.0
n =1.08
0.8
0.8
0.6
0.6
0.4
0.4
0.2
0.2
0.0
400
450
500
=45
1.0
550
600
650
700
0.0
400 450
500
(nm)
550
600
650
700
(nm)
Figure 11. Circularly polarized transmittances for = 1.02, 1.04 and = 0 at

normal ( = 00 ) and obliquely ( = 450 ) incidences.
broader left-circularly polarized band gap which is kept for almost all the incidence angles. Thus, a narrow polarization-universal band gap is located inside
a wider partial band gap.
8.
Chemical Control of Optical Spectra
In this section, the optical spectra, in terms of the chiral order parameter and
the reduced elastic energy c, are calculated, in order to determine the effect of
a chemical solvent over the optical properties of the cholesteric elastomer slab.
We have seen that the optical properties of a cholesteric elastomer could be
tuned by a mechanical stress, in this section we concern on optical control when
the slab is immersed in a racemic solvent Ref. [37].
The objective is to analyze the optical spectra corresponding to a thin elastomer slab whose thickness is smaller than fifteen helix periods, immersed in
a chemical solvent, and we shall review some potential applications of this
system.
140
8.1.
Universal optical filter
The director vector of the elastomer is givenp

by Eq. (35) and the nematic penK2 /D1 , where K2 is the twist
etration depth in rubbery networks is =
elastic constant and D1 is local anchoring of the director to the rubbery network. The robustness of chiral imprinting depends on the nematic penetration
depth , which can be controlled by varying the density of cross-links in the
network (affecting D1 ) [36].
The imprinting efficiency depends on the chiral order parameter = q0 , a
function of elastic constant K2 and D1 proportional to rubbery elasticity modulus which is related with cross-linked density. A spectacular property of an
imprinted network is their capacity to preferentially absorb and retain right or
left molecules from a racemic solvent.
The energy for an elastomer, without deformation, formed under a cholesteric solvent which is subsequently replaced with an achiral one is given by Eq.
#

Z "
K2 d 2
1
+ sin2 ( q0 z) dz.
(101)
F =
2
D1 dz
The equilibrium configuration can be obtained by minimizing F with respect
to the angle, then we have got the Euler-Lagrange equations

F
z
= 0.
(102)
z
which in this case turns out to be
2 d2
+ sin 2 (q0 z ) = 0.
q02 dz 2
(103)
Notice that if = 0 the solution of Eq. (103) is 0 (z) = q0 z which corresponds to an ideal or undistorted cholesteric helix. By introducing the variable
w = q0 z + /2, Eq. (103) transforms in the expression
d2 w
q02
+
sin 2w = 0.
dz 2
2
(104)
note that it is the simple pendulum equation. Hence, for large values of , small
harmonic oscillations of frequency q0 / around = q0 z + /2 are expected.
141
Nevertheless, for smaller values of anharmonic oscillations take place until

w abandons its oscillatory dependence and grows without limit following the
dependence corresponding to a rotatory motion in a simple pendulum. This
behavior can be inferred by using the general solution of Eq. (103) which is
given by
(z) = q0 z Am(e
cz/, 1/e
c2) + /2.
(105)
where Am(z, m) is the Jacobian amplitude and e
c is a constant related with the
reduced elastic energy
Fig. 12 shows a plot of the director vector angle (z) against position for
different values of chiral order parameter and e
c = 1. It is interesting to note
that by increasing from zero, (z) presents oscillations without changing its
amplitude, around the undistorted solution 0 (z) whose spatial period increases,
until reaches the critical vales: ec = 3 and e
c = 1. After this value (z) deviate
considerably from 0 (z) and enlarges its effective q-value for ec which is
equivalent to have an untwisted helix than that of 0 (z).
Figure 12. Director vector angle as function of the position for different values
of chiral order parameter, .
142
Figure 13. Circularly polarized reflectances RRR and RLL versus wavelength
for a cholesteric elastomer slab of 10p. In the absence of solvent ( = e
c = 0)
(a) = 450 and (d) = 600 ; for = 4, e
c = 0.5 with (b) = 450 and (e)
= 600 and for e
c = 2, = 0.2, with (c) = 450 and (f) = 600 . Other
parameters are = 1.91, k = 2.22, h = 1 and p = 2.28nm.
The co-polarized reflectance and transmittances of thin slabs of cholesteric
elastomers of thickness 8, 10, and 15 spatial periods p were calculated in Ref.
[38] for a real cholesteric elastomer material. The transmittance spectrums RRR
and RLLare compared for thin elastomer slabs in the presence and absence of
solvent.
As the elastomer slab gets thinner the band reflection turns out to be less
developed in the absence of the solvent as can be seen in most of these figures
where amplitude reductions are obtained after diminish the thickness from 15
to 10 periods. Even larger reductions are observed for oblique incidence (See
Figures 1315).
143
For obliquely incident light at = 45o and 60o on the elastomer slab, whose
thickness is 10p and which is distorted by a solvent that render the value = 4,
the amplitude increases by 0.1 and the bandwidth enlarges by 10nm (See RRR
in Figs. 13b and 13e) with respect to the plots corresponding to an undistorted
material ( = 0, e
c = 0, See RRR in Figs. 13a, 13d). On the other hand, RLL
almost do not exhibit any band reflection. The same changes for RRR can be
attained by setting e
c = 1 for oblique incidence at 45o and 60o but a very small
amplitude reflection band is obtained for RLL.
It is possible to find circularly polarized filters of 10p thickness whose band
amplitude and bandwidth are enhanced chemically by a solvent. However, there
are exceptions, in this case, where the amplitude and bandwidth of the RRR
band diminishes compared with the RRR band for an undistorted material, for
example, for ( = 0.4, = 45) [38], see Fig. 14.
Moreover, for = 0.15, thickness 15p, and oblique incidence around 33o
the system behaves as a universal filter since both RRR and RLL exhibit the
same band reflections, see Fig. 15. For shorter thicknesses: 10 and 8, the band
amplitudes decrease 20% and 40%, respectively.
Finally, reflection bands of any polarization are not found when the light
impinges elastomer slabs thinner than 8 p, whether the slab is immersed or not
in a racemic solvent.
Therefore, the presence of the solvent on a thin slab (15p, 10p and 8p) is
able to increase the bandwidth and amplitude of the band reflection of RRR
by keeping RLL without band, for incidence angles 45 and for = 4
and e
c = 1. In addition, a 15p, elastomer slab behaves as a universal filter, in
the sense that presents band reflections for any polarization, for = 0.15 and
= 33o . This amount to have a chemically controlled filter which changes from
the circularly Bragg phenomenon to a universal filter because of the presence of
the solvent. The results suggest that it is possible to construct very thin filters
immersed in a racemic solvent that exhibit the circular Bragg phenomenon for
oblique incidence.
8.2.
Optically Monitored Chiral Pumps
Separation of molecules by chirality is an important process in biochemistry and

in the pharmaceutical industry. Over half of the organic compounds in drugs
are chiral whose different enantiomers have different effects. For instance, Ri-
144
Figure 14. Circularly polarized reflectances RRR and RLL versus for a
cholesteric elastomer slab of 10p. In the absence of solvent ( = e
c = 0)
0
0
0
(a) = 45 and (d) = 60 ; for = 0.4, e
c = 0.5 with (b) = 45 and (e)
= 600 and for e
c = 0.7, = 0.5, with (c) = 450 and (f) = 600 . Other
parameters the same as Fig. 26.
talin prevents hyperactivity in children in one enantiomer, whereas it has not
effect when the opposite enantiomer is used. Another example is thalidomide:
one enantiomer of thailomide can cure morning sickness of pregnant women,
whereas the other causes birth defects. The sense of smell is also sensitive to
the chirality of the odor molecules. For instance, limonene has an orange smell
whereas the opposite enantiomer smells like lemon [39]. In this section we review a proposed method to optically monitoring the chiral sorting of molecules
performed by an elastomer liquid crystal.
In Ref. [37] it was shown that optical spectra of a slab of cholesteric elastomer changes with the chiral order parameter, which is defined as the im-
145
Figure 15. Circularly polarized reflectances RRR and RLL as function of for
k0 R = 40 a slab thickness of 15p (a) in the absence of solvent ( = 0) and (b)
for = 0.15, e
c = 0.5.
printing efficiency of the volume fraction of the absorbed molecules from the
racemic solvent, having the preferably absorbed chirality, for obliquely incident
circularly polarized light. This system is proposed as a chemically controlled
optical filter or an optically traced chiral pump. In this section, a method to
determine the volume fraction of preferentially absorbed molecules by measuring the transmittance and reflectance spectra during a preferentially absorbing
process is reviewed. Specifically, the reflectance and transmittance of circularly
polarized light for oblique incidence due to a cholesteric elastomer, assuming
arbitrary values of chiral order parameter, , are calculated, using the same
mathematical formalism described previously.
The optical spectra show (see Fig. 16) that in the absence of solvent ( = 0)
there is only a band reflection for right-circularly copolarize light RRR with the
146
Figure 16. Circularly polarized reflectance RRR and RLL as function of the
wavelength and angle incidence for the ideal helix case = 0 (left column) and
= 0.4 (right column). Other parameters are: = 1.91, k = 2.22, h = 1
and q0 = 218 nm.
147
band width of ' 50nm and maximum amplitude. The center of the reflection band blue-shift whereas the width and amplitude band remain constant as
the incidence angle increases . In contrast, when = 0.4 there appear bands
for both left- and right-copolarized reflectances RRR and RLL . In this particular case the RRR is not as well formed as in the absence of solvent because
is amplitude present various peaks and the bandwidth varies as a function of
the incidence angle, reaching its smaller value for angles around 45 degrees.
Moreover, RLL is very thin since its band width is around 15 nm and contained
in the interval where the RRR band lies. The the cross-polarized reflectances
RRL, RLR are almost zero. We mention that the corresponding transmittances:
for the case without solvent ( = 0) confirms consistently the complementary
behavior of an undistorted cholesteric. The co-polarized transmittances TRR
and TLL exhibit troughs where the transmittance diminish, where TRR is well
defined whereas that of TLL changes is thickness and deep, and the blue-shift
of the trough for large incident angles is also present [37].
Therefore, under the presence of the solvent, there are considerably
changes in the bandwidth of the reflectance for left- and right-copolarized light,
which are susceptible to be detected experimentally.
These results suggest that is possible to utilize the optical spectra as an indirect method to determine the concentration of preferentially absorbed molecules
during a segregation process.
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Chapter 6
PROPERTIES OF ELASTOMERS BASED

ON CAPROLACTONE PREPOLYMERS
Rui Xie
The Dow Chemical Company, Thermoset Research and Development,
Freeport, TX, U. S.
SUMMARY
In recent years, caprolactone based prepolymers have gained more and
more acceptance in the market place because of their balanced properties. In
some applications where high temperature performance, dynamic properties,
abrasion and flex fatigue resistance are desired, the caprolactone-based
prepolymers have become the primary choice. In this paper, properties of
elastomers based on ether, ester and caprolactone polyols were studied sideby-side. Preliminary results demonstrated that the caprolactone-based
elastomers possessed excellent dynamic properties, improved heat resistance,
excellent gasoline resistance, superior abrasion resistance, and better cutting
growth resistance and weatherability. These characteristics make the
elastomers suitable for various applications. Some commercial applications of
such elastomers in pipeline pigs, conveyor belts, and industrial wheels and
tires were discussed in the paper.
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Rui Xie
INTRODUCTION
Over the past several decades, high performance polyurethane elastomers
have been successfully employed in a growing variety of applications due to
their broad range of properties [1]. Polyurethane elastomers based on
prepolymers are composed of short, alternating polydisperse blocks of soft and
hard segments. The soft segment is typically a low glass transition temperature
polyether or polyester, generally of molecular weight 400-5000. The hard
segment is usually a high glass transition temperature, possibly semicrystalline
aromatic diisocyanate, linked with a low molecular weight chain extender.
Depending on the chemical structure of the building blocks, curing conditions,
and the stoichiometry ratio of the components, physical properties of urethane
elastomers are versatile, including excellent dynamic properties, outstanding
adhesion to many substrates, good chemical resistance, superior abrasion
resistance, and the ability to be processed under a variety of different
conditions via a broad range of processing techniques [2-4]. The versatility in
formulations has led to wide acceptance of polyurethane elastomers in a
variety of industrial and consumer applications, such as industrial wheels and
rollers, timing belts, chemical mechanical polishing pads, golf ball covers,
optical lenses, in-line skate wheels, and dental aligners.
To understand and explain how the building blocks affect physical
properties of urethane elastomers, the molecular structure of the polyurethane
elastomers must be taken into account. There exists a degree of immiscibility
between the hard urethane segments and the soft polyol segments, which
means macroscopically polyurethane elastomers are isotropic, but
microscopically they are not structurally homogeneous [5]. Thus, though there
is some degree of mixing of the soft and hard segments, phase separation of
the two segments occurs, producing a structure that can be considered as hard
segment domains dispersed in a soft segment matrix. The resultant two-phase
micro-domain structure exhibited by the urethane elastomers is responsible for
their superior physical and mechanical properties [6-12].
The two-phase micro-domain structure depends on the molecular structure
of the isocyanate, polyol, and chain extender. Processing conditions, such as
temperature, can also change the domain structure significantly. Therefore,
physical properties of urethane elastomers can be tailored by selecting
different isocyanate, polyol and chain extender, or by simply varying the
processing temperature [13-19].
The two most commonly used isocyanates are toluene diisocyanate (TDI)
and 4,4-diphenylmethane diisocyanate (MDI), while polyols available for
Properties of Elastomers Based on Caprolactone Prepolymers
153
elastomer synthesis include many different families, such as polyesters,

polyethers, polycarbonates, hydrocarbons and polydimethylsiloxanes.
Traditionally, polyurethane elastomers have been produced with polyester and
polyether soft segments. Elastomers synthesized from polyesters, such as
polyethylene adipate (PEAG), possess relatively good physical properties.
However, they are susceptible to hydrolytic cleavage of the ester linkage.
Polyether-based elastomers exhibit a relatively high resistance to hydrolytic
cleavage when compared to polyester elastomers, but possess lower physical
properties. The polyether that results in an elastomer with the best physical
properties is polytetramethylene oxide (PTMEG). Nevertheless, elastomers
prepared with PTMEG show a level of mechanical strength inferior to that of
polyester based elastomers, though they possess relatively good hydrolytic
stability and water resistance.
Polycarbonate based elastomers show excellent mechanical properties and
hydrolytic resistance [20-24]. Unfortunately, polycarbonate polyols are much
more expensive compared to traditional polyols, and polycarbonate based
prepolymers are generally viscous thus hard to be processed in many
circumstances. Hydrogenated polybutadiene and polyisobutylene-based
elastomers exhibit excellent resistance to light, thermal degradation and
hydrolysis [25]. However, the physical properties of the resulting elastomers
are poor relative to those of elastomers based on polyester and polyether. The
use of polydimethylsiloxane glycol (PDMS) as a soft segment results in
polyurethane elastomers with improved low-temperature performance.
However, general mechanical strength of these elastomers is relatively poor
compared to conventional urethane elastomers based on polyester and
PTMEG.
Not a single polyol mentioned above can produce an elastomer that brings
out the benefits of both polyester and PTMEG, while possessing good
processability and cost-effectiveness. However, there are many applications
that require elastomers having excellent balanced properties. In addition to
general mechanical strength, hydrolytic resistance, abrasion resistance, and
thermal and UV stability, cutting growth resistance and excellent dynamic
properties are essential for many applications.
Unlike polyether and polyester polyols, polycaprolactone (PCL) polyols
have not been widely used for elastomer applications though past studies
indicates caprolactone based elastomers possessed properties superior to
polyether and polyester based elastomers in many aspects [26]. In this paper,
properties of MDI-PCL and TDI based elastomers were studied side-by-side
with those based on PTMEG and PEAG backbones. In addition to general
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Rui Xie
physical properties, resistance to thermal degradation, abrasion resistance,

weatherability, gasoline resistance, cutting growth resistance and dynamic
properties are discussed. These key engineering properties are essential for
selecting the right compounds for the right applications. Preliminary results
demonstrated that PCL based elastomers had more balanced properties.
Therefore, PCL based elastomers can potentially be used in a more wide range
of applications.
LABORATORY EXPERIMENTAL TECHNIQUES

Commercially, polyurethane elastomers can be synthesized via a onestep process or multistep syntheses. While the one-step process is the
quickest and easiest of the manufacturing techniques, synthesis via more than
one step imparts greater control over the chemistry of the reaction, influencing
the structure, physical properties, reactivity and processability of the finished
product. In this study, a two-step process was used, referred to as the
prepolymer method. The first step involves synthesis of a prepolymer from the
polyol in excess diisocyanate to produce an isocyanate-terminated molecule.
Subsequent reaction of the prepolymer with a diol or diamine chain extender
constitutes the second step, which produces a multi-block copolymer.
For the purpose of this study, PTMEG, PCL and PEAG were reacted with
excess MDI and TDI at 80C for 5-6 hours to form the prepolymers. The MDI
prepolymers were then mixed with 1,4 butanediol at 95% stoichiometry based
on measured NCO content of these prepolymers, while the TDI prepolymers
were mixed with Ethacure 300 at 95% stoichiometry. The mixtures were
degassed and poured into molds preheated at 120C in the case of MDI
prepolymers and 110C in the case of TDI prepolymers. The molds were then
transferred to a 115C oven in the case of MDI prepolymers and 100C in the
case of TDI prepolymers, and kept at the temperature for 16 hours to produce
test specimens.
Stripped TDI prepolymers were obtained by distilling reaction products of
TDI and polyols at 120C using a short path distiller. NCO contents of the
prepolymers reached 95% of the theoretical NCO content with unreacted
monomeric TDI level less than 0.05%. Elastomer samples of stripped TDI
prepolymers were prepared at the same condition as conventional TDI
prepolymers.
All specimens were aged at room temperature for 4-6 weeks before
physical testing. All the physical testing was done per ASTM methods unless
155
otherwise specified. Dynamic Mechanical Analysis was performed in the

tension mold on a Rheometrics RSA II operated at 6.28 rad/s frequency and
2C/minute temperature increment.
RESULTS AND DISCUSSION

Table I listed general physical properties of MDI elastomers based on
PTMEG, PEAG and PCL at 93 Shore A hardness. The PEAG based elastomer
showed better tensile strength, elongation, and superior tear resistance
compared to the PTMEG based elastomer. However, its compression set and
resilience were inferior to the PTMEG based elastomer. Interestingly, the PCL
based elastomer offered very competitive stress-strain properties and tear
resistance compared to the PEAG based elastomer, and significantly improved
compression set and resilience over PEAG based elastomer. Its ability to retain
elastic properties after prolonged compressive stresses was as good as that of
the PTMEG based elastomer, while its resilience was close to that of the
PTMEG based elastomer. It is clear from Table I that the PCL based elastomer
has more balanced properties. It exhibits the excellent tear and stress-strain
properties of polyester based elastomers, while retains superior compression
set and resilience of polyether based elastomers.
Table 1. General Physical Properties of 93 Shore A Elastomers Based on
Conventional MDI Prepolymers Cured By BDO
Properties
100% Modulus, psi
300% Modulus, psi
Tensile Strength, psi
Elongation, %
Tear Strength
Di e C, pli
Split, pli
Compression Set, %
Bashore Rebound, %
PCL-MDI
1250
2385
5900
640
PTMEG-MDI
1230
2200
5400
570
PEAG-MDI
1135
1930
6000
780
615
165
15
56
560
90
17
62
590
164
29
42
One can draw similar conclusions when comparing physical properties of

elastomers based on conventional TDI prepolymers of different polyol
backbones. Table 2 listed physical properties of conventional TDI prepolymers
cured by Ethacure 300 at 95% stoichiometry. The TDI-PCL based elastomer
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Rui Xie
demonstrated the most balanced properties, such as improved resilience over

PEAG-TDI based elastomer, and greater stress-strain and tear properties over
PTMEG-TDI based elastomer.
Table 2. General Physical Properties of 85 Shore A Elastomers based on
Conventional TDI Prepolymer Cured by EthacureTM 300
Properties
100% Modulus, psi
300% Modulus, psi
Elongation, %
Tear Strength
Die C, pli
Split, pli
Bashore Rebound, %
PCL-TDI
876
1672
6155
675
PTMEG-TDI
875
1550
4500
620
PEAG-TDI
734
1415
6853
815
468
110
55
420
65
64
485
114
42
The contribution of the soft segment to physical properties should be

easier to observe if the structure of the hard segment is fixed while varying the
soft segment. This is normally difficult to achieve in the case of conventional
prepolymers, where unreacted residual isocyanate is always present. However,
in the case of stripped TDI prepolymers, monomeric TDI is removed from the
reaction products of polyol and isocyanate. The process results in prepolymers
that mainly consist of the same molecular structure, ABA, where A is TDI and
B is a polyol. Thus, if the stripped prepolymers based on different polyol
backbones are chain-extended with the same curative at the same curing
conditions, one may expect that no matter what the soft segment is, the
molecular structure of the hard segment should remain more or less the same.
Therefore, any difference observed in physical properties among these
elastomers should be originated from the soft segment, the polyol backbone.
Table III listed properties of elastomers based on stripped TDI prepolymers of
PTMEG, PEAG and PCL. The prepolymers reached 95% of their theoretical
NCO content and contained less than 0.05% free TDI. As a result, this was a
prepolymer that contains primarily the ABA structure. Interestingly, though all
prepolymers were based on 2000 molecular weight diols and had similar NCO
content, the PCL based elastomer was about 5 points softer than those based
on PTMEG and PEAG. Even at lower hardness, the PCL based elastomer
demonstrated better stress-strain and tear properties than the PTMEG based
elastomer. Upon removal of free TDI, the PCL based elastomer is much more
resilient than the PEAG based elastomer. Clearly, incorporation of PCL polyol
157
in the structure of urethane prepolymers results in elastomers with more

balanced physical properties.
Table 3. General Physical Properties of 85 Shore A Elastomers based on
Stripped TDI Prepolymers cured by Ethacure 300
Properties
PCL-TDI
PTMEG-TDI
Hardness, Shore A
100% Modulus, psi
300% Modulus, psi
Elongation, %
Tear Strength
Die C, pli
Split, pli
Bashore Rebound, %
80
640
1156
4650
675
85
790
1430
3100
510
PEAGTDI
85
810
1465
7500
800
375
95
60
350
70
65
515
125
41
While a good combination of properties normally suggests toughness of

the material, it does not imply structure parts made from such material would
survive harsh conditions in the real application environment. As discussed
earlier in this paper, polyester based elastomers are generally considered much
tougher than polyether based elastomers. However, because the ester linkage is
susceptible to hydrolytic cleavage, polyester based elastomers break down
rapidly in a hot and humid environment. Therefore, besides general physical
properties, one may need to carefully examine other factors when selecting
compounds for specific applications. Such factors include resistance to thermal
degradation, light, moisture, and abrasion, etc.
Table 4 listed stress-strain and tear properties of the three 93 Shore A
MDI elastomers before and after aging at 120C for a week in air. It is clear
from the data that PCL and PEAG based elastomers retained their original
stress-strain and tear properties after exposed to high temperature and
oxidation, while the PTMEG based elastomer lost 40% to 80% of its original
properties under the same conditions. The results imply that PEAG and PCL
based elastomers are much more resistant to thermal degradation as compared
to the PTMEG based elastomers. There was no clear evidence that PEAG
based elastomers were more resistant to thermal degradation than the PCL
based elastomers.
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Rui Xie
Table 4. Tensile and Tear Properties of 93 Shore A Elastomers
Aged at 120C for 7 days
Elastomers Tensile Strength (psi)

Before
After
PEAG6000
7450
MDI
PCL-MDI 5900
7600
PTMEG- 5400
1025
MDI
Elongation, %
Before
After
780
946
Tear Strength
Before
After
590
600
640
570
615
560
730
200
620
325
Figure 1 is the stress relaxation profile of two 85 Shore A elastomers at

130C in air. Data were obtained by a Rheometrics RSA II at 2% static
extension. Over a 48-hour period, the stress of the PCL based elastomer
remained near its original level, while that of the PTMEG based elastomer
dropped rapidly within the first 15 hours. The data demonstrate that PCL
based elastomers have much better resistance to thermal degradation than the
PTMEG based elastomers, which is in line with the results shown in Table IV.
lo g (f(t )/f (0) )
-1
-2
-3
P TM EG -M D I
-4
PC L-M D I
-5
0
10
20
30
40
50
T im e ( hou rs )
Figure 1. Stress relaxation profile for 85 Shore A PCL and PTMEG based elastomers
in dry air at 130C.
159
While heat exposure may be a concern for certain applications, moisture

exists in virtually all applications. Some applications may require excellent
moisture resistance, and some may not, due to differences of the application
environment. However, situations where heat and moisture coexist pose the
toughest challenge for polyurethane elastomers. Figure 2 shows tensile
strength of elastomers after exposure to 80C in an 80% relative humidity
environment for different periods of time. The variation in the data is primarily
due to the limited number of dogbone samples available for testing (three for
each data point). Under such conditions, the polyester based elastomer lost its
tensile strength after 1 week, while the polycaprolactone based elastomers
retained their tensile properties for about 3 weeks. The PTMEG based
elastomer performed the best: no significant drop in tensile properties was
observed over a period of 15 weeks. However, it is interesting to note that a
modified PCL based elastomer retained its original tensile properties over a
period of 12 weeks. During the period it was examined, the modified PCL
based elastomer performed as well as the PTMEG based elastomer. Ultimate
elongation and energy at break (not shown) of these samples exhibited the
same trend.
% Te ns ile St ren gt h R em ai nin g
14 0
12 0
10 0
80
60
40
PCL
Mo difie d PCL
PEA G
20
P TME G
0
0
10
12
14
16
T im e ( we ek )
Figure 2. Remaining tensile strength of elastomers based on different backbones after
exposed to 80% relative humidity at 80C for different period of time.
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Rui Xie
In addition to heat and moisture, UV stability is required in some urethane

applications, especially for applications where thin sections of large surface
area are exposed to direct sun light, for example, coatings. UV light can cause
discolor to polyurethane coatings, result in cracks and de-bonding. Figure 3
shows weatherability of 93 Shore A MDI prepolymers based on different
polyol backbones. Samples of the elastomers were aged in a Xenon Arc Light
Apparatus for different periods of time. Cycle 1 of ASTM 155 was applied,
where samples were treated by UV light at 340 nm wave length for 102
minutes at 63C, followed by 18 minutes light and water spray. As shown in
Figure 3 (a), in about 2 weeks time, tensile strength of the PTMEG based
elastomer lost more than 50% of its original value, while no decline was
observed for the PCL and PEAG based elastomers. Similar trend was observed
for elongation at break, as shown in Figure 3 (b).
1 00 0
8000
(a )
(b )
C on trol
7000
1 w ee k
6000
2 w ee k
5000
4000
3000
2000
C on tro l
1 W eek
80 0
Elon ga tio n, %
Te ns ile S tren gth (P SI)
9000
2 W eek
60 0
40 0
20 0
1000
0
P EA G
P CL
P T ME G
P EA G
P CL
P T ME G
Figure 3. Weatherability of 93 A MDI elastomers based on different backbones:

(a)Tensile Strength of MDI prepolymers cured by BDO after aged in Xenon Arc
Apparatus for different time; (b)Elongation at Break of MDI prepolymers cured by
BDO after aged in Xenon Arc Apparatus for different time.
As shown in Figure 2, the PTMEG based elastomer performed the best in

an 80% relative humidity environment at 80C, the failure of the PTMEG
based elastomer in such a short period of time in this test can be only
attributed to lack of UV stability of the elastomer. As for the PCL and PEAG
based elastomers, it is reasonable to assume moisture resistance of the
elastomers would play a role in the longer term. As PCL based elastomers
have better hydrolytic stability than PEAG based elastomers, PCL based
elastomers may prevail in this test over a longer period of time.
Besides moisture and UV, polyurethane elastomers often service areas
where contact with chemicals is a norm. In those applications, resistance to the
specific chemicals can have detrimental effect on service life of urethane
161
elastomers. For example, pipeline pigs made of polyurethane elastomers have

been widely used in the oil and gas industry for pipeline cleaning. In this
application, besides potential exposure to moisture, direct contact between the
urethane elastomer and crude oil, or refined oil such as gasoline and motor oil,
is unavoidable. Figure 4 shows change of volume, weight, and hardness after
the three 93 Shore A elastomers were immersed in gasoline at room
temperature for one week. A 40% increase in volume, a 30% increase in
weight and an 8% drop in hardness were observed after the PTMEG based
elastomer was immersed in gasoline for only a week. Under the same
conditions, the PCL based elastomer showed an 8% increase in volume, 6%
increase in weight and 2% drop in hardness. On the other hand, the PEAG
based elastomer only had 4% increase in volume, and a 2.5% increase in
weight, while no change in hardness was observed. Clearly, the PEAG based
elastomer performed the best under those conditions.
While exposure to moisture, heat, UV and chemicals is common in
urethane elastomer applications, direct and abrasive contact between urethane
parts and different substrates is inevitable. For example, abrasion resistance is
highly important in applications such as mining, pipeline pigs, squeegees, and
industry wheels and tires. Figure 5 shows Taber abrasion resistance of the
three 93 Shore A elastomers. The data indicated that elastomers based on PCL
and PEAG had similar abrasive resistance, and performed much better than
PTMEG based elastomer.
1. 4
P TME G
1. 2
PCL
% C h an ge
PEA G
1. 0
0. 8
0. 6
0. 4
0. 2
0. 0
V o lum e
W eigh t
H ard nes s
Figure 4. Changes on volume, weight and hardness of 93 Shore A MDI elastomers

after immersed in gasoline for a week at room temperature.
Rui Xie
Los s of W e igh t ( mg )/ 100 0 Cy cle s
162
80
60
40
20
0
P EA G
PC L
PTME G
Figure 5. Taber abrasion resistance of 93 Shore A MDI elastomers based on different

backbone.
One important application for urethane elastomers is industrial wheels,

tires and rollers. In this application, urethane elastomers are constantly running
at high-speed and under high-load. It is the intrinsic nature of virtually any
material to build-up heat while running at high-speed under load. Wheels, tires
and rollers made from urethane elastomers generate heat when they are
operating at normal conditions. Heat buildup can cause failure of urethane
parts by melting, tearing, or debonding [27]. Depending on how much heat is
generated and how fast the heat is dissipated to the environment, service life of
urethane parts differs. To improve the service life of urethane elastomers in a
dynamic environment, heat dissipation needs to be maximized, while heat
generation has to be minimized. Elastomers with improved dynamic properties
can generate less heat, thus run cool for extended time, therefore must be
selected. Heat dissipation van be addressed by engineering design of the
wheels, tires and rollers, but heat generation has to be solved from the material
standpoint.
Dynamic properties of urethane elastomers can be analyzed using a
Dynamic Mechanical Analyzer. A good compound for dynamic applications is
generally represented by low tan values and constant modulus values over
the working temperature range in which the parts will be utilized. As tan =
G/G, where G is the loss modulus and G is the storage modulus, a lower
tan value means that energy transferred to heat is much lower than energy
163
stored. Therefore, lower heat buildup occurs in high-speed, high-load bearing

applications. Figure 6 compares tan value for the three 93 Shore A
elastomers in a temperature range between 0C and 180C. The PEAG based
elastomer had a much higher tan value across the temperature range
compared to PCL and PTMEG based elastomers. PCL based elastomer had
higher tan value than the PTMEG based elastomer at low temperature, but its
tan value was comparable to that of the PTMEG based elastomer at higher
temperature.
0.1 4
PCL-MDI
P TME G-MDI
0.1 2
PEA G-MDI
T an
0.1 0
0.0 8
0.0 6
0.0 4
0.0 2
0.0 0
0
50
10 0
15 0
o
Te mp era tu re ( C )
Figure 6. Tan values of the three 93 Shore A elastomers at different temperatures.
Obviously, a PEAG based elastomer might not be the best choice for
dynamic applications if similar grades of PTMEG and PCL based elastomers
are readily available. As for PCL and PTMEG based elastomers, though the
PCL based elastomer has higher tan value at low temperature, some
engineers believe that it is the tan value at higher temperature that really
matters. The higher tan value at low temperature may suggest that a wheel
made from PCL based elastomers may build up heat faster than a wheel made
from PTMEG based elastomers when the wheel is cold. However, as the
164
Rui Xie
temperature increases, tan value decreases. At normal operating conditions,

temperature of the wheel will stabilize at a point where heat generated is equal
to the heat dissipated (the operating temperature of the wheel). This operating
temperature for a PCL based elastomer wheel might be slightly higher than
that of a PTMEG based elastomer, depending on the engineering design of the
wheels. However, considering the enhanced mechanical strength and
resistance to thermal degradation of the PCL based elastomers, whether PCL
based elastomers will out perform PTMEG based elastomers in the field will
likely depend on the real application environment.
Figure 7 shows the storage modulus, G, for the three 93 Shore A
elastomers over a temperature range of -100C to 200C. From the slope of the
profile between 50C to 150C, it is clear that PCL and PTMEG based
elastomers hold modulus better as temperature increases. This is very
important for dynamic applications accompanied by heat buildup that could
soften the elastomers, thus causing failure. Modulus starts to drop significantly
when the temperature is higher than 150C for all elastomers. However, the
PTMEG based elastomer has the lowest glass transition temperature (-56C),
followed by the PCL based elastomer (-31C). The PEAG based elastomer has
the highest glass transition temperature (-20C). The data suggest that PTMEG
based elastomers have the best low temperature performance, followed by the
PCL based elastomers, then the PEAG based elastomers.
As important as the dynamic properties of elastomers to the success of
wheel, roller and tire applications, cutting growth (flex fatigue) resistance has
been proved to be a key element that determines service life of wheels, tires
and rollers. As wheels, tires and rollers are constantly running at high speed
under load, small cracks in the structures can propagate over time, which
eventually results in failure. An elastomer with lower cutting growth resistance
leads to a rapid growth of the cut, thus cause an earlier failure. Generally,
polyester based elastomers possess much better flex fatigue resistance than
polyether based elastomers. However, polyester based elastomers, such as
elastomers made from the MDI-PEAG prepolymer, have much higher Tan
value compared to PTMEG based elastomers, as shown in Figure 6. As a
result, polyester based elastomers are not the best compound for dynamic
applications. Therefore, it is highly desirable to have a compound that
possesses dynamic performance of a polyether elastomer while maintaining
flex fatigue resistance of a polyester elastomer.
165
G ' (d yn /cm 2 )
1 0 10
P E A G -M D I
1 09
1 08
P CL -M D I
1 07
P TM E G -M D I
-10 0
-5 0
50
10 0
15 0
20 0
Te mp era tu re ( C )
Figure 7. Elastic modulus of the three 93 Shore A elastomers at different temperatures.
Figure 8 shows flex fatigue resistance of conventional MDI prepolymers

and stripped TDI prepolymers based on different polyol backbones. The MDI
prepolymers were chain-extended by BDO at 95% theory, which yielded
elastomers of 93 A hardness. The TDI prepolymers were chain-extended by
Ethacure 300 at 95% theory, which yielded elastomers of 80 A to 85 A
hardness. Flex fatigue results were obtained by using ASTM D3629.
Specimens were run at 500 rpm at 60 flex angle at room temperature. A
specimen is considered to fail when the cut growth reaches 0.8 inch. As shown
in Figure 8 (a), PCL and PEAG based elastomers failed at 40000 to 45000
cycles, while PTMEG based elastomer failed at 25000 cycles. The result
implies that PCL and PEAG based elastomers last 1.6 to 1.8 times longer than
PTMEG based elastomer. Similarly, as shown in Figure 8 (b), elastomers
based on stripped TDI-PCL and TDI-PEAG prepolymers last 2 times longer
than elastomer based on stripped TDI-PTMEG prepolymers. Due to the
shortcoming of PEAG based elastomers in dynamic performance and the
limitation of PTMEG based elastomers in flex fatigue resistance, PCL based
elastomers thus become the ideal choice for wheel, tire and roller applications.
Rui Xie
Number of Cycles @ Failure
50 00 0
(a )
40 00 0
30 00 0
20 00 0
10 00 0
0
P CL
P EA G
P T ME G
Number of Cycles @ Failure
166
18 00 0
(b )
15 00 0
12 00 0
9 00 0
6 00 0
3 00 0
0
P CL
P EA G
P T ME G
Figure 8. Cutting growth resistance of elastomers based on different backbones: (a)

93A MDI prepolymers cured by BDO at 95% theory; (b)85A stripped TDI
prepolymers cured by Ethacure 300 at 95% theory.
Table V. Application Advantages of PCL Based Elastomers.

Key Engineering
Properties
PTMEG Based
Elastomers
PCL Based
Elastomers
Stress-Strain
Tear Resistance
Compression Set
Resilience
Abrasion Resistance
Moisture Resistance
Gasoline Resistance
Resistance to Thermal
Degradation
Dynamic Performance
Cutting Growth
Resistance
Weatherability
+
+
+
+
+
+
+
+*
+
+
PEAG
Based
Elastomers
+
+
+
+
+: Good if this property is highly desired for the application

: Not very good if this property is highly desired for the application.
*: Need to be modified to perform.
CONCLUSION
Polyurethane elastomers based on PCL, PTMEG and PEAG were studied
side by side. PTMEG and PEAG are the most commonly used polyols for high
performance cast elastomers. Among the elastomers studied, PCL based
elastomers showed the best balance of properties. Table 5 summarized
167
findings of this study. As shown in the Table, PCL based elastomers are the
preferred choice for applications where a combination of engineering
properties is required. For example, for conveyor belt applications, toughness,
good dynamic properties, and in some cases excellent resistance to thermal
degradation are required. Due to superior performance in the areas above PCL
based elastomers should be the right choice for this type of application.
Furthermore, as PCL polyols offer a better balance of properties that
traditional polyols, such as PTMEG and PEAG, can not achieve, PCL based
elastomers may become the choice for many other applications.
BIOGRAPHIES
Rui Xie
Rui Xie earned a B.S. degree in physics from Jiangxi Normal University,
Nanchang, China in 1998 and a Ph.D. in polymer science from the Chinese
Academy of Sciences, Changchun, China in 1994. He was an assistant
professor for Changchun Institute of Applied Chemistry, Chinese Academy of
Sciences from 1994 to 1995, and a guest scientist of Institute of Material
Sciences, University of Connecticut at Storrs and National Institute of Science
and Technology, Gaithersburg, MD from 1996 to 1997. He Joined Uniroyal
Chemical Company, Inc. in 1998 as a research scientist for the
Adiprene/Vibrathane business. Rui joined the Dow Chemical Company in
2001 as a research specialist for the Polyurethane Systems House. Currently,
Rui is the technical leader for the Epoxy Specialty Platform, Dow Epoxy
Products.
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[3]
[4]
Z. Wirpsza, Polyurethanes: Chemistry, Technology and Applications.

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R.P. Redman, Developments in Polyurethanes, Vol. 1, Ch. 3, J.M.
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K. Kojio, S. Nakamura, M. Furukawa, Polymer 45, 8147(2004)
168
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Chapter 7
THE EFFECT OF BROMINATED FIRE

RETARDANTS ON THE PROPERTIES OF
THERMOPLSTIC ELASTOMERS BASED
ON PP AND EPDM
N. A. Khalturinskii, D. D. Novikov, L. A. Zhorina,
L. V. Kompaniets, T. A. Rudakova, L. A. Tkachenko
and E. V. Prut
Semenov Institute of Chemical Physics, Russian Academy of Sciences,
ul. Kosygina 4, Moscow, 119991 Russia
Abstract
The effect of fire retardants on the combustion and mechanical
properties of thermoplastic vulcanizates based on PP and EPDM was
studied. A modified mixture of decabromodiphenyl oxide and antimony
trioxide was used as a fire retardant. It was shown that the addition of fire
retardants results in a considerable increase of the oxygen index from
17.2 to 27.9% and the thermoplastic vulcanizate passes into the category
of low-combustible materials according to V0. The mechanical properties
of the blends containing up to 20 wt % fire retardant change
insignificantly and their rheological properties are deteriorated. The
mechanism of combustion of thermoplastic vulcanizates is proposed.
170
N. A. Khalturinskii, D. D. Novikov, L. A. Zhorina et al.
Keywords: thermoplastic elastomers, combustion, fire retardancy, coke

formation.
In recent years among multicomponent polymer systems, the materials

belonging to the class of thermoplastic elastomers (TPEs) have received wide
recognition. Thermoplastic elastomers are polymer materials, which combine
the mechanical properties of vulcanized rubbers with the processability by the
technology typical of linear thermoplastics. The production of such materials
allows one to combine two important qualities of each component, namely, to
retain elastic (rubberlike) properties of the resulting material with its
processability as a thermoplastic polymer [1, 2].
Among TPEs of different types, the compositions produced by the method
of dynamic vulcanization (which is based on the elastomer crosslinking in the
course of its blending with a thermoplastic) have a wide application. The
process of dynamic vulcanization allows one to decrease the particle size of
crosslinked elastomer and to obtain a more uniform particle distribution in the
polyolefin matrix. These TPEs were called thermoplastic vulcanizates (TPVs).
The blends of isotactic polypropylene (PP) with ethylenepropylenediene
elastomer (EPDM) present the most abundant and important group of TPEs
and TPVs due to their best mechanical properties and rather high service
temperature [3, 4]. TPVs based on PP and EPDM have a high resistance to the
action of ozone, UV radiation, chemicals, the minimum size tolerance for a
product, low shrinkage, impact resistance, bending strength, etc. The
mentioned materials can be used for manufacturing flexible parts in the
automobile, aircraft, cable, building and other branches of industry.
However, a low fire resistance of these materials presents a considerable
disadvantage. For example, the TPVs based on PP/EPDM have the oxygen
index OI = 18 that is an essential limitation for their application. When using
an oil-extended rubber (the content of paraffin oil up to 50%), which is
necessary for providing the desired properties of TPEs, results in even lower
fire resistance of material, i.e., in a higher flammability.
In the same time few works on the reduction of the TPV flammability are
known. For this purpose, brominated fire retardants (FRs) based on
tetrabromophthalate diol, tetrabromobenzoate, decabromodiphenyl oxide or
phosphorus-containing fire-resistant compositions on the base of
triarylphosphates, ammonium polyphosphate or ethylenediamine phosphate
are used. The desired level of fire resistance is attained at more than 30 percent
FR that results in a loss of the material performance and makes it significantly
more expensive [5, 8].
171
For example, ammonium polyphosphate (Hostaflame microencapsulated

by melamine resin) and ethylenediamine phosphates (Amgard NL,
ethylenediamine phosphate with amorphous silica gel) were used as FRs at
different ratios [5]. The satisfactory decrease of TPE flammability was
reached: when adding 3045% FR, a material with OI > 26 and
correspondence to V0 by UL-94 was obtained [6, 7]. Moreover, the authors
indicate that the addition of polyphosphates affects the process of dynamic
vulcanization.
The brominated FR composition based on decabromodiphenyl oxide and
antimony trioxide was described in [8], with the latter component being a
synergist of FR [9]. The maximum OI = 25.4 was obtained with 32% FR (25%
FR-10 and 7% Sb2O3).
In this work, the properties of TPV based on PP/EPDM with a modified
mixture of decabromodiphenyl oxide and antimony trioxide as a fire retardant
were studied.
The aim of this work was to estimate the effect of combination of FR and
polymer matrix on the flammability and mechanical characteristics of TPVs.
EXPERIMENTAL
In experiments, isotactic PP 21030-16 (Russia) with Mn = 7.7 x 104 and
Mw = 3.4 x 105, density 0.907 g/cm3, degree of crystallinity 55%, Tm = 165C,
MFI = 2.3 g/10 min (190C, 2.16 kg) and EPDM rubber Dutral TER 4535
(Polimeri Europa, Italy) with 50% oil introduced in the course of synthesis,
density 0.890 g/cm3, 34% propylene units and the Mooney viscosity 32 (at
125C) were used. 5-Ethylidene-2-norbornene (45%) was used as a diene
component of EPDM. Two rubbers differing in molecular mass were used in
experiments.
The dynamic vulcanization of PP/EPDM blends and their modification
with FRs were carried out in a closed Brabender mixer for 10 min at 190C
and rotor velocity of 100 rpm. A sulfur-based system (sulfur 1.00, zinc oxide
2.53, stearic acid 1.00, di-(2-benzthiazolyl) disulfide 0.25, and
tetramethylthiuram disulfide 0.73 phr) was used as a curative. The amounts of
the curative components were calculated for 100 phr EPDM [10].
A modified mixture based on decabromodiphenyl oxide (Chemtura) and
antimony(III) oxide (specifications 6-09-3267-84) was used as an FR. A
172
layered silicate Cloisite 20A (Southern Clay), which is a natural Na+montmorillonite modified by organic compounds was used as a nanofiller.
The plates (1.0 and 4.0 mm thick) from the prepared mixtures were
pressed at 190C and 10 MPa for 10 min with further cooling under pressure
to room temperature.
The dumbbell-shaped samples for mechanical tests with the working part
of 35 x 5 mm were cut from the obtained plates. The tests were carried out on
an Instron 1122 universal test machine at room temperature and the rate of the
upper traverse movement of 50 mm/min. >From the stressstrain curves, the
elastic modulus E (by the initial portions of curves), the ultimate tensile
strength b, elongation at break b, and stress at 100% elongation 100 were
determined. The results were averaged by 68 samples.
MFI of the compositions was measured on an IIRT-5 unit at 190C and
load of 10.6 kg according to GOST (State Standard) 11645-73.
The measurements of fire resistance were performed by OI according to
IS04589-2 [6].

Under real conditions, the combustion of polymer materials passes
through several successive stages, which sometimes can be superimposed. The
character of combustion process and the rate of weight loss upon burning of
polymer compositions are essentially influenced by the nature and content of
FR.
At present PP is most widespread synthetic polymer, however, relatively
low characteristics of heat and fire resistance present serious restrictions to the
conditions and range of its practical applications. Owing to its fully aliphatic
carbon structure, pure PP burns out rapidly and completely.
As was shown in [11], upon degradation at 280C, weight loss of PP
EPDM blends decreases some 520 times compared to pure PP. In this case
the weight loss is the same whether the rubber is vulcanized or not. This result
is related to the formation of a protective layer of degradation products on the
particle surface hindering the oxygen diffusion.
Currently it was shown that the fire retardation is favored by the presence
of two or more compounds, which hinder the inflammation of compositions.
In this case a significantly higher effect is attained compared to the effects
observed with individual FRs. This phenomenon is known as synergism.
173
The properties of TPVs with different contents of FR are given in Table 1.

Table 1. The effect of FR content on combustibility and mechanical
properties of TPVs
FR
content, wt
%;
,
MPa
100,
MPa
b,
MPa
b,
%
MFI,
g/10
min
Oxygen
index, %.
60.6
4.0
6.3
390
6.0
17.2
10
20
46.5
53.0
3.5
3.5
6.7
6.7
380
370
1.7
1.0
26.4
27.9
As can be seen from Table 1, the addition of FR results in a considerable

increase of OI from 17.2 to 27.9% and TPV passes into the category of lowcombustible materials according to V0. In this case the mechanical properties
of TPVs up to the FR content of 20 wt % are changed rather weakly. In the
same time the MFI drops, i.e., the processability of TPVs is deteriorated as the
FR content increases.
For PP nanocomposites, the combustibility decreases due to formation of
heat-resistant coke on the surface of burning polymer [12, 13]. In this case at
the filler content exceeding 5 wt %, the elastic modulus increases, and the
ultimate parameters (tensile strength and elongation at break) decrease.
The data on the effect of an FR/nanofiller composition (2.5/1) on the
combustibility and mechanical properties of TPVs are given in Table 2.
It is evident that the introduction of an FR/nanofiller composition results
in a gain in OI and elastic modulus, whereas the elongation at break and MFI
decrease. Such change is related to the presence of nanofiller, which is
obviously responsible for an increase in the elastic modulus and a lower
elongation at break [13].
The behavior of similar compositions on heating was studied by TGA and
it was shown that the addition of individual decabromophenyl oxide or
antimony trioxide does not change the patterns of degradation of the initial
composition [8]. The introduction of an FR/antimony trioxide mixture into
TPVs leads to essential changes in the process of degradation of the original
composition. In this case the synergistic effect of decabromophenyl oxide and
antimony trioxide manifests itself.
In all discussions on the mechanism of the joint action of halogenated
inhibitors and antimony oxides, as a rule, the mechanism related to the chain
174
termination and hence a decrease in reaction rates of gas-phase reactions

accompanying the polymer burning is suggested.
Table 2. The effect of composition based on FR and Cloisite 20A on
flammability and mechanical properties of TPVs
FR
content,
wt %;
0
,
MPa
100,
MPa
b,
MPa
b,
%
MFI,
g/10 min
Oxygen
index, %.
57.8
3.4
5.1
290
3.1
17.3
35
84.8
4.1
4.9
185
25.4 (V0)
As was shown in [14], the critical condition of diffusion combustion of

polymers is reduced to providing a lower concentration limit by fuel, i.e., the
generation of volatile combustible products of polymer degradation under the
action of heat flow at its surface. However, in all works dealing with the
mechanism of the action of halogenated inhibitors combined with antimony
trioxide, no mention has been made.
The thermograms (Figure 1) show that the degradation of TPVs
containing the composition as well as a decabromophenyl oxide/antimony
trioxide FR occurs in two stages [8]. This corroborates the assumption that the
addition of decabromophenyl oxide/antimony trioxide mixture results in the
synergistic effect in condensed phase at the stage of thermal degradation of
polymer material. The DTA data show that the introduction of FR into TPVs
changes essentially the position of heat evolution curves, which are shifted to
higher temperature region. At T = 400500C, due the processes of coke
formation, a protective layer of the degradation products is formed on the
material surface. This layer hinders the flow down and dropping of burning
melt and this was really observed upon combustion of TPVs synthesized in
this work.
175
Figure 1.TGA and DTA curves of (1) original TPV sample and (2) TPV sample with
the FR composition.
Thus, the following conclusions can be made:
the addition of a modified mixture of decabromophenyl oxide with

antimony trioxide increases the oxygen index of TPVs up to 27.9%
without deterioration of their mechanical properties;
in discussion on the mechanism of action of halogenated
inhibitors/antimony trioxide mixtures, not only the classical schemes of
inhibition must be considered, but the processes of degradation in
condensed phase on the burning surface are noteworthy. This, in turn, will
be an indication of the effectiveness of specific inhibitors for different
systems.
176
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[1]
Abdou-Sabet, S. and Datta, S., in Polymer Blends, Ed. by Paul, D.R.

and Bucknall, C.B., New York: Wiley, 2000, p. 998.
[2]
Prut, E.V., Klei Germet. Tekhnol., 2007, No 6, p. 6.
[3]
Coran, A.Y., Thermoplastic Elastomers: A Comprehensive Review, Ed.

by Legge, N.R., Holden, G.and Schroeder, H.G., Munich: Hanser, 1987,
p.133.
[4]
Karger-Kocsis, J. in Polymer Blends and Alloys, Ed. by Shonaike,

G.O.and Simon, G.P., New York: Marcel Dekker, 1999, p.125.
[5]
Kiran Pal and Rostorgi, J.N., J. Appl. Polym. Sci., 2004, vol. 94, p. 407.
[6]
Standard Test Method for Measuring the Minimum Oxygen,

Concentration to Support Candle Like Combustion of Plastic. Limiting,
Oxygen Index, LOI, ASTM2863 Philadelphia, 1990, p. 329.
[7]
UL-94. The Standard for Flammability of Plastic Materials for Parts in

Devices and Appliances, www. ul.com/plastics/flame.html .
[8]
Li Yu, Wenjun Wang and Weidong Xiao, Polym. Degrad. Stab., 2004,
vol. 86, p. 69.
[9]
Montezin, F., Lopez Cuesta, J.M., Crespy, A. and Georlette, P., Fire
Mater., 1997, vol 21, p. 245.
[10] 10 RF Patent No 2 069 217, 1996, Byull. Izobret., No 32.

[11] Skachkova, V.K., Erina, N.A. and Prut, E.V., Vysokomol. Soedin., Ser.
A, 2000, vol. 42, p. 1563.
[12] Lomakin, S.M., Dubnikova, I.L., Berezina, S.M. and Zaikov, G.E.,
Vysokomol. Soedin., Ser. A, 2006, vol. 48, p. 90-105.
[13] Dubnikova, I.L., Berezina, S.M., Korolev, Yu.M., et al., J. Appl. Polym.
Sci., 2007, vol. 105, p. 3834.
[14] Rudakova, T.A., Candidate Dissertation in Chemistry (Moscow, 2008).

Chapter 8
INTERFACIAL INTERACTION IN BLENDS OF

ELASTOMERS WITH DIFFERENT POLARITIES
N. M. Livanova*
Semenov Institute of Chemical Physics, Russian Academy of Sciences,
ul. Kosygina 4, Moscow, 119991 Russia
Abstract
The effects of isomers of butadiene units, the ratio of comonomers in
ethylene-propylene-diene terpolymers, and the degree of isotacticity of
propylene units in the layer on the intensity of interfacial interaction in
covulcanizates of butadiene-acrylonitrile rubbers of different polarities
and ethylene-propylene-diene terpolymers have been analyzed.
INTRODUCTION
The effects of isomers of butadiene units, the ratio of comonomers in
ethylene-propylene-diene terpolymers, and the degree of isotacticity of
propylene units in the layer on the intensity of interfacial interaction in
heterophase crosslinked blends of butadiene-acrylonitrile rubbers of different
polarities and ethylene-propylene-diene terpolymers have been analyzed.
E-mail address: livanova@sky.chph.ras.ru
178
N. M. Livanova
The density of the interfacial layer and the amount of crosslinks in it were
determined via study of the swelling in the selective solvent n-heptane (the
Zapp method [1, 2]) through deviation of the equilibrium degree of swelling
from the additive value. It was proposed that the interfacial layer in the
crosslinked blend of copolymers with different polarities may develop via
diffusion penetration of EPDM units into the nonpolar regions of BNR [3-8].
The goal of this study was to investigate the density of the interfacial
layer, which determines the amount of chemical crosslinks between phases
and its volume in heterophase crosslinked blends of elastomers of different
polarities.
The goal of this study was to compare intensities of interaction between
contacting phases involving various isomers of butadiene units, on the one
hand, and propylene portions of EPDM molecules with different degrees of
stereoregularities on the other hand.
EXPERIMENTAL
The objects of research were heterophase crosslinked BNR-EPDM (70 :
30) blends. At this content of the nonpolar component, a system of
interpenetrating crosslinked networks appears. The size of EPDM particles in
the blend depends on compatibility of the components and increases with the
polarity of BNR.
The commercial BNR of BNRS-18, BNRS-28, and BNRS-40 brands
containing 18, 28, and 40 wt % acrylonitrile units and having the Mooney
viscosity value (at 100C) 40-50, 45-65, and 45-70 arb. units, respectively,
were used. The amounts of 1,4-trans-, 1,2- and 1,4-cis-butadiene units (bands
at 967, 911, and 730 cm-1) were determined by IR spectroscopy with the use of
extinction coefficients taken from [9] (table 1).
We used EPDM of the Royalen brand (Uniroyal, USA) and of the Keltan
brand (DSM, Holland) with different proportions of ethylene and propylene
units and of the diene comonomer, ethylidenenorbonene (ENB). The
composition; the molecular-mass characteristics [10]; the Mooney viscosity;
the degree of isotacticity of propylene units of EPDM; and the units' content,
as estimated by IR spectroscopy [11, 12], and the amount of fraction insoluble
in toluene at room temperature are summarized in table. 2. The length
distributions of ethylene and propylene sequences as estimated by IR
spectroscopy [13, 14], are listed in table 3 [15,16]. The optical density of
bands is normalized to the optical density of the 1465 cm-1 band, which is
179
common for PP and PE [13]. For the ethylene comonomer, the content of
sequences of various lengths was calculated from extinction coefficient
measurements [14]. The amounts of 1-butene (765 cm-1) and poly(l-butene)
(787 cm-1) in CCL4 solution with a gel (dissolution for 1 day at 20C) and
without any gel, was estimated [13]. For high-ethylene content EPDMs of both
companies (R 512 and EPDM 778), a great amount of I-butene and poly(1butene) is concentrate in the gel (table 3).
In the case of BNR and EPDM, the sulfur-sulfen-amide and peroxide [17]
vulcanization systems, respectively, were employed. Each rubber was mixed
with the corresponding vulcanization system on a roller mill at 40-60C for l5
min. Then, the rubbers were blended under the same conditions. The blends
were vulcanized at 170C for 15 min.
Table 1. Isomeric composition of butadiene units in butadieneacrilonitrile copolymers
Copolymer
BNRS-18
BNRS -28
BNRS -40
Content of units, %
1,4- trans
1,2
82.0
8.2
76.4
1.4
93.0
4.4
1,4-cis
9.8
9.2
2.6
The density of the interfacial layer and the amount of crosslinks in this
layer were characterized by calculation of the deviation of the equilibrium
degree of swelling Qeq from additive values toward increase in the nonpolar
solvent n-heptane [1, 2]. The deviation is related to a weak interfacial
interaction between thermodynamically incompatible polymer components,
one of which contains polar units. In such systems, only local segmental
solubility of nonpolar chain portions is possible [3-7] under the assumption of
pair interaction between dissimilar molecules [4]. A lower density of chain
packing in the interfacial layer and a smaller amount of crosslinks result not
only from the low com-patibility of polybutadiene and polyolefin copolymers
but also from chemical bonds between butadiene units and polar acrylonitrile
units that are statistically distributed in BNRS-18 or occur as multiblocks in
BNRS-40 [18, 19] reducing the compatibility of the components. The
looseness of the interfacial layer provides a smaller amount of crosslinks [7].
The Flory-Huggins interaction parameters for polybutadienes and
EPDM with n-heptane and the solubility parameter are adduced in [20, 21].
Table 2. Composition and basic characteristics of ethylene-propylene-diene elastomers
Elastomer
Ethylene:
propylene
weight
ratio
Degree of
isotacticity,%
Content
of
propylene,
wt %
Content of
the gel
fraction,
%
Content
of ENB,
wt %
w 10-5
Mn 10-5
Mw/Mn
EPDM
778
EPDM
714
EPDM
712
EPDM R
521
EPDM R
505
65:35
50:50
52:48
13
12
11
32
46
46
15
9
13
4.5
8
4.5
2.0
3.01
1.35
1.60
1.48
1.88
52:48
57:43
22
24
46
41
13
7
5
8
2.11
-
EPDM R
512
68:32
20
37
25
1.95
1.61
Narrow
molecularmass
distributionx
1.50
Certificate data.
Mooney
viscosity
at 125
(rel.
units)
63
63
63
29
55
57
Table 3. Content of ethylene (Gn) and propylene sequences (Dm) of various lengths, 1-butene
and poly(l-butene) in EPDM
Elastomer
Ethylene::
propylene
Degree of
isotacticity,%
G n=1
(815 cm-1)
Gn=2
(752 cm -1)
Gn=3
(735 cm -1)
Gn5
(722 -1)
Dm4
(973 cm -1)
Dm<10
(1155 cm -1)
1-Butene
(765 cm -1)
EPDM R 512
(solution)
EPDM R 512
(with gel)
EPDM R 505
(solution)
EPDM R 521
(solution)
55:45
15
0.041
0.043
0.092
0.167
0.053
0.074
0.014
Poly-(1Butene)
(787 cm -1)
0.001
63:37
19
0.40
0.146
0.185
0.249
0.062
0.079
0.259
0.349
59:41
24
0.079
0.035
0.085
0.184
0.061
0.052
~0
~0
54:46
22
0.048
0.024
0.045
0.146
0.060
0.173
~0
~0
EPDM R 521
(with gel)
EPDM 778
(solution)
EPDM 778
(with gel)
EPDM 714
(solution)
EPDM 712
(solution)
EPDM 712
(with gel)
54:46
30
0.065
0.016
0.024
0.131
0.076
0.087
0.055
0.048
70:30
13
0.043
0.030
0.069
0.279
0.049
0.073
0.025
0.051
68:32
13
0.119
0.142
0.124
0.293
0.040
0.067
0.208
0.256
57:43
12
0.045
0.020
0.051
0.175
0.043
0.079
~0
~0
57:43
11
0.053
0.027
0.096
0.167
0.035
0.065
~0
~0
57:43
20
0.079
0.040
0.053
0.176
0.054
0.083
0.048
0.044
Our data
182
N. M. Livanova
The deviation of Qeq from additive values - was calculated by the

formula [2]:
- = [(Qad - Qeq)/( Qad Q2)] x 100%,
where Qeq is the equilibrium degree of swelling of a covulcanizate; Qad is the
additive value of swelling in a given solvent, as calculated from the
equilibrium degree of swelling of vulcanizates for each rubber; and Q2 is the
share of swelling of the second elastomer (BNR).

Calculations showed that the value of - for BNRS-28 is somewhat lower
than that for BNRS-18, even though the polarity of the former rubber is
higher. This phenomenon was attributed to the effect of various butadiene
isomers on compatibility with ethylene-propylene-diene elastomers (table 1).
The value of -a depends on the amount of crosslinks in the interfacial layer
and its volume. Let us assume that the major fraction of polar units of BNR is
uninvolved in its formation and the value of -a was recalculated to the 100%
content of butadiene units -100% (figure 1) and used to characterize the
structure of the interfacial interaction zone and the amount of crosslinks
contained in it. In such a manner, the effect of the interfacial layer volume
could be minimized. As will be shown below, this situation may not be
attained in all cases.
Figure 1 plots the value of -100% as a function of the total content of 1,4cis- and 1,2-butadiene isomers. It is seen that a linear decrease in the value of 100% with an increase in the total content of 1,4-cis and 1,2 units is observed
for the crosslinked blends of BNR with all DSM EPDM samples characterized
by a low isotacticity of propylene (table 2). The fact that the value of -100%
decreases in proportion to the amount of 1,4-cis and 1,2 isomers of butadiene
units for EPDM-based blends provides evidence that the density of the
transition layer increases. This circumstance implies that the mutual solubility
of EPDM comonomers and butadiene units that occur for the most part in the
1,4-trans configuration in the neighborhood of these isomers is improved.
The region of interfacial interaction is bounded by nonpolar BNR units.
The compatibility of chain portions of these EPDM samples with the polar
acrylonitrile groups is ruled out. As the proportion of propylene units in
EPDM is increased, the compatibility of the components, the density of the
interfacial layer, and the amount of crosslinks in it drop sharply (the absolute
183
- 1 0 0 % ,%
value of -100% increases). Thus, the higher the content of atactic propylene
units in EPDM, the lower the adhesion interaction of the components and the
worse its compatibility with BNR. The strengthening of interfacial interaction
with an increase in (l,4-cis and 1,2 units) for EPDM 778, EPDM 714, and
EPDM 712 by 2.0, 1.4, and 1.3 times, respectively, is apparently explained by
the loosening effect of these isomers on the structure of the nonpolar phase of
BNR comprising for the most part 1,4-trans units (table 1), which show the
tendency toward ordering at the low content of acrylonitrile and other isomers
[18, 19, 22]. Ordered structures worsen compatibility of polymers even to a
higher extent [3-8, 23].
1
2
3
120
4
5
6
80
40
15
25
c, %
Figure 1. The plot of -100% vs. the total content of 1,4-cis and 1,2 units in BNR for
EPDM-based covulcanizates. Here and in Figs. 2-4: (/) R 512, (2) R 505, (3) R 521, (4)
778, (5) 714, and (6) 712.
When the Uniroyal EPDM, which is characterized by a high

stereoregularity of propylene sequences, was tested in blends, no
proportionality between the values under consideration was observed
(figure 1).
184
N. M. Livanova
120
100%
,%
For BNR covulcanizates with EPDM R 512 containing a large proportion

of ethylene units and distinguished by the presence of stereoregular propylene
sequences, the value of -100% linearly decreases with the content of butadiene
units by a factor of 2.6 (figure 2). This fact leads us to infer that, firstly,
ethylene units adjoining predominantly short isotactic propylene sequences are
well compatible with all isomers of butadiene units. Secondly, an increase in
the density of the interfacial layer and in the amount of crosslinks in it with a
rise in the proportion of nonpolar units in BNR implies that EPDM molecular
frag-ments may penetrate into BNR regions that apparently contain single
polar acrylonitrile groups. Otherwise, the value of -100% should be
independent of the proportion of polar units in BNR since calculations have
been made with due regard for their influence on the size of the interfacial
interaction zone. Possibly, rigid isotactic propylene helices occurring in
EPDM can penetrate into regions largely composed of single acrylonitrile
units.
80
40
0
55
75
C,%
Figure 2. The plot of - 100% vs. the total content of butadiene units in BNR for
EPDM-based covulcanizates.
For the covulcanizates of R 521 EPDM, which contains a large amount of

isotactic propylene sequences [15, 24], the proportional decrease in the value
of - by a factor of 1.85 is observed in the - - (l,4-cis and 1,2 units)
coordinates (figure 3). Consequently, at a high content of isotactic propylene
units, EPDM shows better compatibility with BNR if the butadiene
comonomer is enriched with 1,4-cis and 1,2 units. The values of - do not take
185
into consideration restrictions related to the mutual interpenetration of

segments of dissimilar chains associated with the presence of polar groups in
BNR. As a result, it is not improbable that BNR portions containing polar
groups may be involved in the interfacial interaction region. This circumstance
is related to the specific features of BNR interaction with EPDM containing a
large proportion of isotactic propylene chain fragments. This observation may
be attributed to the rigidity of isotactic propylene sequences arising from
hindered conformational transitions. The potential barrier to transitions
between rotational isomers of monomer units for the isotactic PP is 21 kJ/mol,
while for PE, the potential barriers of T-G and G-G transitions are 2.5 and 8.810 kJ/mol, respectively [25]. An increase in the volume of the interfacial layer
may result from penetration of isotactic propylene fragments into regions
containing single polar groups; as a consequence, the total amount of
crosslinks increases with the local reduction in density.
- , - cis+1,2
60
40
20
0
5
15
25
c, %
Figure 3. The plot of -a for EPDM R 521 (1) and -acis + 1,2 for EPDM R 505 (2) vs. the
total content of 1,4-cis and 1,2 units in BNR for EPDM-based covulcanizates.
For blends with EPDM R 505, which contains a large amount of ENB, the
linear dependence is attained when the values of -100% are recalculated to the
1 % of the sum of 1,4-cis and 1,2 units in BNR(-cis+1,2) (figure 3). An analysis
of -cis+1,2 the versus (l,4-cis and 1,2 units) curves demonstrates that -cis+1,2
decreases by a factor of 5.3 with an increase in the total amount of these
butadiene unit isomers. The data presented above suggest that the chain
fragments of this EPDM are well compatible only with those portions of
butadiene chains that contain 1,4-cis and 1,2 isomers, while in the case of 1,4trans units, compatibility is much worse. It appears that the bulky diene group
186
N. M. Livanova
significantly hinders the incorporation of EPDM chain portions into butadiene

regions of BNR.
Thus, the structure of interfacial interaction zone depends on the
comonomer composition of EPDM, the stereoregularity of propylene units,
and the isomerism of butadiene units. The amount of interphase crosslinks
grows with an increase in the total content of 1,4-cis-and 1,2-butadiene units in
BNR except EPDM with a high content of ethylene units and a low content of
pre-dominantly isotactic propylene units. A high compatibility of BNR with
this EPDM may be provided by interaction with butadiene units regardless of
their isomeric composition.
Owing to conformational restrictions, stereoregular propylene units can
penetrate into BNR regions that apparently contain single polar acrylonitrile
units. As a result, the volume of the interfacial zone increases but its density
and the amount of crosslinks contained in it decrease locally. The
compatibility of propylene fragments of EPDM chains that predominantly
occur in the atactic configuration with butadiene units is much worse. The
interfacial layer is looser, and the region of diffusion penetration of phases is
confined by the presence of nonpolar units. The proportional growth of the
density of interfacial layer and the amount of crosslinks with an increase in the
total amount of isomers of buta-diene units contained in BNR in a smaller
amount is explained by disordering of 1,4-trans units. As a result, their
compatibility with portions of EPDM molecules is facilitated.
The ability of EPDM that contains a large amount of diene units and
stereoregular propylene units to compatibilize with butadiene units of BNR is
close to that of EPDM with a low degree of isotacticity of the propylene
comonomer and is determined by steric hindrances related to the presence of
the bulky diene. However, a higher content of diene groups ensures better
crosslinking of EPDM with the matrix. As a result, the total amount of
crosslinks between phases is higher than that for blends with EPDM having
the same ratio of ethylene and propylene units but a smaller amount of diene
(cf. EPDM R 505 and R 521, EPDM 714 and EPDM 712).
The largest amount of crosslinks in the interfacial layer forms when
EPDM with a high content of ethylene units is used despite the moderate
amount of diene contained in it.
187
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INDEX
A
accessibility, 39
acetone, 52
acid, 68, 173
acidic, 66, 77
acrylate, viii, 37, 40, 41
acrylonitrile, xii, 179, 180, 181, 184, 186,
188
actuation, 91, 92
actuators, 91
adhesion, ix, 38, 39, 40, 44, 48, 49, 50, 51,
52, 53, 54, 61, 154, 185
adhesion interaction, 185
adhesions, 55
adhesive properties, 47, 57
adjustment, ix, 59
adsorption, viii, ix, 38, 39, 44, 49, 50, 51
amine, 24
amino, 24
ammonium, 172, 173
amorphous, 173
amplitude, 82
anchorage, 39
antimony, xii, 171, 173, 175, 176, 177
atomic force, 47
B
band gap, xi
bandwidth, xi
barriers, 187
base, ix, 54, 59, 60, 67, 70, 172, 173
beams, 81
behavior, 175
behaviors, 11, 12
bending, 172
benefits, 155
binary blends, 27
biochemistry, 55
biocompatibility, 39
biological fluids, 39
biological systems, 87
biomaterials, ix, 38, 39, 40, 48, 52, 54, 56
biomedical applications, vii, ix, 38, 39, 54
biosensors, 39
biosynthesis, 55, 57
biotechnological applications, 48
blends, vii, viii, xii, 1, 2, 3, 7, 10, 16, 18, 20,
24, 25, 26, 27, 28, 29, 31, 32, 171, 172,
173, 174, 179, 180, 181, 184, 185, 187,
188
blood, 39, 52
bonding, 65, 162
bonds, 63, 181
branching, 10, 18, 29
brittleness, 3
building blocks, 154
burning, 174, 175, 176, 177
butadiene, xii, 3, 179, 180, 181, 184, 186,
187, 188
190
Index
C
carapace, x, 79, 83, 88, 89
carbon, 63, 174
casting, 80, 82, 83, 88
cell culture, viii, ix, 38, 40, 42, 44, 50, 52,
56
cell line, 51, 52, 53
chain molecules, 14
chain termination, 176
challenges, 39
chiral molecules, x
classes, 39, 40
classical, 177
cleaning, 163
cleavage, 155, 159
clusters, 50
coatings, 39, 162
coke, 172, 175, 176
collagen, 55, 57
color, x, 80, 91, 93
combustibility, 175
combustion, xii, 171, 172, 174, 176
commercial, xi, 153, 180
commodity, 38
compatibility, viii, 2, 24, 25, 27, 180, 181,
184, 186, 187, 188
competition, 12, 17
compilation, vii
components, 173, 180, 181, 184
composition, ix, 39, 41, 43, 59, 61, 69, 74,
76, 173, 175, 176, 177, 180, 181, 188
compounds, 156, 159, 174
compression, 4, 5, 11, 12, 19, 157
computer, 27
concentration, 176
conduction, 12
conductivity, 61
configuration, 14, 80, 184, 188
confinement, viii, 2, 18, 19, 20, 32
connective tissue, 52
conservation, 81
controversial, 9
cooling, 12, 13, 17, 19, 92, 174
copolymer, 3, 18, 24, 156
copolymers, 56, 180, 181

correlation, 5, 49
cost, ix, 24, 25, 79, 80, 155
covering, 83
cracks, 8, 162, 166
critical value, xi
crosslinking, 172
crude oil, 163
culture, ix, 38, 40, 44
cycles, 21, 22, 167
cytocompatibility, ix, 38, 39, 52
cytotoxicity, 50, 52
D
damping, 30
decabromodiphenyl oxide, xii, 171, 172,
173
decay, 68
deformation, 3, 5, 8, 10, 24, 26, 30, 45, 46,
91
degradation, 4, 22, 159, 174, 175, 176, 177
degree of crystallinity, 173
denaturation, 49
density, 173, 180, 181, 184, 186, 187, 188
depth, xi, 90
derivatives, 48
deviation, 180, 181, 184
diffraction, x, 6, 7, 21, 79, 80, 82, 85, 86,
87, 90, 91, 92, 93
diffusion, 174, 176, 180, 188
dimethacrylate, 40
discretization, 12
dispersion, 16, 86, 93
displacement, 7, 8, 80, 84
distribution, 12, 27, 80, 82, 83, 172
disulfide, 173
domain structure, 154
dosage, 5, 24
drawing, 10
drug delivery, 39
drying, 82
ductility, 9, 10
dynamic mechanical analysis, 43
Index
E
elastic fracture, 4
electrolyte, 65
electron, 16, 87
elongation, x, 79, 82, 84, 85, 87, 157, 161,
162, 174, 175
embossing, 45, 46
encoding, 80
endurance, 69, 71, 76
energy, 5, 10, 14, 19, 23, 27, 30, 31, 44,
161, 164
engineering, 39, 53, 54, 56, 60, 87, 156,
164, 166, 169
entropy, viii, 2, 14, 32
environment, 20, 61, 63, 65, 71, 74, 76, 77,
159, 161, 162, 164, 166
epitaxial growth, 30
equilibrium, 42, 82, 180, 181, 184
equipment, 3
ester, xi, 153, 155, 159
etching, 29, 87
ethanol, 52
etherification, ix, 59, 63, 76
ethylene, vii, viii, xii, 1, 3, 24, 37, 40, 54,
55, 56, 57, 179, 180, 182, 183, 184, 186,
188
ethylenediamine, 172, 173
evidence, 30, 159, 184
evolution, 20, 32, 176
exposure, 161, 163
extinction, 180, 181
extrusion, 20, 24
F
fabrication, x, 56, 79, 80, 87, 91, 93, 94
families, 155
fiber, 16, 18, 19
fibroblasts, ix, 38, 50, 52
films, 4, 5, 10
filters, x
financial, 33, 54
flame, 178
191
flammability, 172, 173, 176

flex, xi, 153, 166, 167
flexibility, 55
flow, 19, 176
fluid, ix, 44, 59, 60
fluorescence, 52, 54
fluorine, 52
force, 19, 30, 92
formation, 11, 14, 32, 39, 52, 65, 172, 174,
175, 176, 184
formula, 184
fouling, 48
fracture toughness, vii, 2, 20, 22, 23, 32
fragments, 187, 188
free energy, 14
friction, 44
fuel, 176
functionalization, 41, 54
fusion, 3
G
gas, 176
gel, 41, 44, 47, 65, 173, 181, 182, 183
generation, 176
geometry, ix, 38, 51, 53
glass transition, 44, 154, 166
glucose, 63
glycol, 40, 56, 155
gold nanoparticles, 47, 48, 49
grades, 165
gratings, x, 79, 80, 82, 85, 93
groups, 184, 186, 187, 188
growth, xi, 7, 10, 12, 14, 17, 19, 24, 29, 39,
44, 48, 55, 57, 153, 155, 156, 166, 167,
168, 188
H
halogenated, 175, 176, 177
handedness, x, 10
hardness, 157, 158, 163, 167
heat, 174, 175, 176
heating, 175
192
Index
heavy metals, 67, 68

height, 11
heptane, 180, 181
hexane, 52
history, 11
hologram, 81, 84
human, ix, 38, 52, 53
humidity, 161, 162
hydrocarbons, 155
hydrogels, viii, ix, 38, 41, 43, 48, 49, 50, 51,
54, 55, 57
hydrolysis, 155
hydrolytic stability, 155, 162
hydrophilicity, 48
hydrophobicity, 39, 44, 49
hydroxyl, 24
I
ideal, x, 79, 80, 167
illumination, viii, 37
image, x, 27, 47, 48, 53, 79, 82, 84, 89
impact strength, viii, 2, 3, 25, 26, 32
implants, 39, 55
imprinting, 40, 48
in vitro, 39
in vivo, 39
incidence, xi, 86, 87, 90, 93
indication, 177
industries, 3
industry, 163, 172
inflammation, 39, 174
inflammatory responses, 53
inhibition, 177
inhibitors, 175, 176, 177
initiation, 31
intensity, xii, 179
interaction, xii, 179, 180, 181, 184, 186,
187, 188
interface, 27, 39, 57, 90
interfacial adhesion, 25
interfacial layer, 180, 181, 184, 186, 187,
188
interference, 80
interphase, 27, 188
inversion, 89
ions, 63, 65
isolation, 18
isomers, xii, 179, 180, 184, 185, 186, 187,
188
isotactic polypropylene, vii, 1, 172
J
joints, 60, 62, 71, 78
L
lamella, 11, 30
landfills, 66, 77
lead, 10, 18, 39
leakage, 73
ligament, 5, 6, 7, 9, 23, 27, 28
light, viii, x, 37, 86, 93, 155, 159, 162
limitation, 172
linear, 85, 172, 187
lithography, x, 44, 45, 55, 56, 79, 80, 85, 87,
88, 89, 93
M
macromolecular chains, 22
macromolecules, 14, 40
macrophages, ix, 38, 52, 53
man, 87
manipulation, 5
manufacturing, 156, 172
mass, 173, 180, 182
matrix, viii, 2, 3, 16, 20, 24, 25, 27, 28, 30,
31, 154, 172, 173, 188
matter, 158
measurement, 6, 8, 12, 42, 90, 174, 181
mechanical properties, viii, xii, 2, 3, 20, 22,
24, 25, 26, 32, 40, 41, 42, 43, 54, 155,
171, 172, 175, 176, 177
medicine, 39
melamine, 173
melt, vii, 1, 3, 4, 176
melting, 3, 11, 164
Index
melting temperature, 3
memory, x, 80, 91, 92, 93
metals, 67
microfabrication, 39
micrometer, ix, 38, 41, 47, 50, 51
micropatterns, ix, 38, 40, 52, 53
microscope, 6, 16
microscopy, 47, 52, 54
microstructure, 9
microstructures, 89, 90
migration, 40
mixing, vii, 1, 3, 154
modifications, xi, 2
modulus, 22, 24, 25, 26, 42, 43, 82, 164,
166, 167, 174, 175
moisture, 159, 161, 162, 163
mold, 4, 45, 46, 47, 80, 82, 83, 86, 89, 156,
157
molecular mass, 173
molecular structure, 154, 158
molecular weight, 40, 41, 154, 158
molecules, xi, 10, 14, 30, 48, 65, 180, 181,
188
monomer, 187
montmorillonite, 174
morphology, 3, 10, 16, 18, 20, 31, 52, 90
movement, 174
multicomponent polymer systems, 172
muscles, x, 91
N
nanocomposites, 175
nanofabrication, 39
nanofiller, 174, 175
nanoimprint, 44, 45, 56
nanolithography, 40
nanometers, 43
nanostructures, 56
natural, 174
norbornene, 173
nucleating agent, vii, 1, 3
nucleus, 29, 30
193
O
oil, 3, 163, 172, 173
one dimension, 12, 81
opportunities, 54
organic, 52, 67, 174
oxidation, 159
oxide, xii, 171, 172, 173, 175, 176, 177
oxygen, xii, 171, 172, 174, 175, 176, 177,
178
ozone, 172
P
parallel, xi, 29
parameter, 181
particles, 180
percolation, 27
periodicity, ix, x, 38, 53, 79, 89
permeability, 78
permission, 6, 7, 8, 9, 11, 12, 13, 15, 17, 18,
19, 21, 22, 23, 41, 43, 44, 45, 46, 47, 48,
49, 50, 51, 52, 53
peroxide, 181
pH, 62, 65, 66, 67, 77
phase transformation, 91
phenotype, ix, 38, 53
phosphate, 172, 173
phosphorus, 172
photographs, 27
physics, 169
pigs, xi, 153, 163
pitch, 86, 87, 90
plastic deformation, 4, 5, 6, 10, 24, 30
plasticity, 5
plastics, 20, 24, 38, 178
platform, ix, 38
polar, 181, 184, 186, 187, 188
polarity, 180, 184
polybutadiene, 155, 181
polydimethylsiloxane, 155
polyesters, 155
polyether, viii, 37, 40, 54, 56, 154, 155, 157,
159, 166
194
Index
polyisobutylene, 155
polyolefin, 172
polyphosphates, 173
polypropylene, vii, 1, 2, 172
polystyrene, ix, 38, 44
polyurethane, 154, 155, 156, 161, 162
porosity, 41, 42
preparation, viii, ix, 2, 24, 31, 79, 80
pressure, 174
prevention, viii, 38
production, 172
production costs, 94
pro-inflammatory, 53
propagation, x
proportionality, 5, 185
propylene, vii, xii, 1, 3, 40, 173, 179, 180,
182, 183, 184, 185, 186, 188
proteins, 39, 48, 55, 57
pumps, xi
R
radiation, 172
radius, 91
range, 174
reaction rate, 176
reactions, viii, 37, 39, 176
reactive groups, 41
reactivity, 41, 156
reading, 6
recognition, 172
reconstruction, x, 79, 82
recrystallization, 10
recycling, 20
reduction, 187
reflectivity, 87
refractive index, 81, 90
regression, 5, 8, 23
relaxation, 160
relief, 80
remittances, xi
repellent, 48, 49, 54
replication, 43, 45, 47, 80, 82, 83, 94
reproduction, 86
requirements, 5, 8
researchers, 9
residues, 50
resilience, 86, 157, 158
resin, 173
resistance, ix, xi, 3, 8, 44, 49, 60, 61, 69, 71,
73, 74, 75, 76, 77, 153, 154, 155, 156,
157, 159, 160, 161, 162, 163, 164, 166,
167, 168, 169, 172, 174
resolution, 55
response, 52, 53, 54, 55, 87, 91
restrictions, 174, 187, 188
retardation, 174
rheological properties, xii, 171
rheometry, 42
rigidity, 187
rods, 18
room temperature, 4, 40, 45, 156, 163, 167,
174, 180
roughness, 39, 90
S
salinity, 65
salts, 65
sample, 177
scattering, 7, 90
science, 54, 169
scope, 47
screw dislocations, 10
selectivity, x, 4, 39, 79, 82, 84, 93
self-similarity, 7
sensitivity, 39
serum, 39
shape, viii, x, 5, 16, 18, 38, 51, 80, 89, 91,
92, 93
shear, vii, 1, 3, 16, 27
showing, 25, 27, 63, 77
silica, 173
silicate, 174
silicon, 40, 46, 47, 48, 49
simulation, 32
skeleton, 18, 19
soft lithography, vii, x, 44, 79, 80, 82, 86,
87, 89, 91, 94
solubility, 181, 184
Index
solution, 18, 40, 57, 65, 68, 181, 183
solvents, 67, 68
specifications, 173
spectroscopy, 85, 180
spherulite, 18, 29, 30
stability, 77, 155, 162
standard deviation, 42
state, 14, 39, 43, 82, 91, 92
steel, 60, 61, 62, 71, 76, 77
stem cells, 54
stoichiometry, 154, 156, 157
storage, x, 4, 79, 80, 81, 93, 164, 166
strength, 172, 174, 175
stress, xi, 8, 27, 30, 157, 158, 159, 160, 174
stretching, 81, 84, 85
structure, xi, 9, 16, 17, 18, 19, 29, 30, 34,
154, 156, 158, 159, 174, 184, 185, 188
substrate, 40, 47, 50, 53, 55, 57, 80, 85, 86,
93, 154, 163
sulfate, 68
sulfur, 173, 181
swelling, ix, 40, 41, 59, 60, 61, 62, 63, 64,
65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75,
76, 77, 180, 181, 184
symmetry, x, 17
synergistic, 175, 176
synthesis, 41, 155, 156, 173
synthetic polymers, 40
systems, 181
195
therapeutics, 39
thermograms, 176
thermoplastic, xii, 171, 172
thermoplastics, 3, 172
time frame, 52
tissue, ix, 38, 39, 44, 53, 54, 56
tolerance, 172
toluene, 154, 180
transformation, xi, 12, 21, 30
transmission, 90
transparency, 80
treatment, ix, 59, 60, 61, 62, 76
U
uniform, 3, 65, 81, 172
universal test machine, 174
urethane, 154, 155, 159, 162, 163, 164
V
values, 181, 184, 185, 186, 187
variations, 22, 42
velocity, 173
versatility, 80, 91, 94, 154
viscosity, 16, 173, 180, 182
voiding, 10
vulcanizates, vii, xii, 1, 3, 10, 171, 172, 184
vulcanization, 3, 172, 173, 181
T
techniques, ix, 40, 79, 80, 87, 94, 154, 156
technologies, 91
technology, x, 39, 172
teflon, ix, 38, 40, 47
tensile, 22, 157, 161, 162, 174, 175
tension, 5, 6, 157
testing, 6, 69, 156, 161
W
wettability, ix, 38, 39, 44, 48, 49
Y
yield, 5, 22, 25, 26, 45, 47, 49

Elastomer S

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MATERIALS SCIENCE AND TECHNOLOGY

MATERIALS SCIENCE AND

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MATERIALS SCIENCE AND TECHNOLOGY

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Published by Nova Science Publishers, Inc. New York

-Nucleated ThermoplasticVulcanizates Based

Patternable Biomaterials; Elastomers for

Jovan Balcazara and Edgardo Paules

entropy in the temperature gradient field, resulting from a decrease of the

adhesion. PFPE-elastomers were also expected to be anti-adhesive to cells,

Jovan Balcazara and Edgardo Paules

and versatile fabrication protocols, have proven to be ideal materials for

Jovan Balcazara and Edgardo Paules

Chapter 7 - The effect of fire retardants on the combustion and mechanical

In: Elastomers: Types, Properties and Applications ISBN 978-1-61470-198-9

Corresponding authors. Tel.:/fax: + 86 28 8546 0130. E-mail address: ysjsanjin@163.com.

Wei-Kang Wang, Xue-Gang Tang, Rui-Ying Bao et al.

-Nucleated Thermoplastic Vulcanizates Based

Wei-Kang Wang, Xue-Gang Tang, Rui-Ying Bao et al.

-Nucleated Thermoplastic Vulcanizates Based

where L is the ligament length; B is the specimen thickness; Wf is the total

Wei-Kang Wang, Xue-Gang Tang, Rui-Ying Bao et al.

Wide-angle X-ray diffraction (WAXD) measurement was carried out to

-Nucleated Thermoplastic Vulcanizates Based

where I 1 is the intensity of the (300) reflection of the phase and I 1 , I 2

nucleating agent content (%)

The load-displacement curves of DENT specimens of TPV1 and TPV6 are

Wei-Kang Wang, Xue-Gang Tang, Rui-Ying Bao et al.

displacement to failure all increased regularly with increasing ligament length

Ligment length increasing

Ligment length increasing

The plot of wf versus L in different TPVs is shown in Fig. 4. It indicates

-Nucleated Thermoplastic Vulcanizates Based

Ligment length (mm)

It has been widely reported that -PP exhibits a superior impact

Wei-Kang Wang, Xue-Gang Tang, Rui-Ying Bao et al.

very complex (branching on screw dislocations, three dimensional

-Nucleated Thermoplastic Vulcanizates Based

3.2. Effect of Temperature Gradient on the Development of iPP in TPVs

The melting behaviors of the heat-treated samples were studied by

Wei-Kang Wang, Xue-Gang Tang, Rui-Ying Bao et al.

degree of perfection of phase was presented in TPV samples with larger

The thickness of TPV sample (mm)

The thickness of TPV sample (mm)

-Nucleated Thermoplastic Vulcanizates Based

samples, but the strength of the temperature gradient (the temperature

Temperature gradient ( C/mm)

900 1000 1100

900 1000 1100 1200

The relationship among the -PP content, sample thickness, and

Wei-Kang Wang, Xue-Gang Tang, Rui-Ying Bao et al.

Based on a lot of related researches [38-41], we can safely draw the

-Nucleated Thermoplastic Vulcanizates Based

Wei-Kang Wang, Xue-Gang Tang, Rui-Ying Bao et al.

3.3. Effect of Spatial Confinement on the Development of theiPPin TPVs

-Nucleated Thermoplastic Vulcanizates Based

the content of PF is up to 6wt%, the crystallization temperature is 114.07 C,

Wei-Kang Wang, Xue-Gang Tang, Rui-Ying Bao et al.

cross-hatched structure, even in the absence of nucleating foreign particle