11-13-09-Wen Bai PHD Thesis PDF

AN ABSTRACT OF THE DISSERTATION OF
Wen Bai for the degree of Doctor of Philosophy in Wood Science and Chemical
Engineering presented on November 3, 2009.
Title: New Application of Crystalline Cellulose in Rubber Composites.
Abstract approved:
___________________________
Kaichang Li
___________________________
Christine J. Kelly
Rubber without reinforcement has limited applications.
The strength of
reinforced rubber composites can be ten times stronger than that of unreinforced
rubbers. Therefore, rubber composites are widely used in various applications ranging
from automobile tires to seals, valves, and gaskets because of their excellent
mechanical elastic properties. Silica and carbon black are the two most commonly
used reinforcing materials in rubber tires. They are derived from non-renewable
materials and are expensive. Silica also contributes to a large amount of ash when
used tires are disposed of by incineration. There is a need for a new reinforcing filler
that is inexpensive, renewable and easily disposable. Cellulose is the most abundant
natural polymer. Native cellulose includes crystalline regions and amorphous regions.
Crystalline cellulose can be obtained by removing the amorphous regions with the
acid hydrolysis of cellulose because the amorphous cellulose can be hydrolyzed faster
than crystalline cellulose. We recently discovered that the partial replacement of silica
with microcrystalline cellulose (MCC) provided numerous benefits: 1) low energy
consumption for compounding, 2) good processability, 3) strong tensile properties, 4)
good heat resistance, and 5) potential for good fuel efficiency in the application of
rubber tires.
Strong bonding between fillers and a rubber matrix is essential for imparting
rubber composites with the desired properties for many specific applications. The
bonding between hydrophilic MCC and the hydrophobic rubber matrix is weak and
can be improved by addition of a coupling agent or surface modifications of MCC. In
this study, MCC was surface-modified with acryloyl chloride or alkenyl ketene dimer
(AnKD) to form acrylated MCC (A-MCC) and AnKD-modified MCC (AnKD-MCC).
The surface modifications of MCC did not change the integrity and mechanical
properties of MCC, but provided functional groups that were able to form covalent
linkages with the rubber matrix during the vulcanization. Both A-MCC and AnKDMCC facilitated the process and production of rubber composites and improved tensile
properties and heat resistance of the resulting rubber composites as MCC did when
they were used for the partial replacement of silica in rubber composites.
Furthermore, A-MCC and AnKD-MCC were superior to MCC in terms of improving
tear properties of rubber composites.
It has been well-established that the size and the geometrical features of
reinforcing fillers play important roles in the mechanical properties of the reinforced
composites. MCC was further hydrolyzed with acid to form nanocrystalline cellulose
(NCC), i.e., cellulose crystals with their width of less than 100 nm.
A novel
differential centrifugation technique has been developed for separation of NCC

mixtures into fractions with a narrow size distribution. The NCC was investigated as a
filler in rubber composites through a dry blending process, but saw little success.
NCC had to be dried before it could be blended with rubbers.
However, NCC
particles tended to aggregate after drying and could not be uniformly dispersed into
the rubber matrix during the dry blending. As a result, NCC had poor reinforcing
effect on rubbers. For future research, the mixing of aqueous suspension of NCC and
rubber latex may improve the dispersion of NCC particles in rubbers, thus improving
the reinforcing effects of NCC in rubbers.
Copyright by Wen Bai

November 3, 2009
All Rights Reserved
New Application of Crystalline Cellulose in Rubber Composites

by
Wen Bai
A DISSERTATION
submitted to
Oregon State University
in partial fulfillment of
the requirements for the
degree of
Doctor of Philosophy
Presented November 3, 2009

Commencement June 2010
Doctor of Philosophy dissertation of Wen Bai presented on November 3, 2009.

APPROVED:
_____________________________________________________________________
Co-Major Professor, representing Wood Science
_____________________________________________________________________
Co-Major Professor, representing Chemical Engineering
_____________________________________________________________________
Head of the Department of Wood Science & Engineering
_____________________________________________________________________
Head of the School of Chemical, Biological & Environmental Engineering
_____________________________________________________________________
Dean of the Graduate School
I understand that my dissertation will become part of the permanent collection of

Oregon State University libraries. My signature below authorizes release of my
dissertation to any reader upon request.
_____________________________________________________________________
Wen Bai, Author
ACKNOWLEDGEMENTS
First and foremost, I would like to express my sincere appreciation to my

advisor Dr. Kaichang Li and Dr. Christine Kelly for their continuous support and
guidance throughout my Ph.D. study. I am very grateful for their encouragement
during the ups and downs of my Ph.D. research. What I learned from them will
definitely benefit my future career. I would also like to extend my appreciation to my
committee members, Dr. Everett Hansen, Dr, Joe Karchesy, and Dr. Skip Rochefort.
I am grateful to all graduate students and group members for their help and
companionship during my study.
Many thanks also go to the faculty and staff
members of Department of Wood Science and Engineering and School of Chemical,

Biological & Environmental Engineering.
I would like to acknowledge the financial support from Schill + Seilacher
Struktol AG, Hamburg, Germany.
Finally, I would like to thank my family for their unconditional love, support
and trust throughout these many years.
CONTRIBUTION OF AUTHORS
Dr. Kaichang Li was involved in all experimental design and revising of all
manuscripts.
Dr. James Holbery was involved in the experiment and revising of manuscript
of Chapter 5 (A technique for production of nanocrystalline cellulose with a narrow
size distribution).
TABLE OF CONTENTS
Page
Chapter 1 General introduction and literature review................................................. 1
1.1 General introduction......................................................................................... 1
1.2 Literature review .............................................................................................. 2
1.2.1 Fillers from renewable sources ............................................................. 2
1.2.2 Main fillers in rubber composites.......................................................... 6
1.2.3 Rubbers.................................................................................................. 9
1.2.4 Vulcanized rubbers.............................................................................. 11
1.2.5 Rubber composites .............................................................................. 17
1.2.6 Adhesion between fillers and rubber matrix ....................................... 19
1.2.7 Surface modifications for microcrystalline cellulose.......................... 22
1.3 References ...................................................................................................... 31
Chapter 2 Partial replacement of silica with microcrystalline cellulose for a new
rubber composite.............................................................................................. 39
2.1 Abstract .......................................................................................................... 40
2.2 Keywords ....................................................................................................... 40
2.3 Introduction .................................................................................................... 41
2.4 Experimental methods.................................................................................... 42
2.4.1 Materials.............................................................................................. 42
2.4.2 Compounding recipe and procedure ................................................... 44
2.4.3 Evaluation of viscoelastic properties of un-vulcanized rubber
composites.................................................................................................... 46
2.4.4 Evaluation of mechanical properties of vulcanized rubber
composites.................................................................................................... 47
2.4.5 Statistical analysis of experimental data ............................................. 50
TABLE OF CONTENTS (Continued)

Page
2.5 Results and discussion.................................................................................... 50
2.5.1 Compositions of rubber composites and compounding procedures.... 50
2.5.2 Compounding of the rubber composites in an internal rubber mill .... 51
2.5.3 Mooney viscosity of the rubber composites........................................ 53
2.5.4 Pre-vulcanization characteristics of the rubber composites ................ 57
2.5.5 Rheological properties of the rubber composites ................................ 58
2.5.6 Cure Characteristics of the rubber composites.................................... 60
2.5.7 Tensile properties of unaged and heat-aged rubber composites ......... 61
2.5.8 Tear strengths of the rubber composites and hot rubber composites .. 67
2.5.9 Heat build up and heat blow out time of the rubber composites......... 68
2.5.10 Dynamic mechanical properties of the rubber composites .............. 70
2.6 Conclusions .................................................................................................... 72
2.7 Acknowledgments.......................................................................................... 73
2.8 References ...................................................................................................... 74
Chapter 3 Effect of acrylated microcrystalline cellulose on the properties of
silica-filled rubber composites ......................................................................... 76
3.1 Abstract .......................................................................................................... 77
3.2 Key words ...................................................................................................... 77
3.3 Introduction .................................................................................................... 77
3.4 Experimental .................................................................................................. 79
3.4.1 Materials and equipment ..................................................................... 79
3.4.2 Surface-modification of microcrystalline cellulose (MCC) with
acryloyl chloride........................................................................................... 81

Page
3.4.3 Compounding recipes and procedures ................................................ 82
composites.................................................................................................... 84
composites.................................................................................................... 85
3.4.6 Statistical analysis of experimental data ............................................. 86
3.5 Results and discussion.................................................................................... 86
3.5.1 Verification of surface modification of MCC ..................................... 86
3.5.2 Mooney viscosity of rubber composites.............................................. 87
3.5.3 Pre-vulcanization characteristics of rubber composites ...................... 88
3.5.4 Curing characteristics of the rubber composites ................................. 89
3.5.5 Tensile properties of unaged and oven-aged rubber composites ........ 90
3.5.6 Hardness of the unaged and oven-aged rubber composites ................ 93
3.5.7 Tear strength and hot tear strength of the rubber composites ............. 94
3.6 Conclusions .................................................................................................... 95
3.7 Acknowledgments.......................................................................................... 96
3.8 References ...................................................................................................... 97
Chapter 4 Effect of alkenyl-ketene-dimmer-modified microcrystalline cellulose
on the properties of silica-filled rubber composites......................................... 98
4.1 Abstract .......................................................................................................... 99
4.2 Key words ...................................................................................................... 99
4.3 Introduction .................................................................................................... 99
4.4 Experiment ................................................................................................... 101
4.4.1 Materials and equipment ................................................................... 101

Page
4.4.2 Surface modification of MCC with AnKD ....................................... 103
4.4.3 Compounding recipes and procedures .............................................. 105
composites.................................................................................................. 105
composites.................................................................................................. 107
4.4.6 Statistical analysis of experimental data ........................................... 108
4.5 Results and discussion.................................................................................. 108
4.5.1 Verification of surface modification of MCC ................................... 108
4.5.2 Mooney viscosity of rubber composites............................................ 109
4.5.3 Pre-vulcanization characteristics of rubber composites .................... 110
4.5.4 Cure characteristics of the rubber composites................................... 111
4.5.5 Tensile test and heat-aged tensile test ............................................... 111
4.5.6 Hardness of the unaged and aged rubber composites ....................... 113
4.5.7 Tear strength and hot tear strength of the rubber composites ........... 114
4.6 Conclusions .................................................................................................. 115
4.7 Acknowledgment ......................................................................................... 116
4.8 References .................................................................................................... 117
Chapter 5 A technique for production of nanocrystalline cellulose with a narrow
size distribution .............................................................................................. 118
5.1 Abstract ........................................................................................................ 119
5.2 Keywords ..................................................................................................... 119
5.3 Introduction .................................................................................................. 119
5.4 Experimental methods.................................................................................. 121

Page
5.4.1 Chemicals .......................................................................................... 121
5.4.2 Preparation of NCC suspensions....................................................... 121
5.4.3 Transmission electron microscopy (TEM) graphs ............................ 122
5.4.4 Fractionation of NCC suspensions using a differential
centrifugation technique............................................................................. 122
5.4.5 Determination of the diameter, length, and volume of NCC ............ 125
5.4.6 Mechanism of differential centrifugation.......................................... 126
5.5.1 Verification of NCC size by TEM .................................................... 128
5.5.2 Yields of NCC in different fractions ................................................. 129
5.5.3 The relationship between RCF and the volume of NCC in each
fraction ....................................................................................................... 130
5.5.4 Length distributions of NCC by differential centrifugation method. 137
5.5.5 Aspect ratio distribution of NCC whiskers by differential
centrifugation ............................................................................................. 143
5.6 Conclusions .................................................................................................. 146
5.7 Acknowledgements ...................................................................................... 146
5.8 References .................................................................................................... 147
Chapter 6 Nanocrystalline cellulose reinforced rubber composites........................ 149
6.1 Abstract ........................................................................................................ 150
6.2 Introduction .................................................................................................. 150
6.3 Experimental methods.................................................................................. 152
6.3.1 Chemicals and equipment ................................................................. 152

Page
6.3.2 Preparation of
methacrylamidopropyl,dimethyl,glycidylammonium chloride (I)............. 154
6.3.3 Preparation of NCC suspension ........................................................ 155
6.3.4 Preparation of NCC suspension with a stabilizer and freeze-dried
NCC............................................................................................................ 155
6.3.5 Preparation of NCC-reinforced rubber composites by dry-blending 156
6.3.6 Preparation of NCC-reinforced rubber composite films in organic
solvent ........................................................................................................ 157
6.3.7 Microscopic images of NCC suspensions and NCC-rubber
composites.................................................................................................. 157
6.3.8 Tensile properties of NCC-reinforced rubber composites ................ 158
6.4.1 Synthesis of compound I................................................................... 158
6.4.2 Stability of NCC suspensions............................................................ 160
6.4.3 Micro-images of re-dispersed NCC suspensions .............................. 163
6.4.3 Tensile properties of NCC-reinforced rubber composites ................ 165
6.4.4 Morphology of freeze-dried unmodified and modified NCCreinforced rubber composite films ............................................................. 166
6.5 Conclusions .................................................................................................. 169
6.6 Acknowledgement........................................................................................ 169
6.7 References .................................................................................................... 170
Chapter 7 General conclusions................................................................................ 171
Bibliography............................................................................................................... 173
LIST OF FIGURES
Figure
Page
1.1 Molecular structure of cellulose.............................................................................. 2

1.2 Nanocrystalline cellulose from trees....................................................................... 5
1.3 Morphology of carbon black................................................................................... 7
1.4 Morphology of silica............................................................................................... 9
1.5 Chemical structures for butadiene rubber ............................................................. 10
1.6 Chemical structure for SBR .................................................................................. 11
1.7 The vulcanization process in rubber ..................................................................... 11
1.8 The schematic for free radical mechanism of sulfur vulcanization without
accelerators ........................................................................................................... 13
1.9 Different accelerators for vulcanization................................................................ 14
1.10 The mechanism of sulfur vulcanization with accelerators................................... 15
1.11 Vulcanization of rubber composites by Curemeter.............................................. 17
1.12 The effects of vulcanization on properties of vulcanized rubber composites...... 19
1.13 a) The working mechanism of a silane coupling agent for silica-reinforced
rubber composites, b) Scorch reaction between the silica filler and the rubber
matrix .................................................................................................................... 21
1.14 The working mechanism of a silane coupling agent in MCC-reinforced
epoxy composites.................................................................................................. 25
1.15 PMDI as a coupling agent for MCC-PS composites............................................ 26
1.16 MA-polymer as a coupling agent for MCC-polymer composites........................ 28
1.17 Acryloyl chloride as a coupling agent in polymer composites ............................ 29
1.18 AKD open ring reactions ..................................................................................... 30
2.1 Energy consumptions of Batch 1, Batch 2, Batch 3, Batch 4, and Batch 5
during internal rubber mill processing.................................................................. 52
LIST OF FIGURES (Continued)

Figure
Page
2.2 Temperature profiles of Batch 1, Batch 2, Batch 3, Batch 4, and Batch 5

during internal rubber mill processing.................................................................. 53
2.3 The apparent shear stresses in each batch at two different apparent shear
velocities 500 s-1 and 1000 s-1 ............................................................................... 59
2.4. The apparent shear viscosities in each batch at two different apparent shear
velocities of 500 s-1 and 1000 s-1........................................................................... 60
2.5 The scorch time (Ts-2) and cure time (Tc-90) of each batch at 160C ................. 61
2.6. The tensile strength of unaged and aged rubber composites ................................ 63
2.7 The modulus at 100%, 200% , and 300% elongation of unaged rubber
composites and the modulus at 100%, 200%, and 300% elongation of aged
rubber composites ................................................................................................. 65
2.8 The elongation-at-break of unaged and aged rubber composites ......................... 66
2.9 Hardness (type A) of unaged and aged rubber composites................................... 67
2.10 The tear strength of rubber composites and hot rubber composites..................... 68
2.11 The inside temperature of rubber composites from the heat buildup test and
the blowout time of rubber composites from heat blowout test............................ 70
2.12 Viscoelastic property (tan) of each batch at 23C and 100C............................ 72
3.1 FT-IR spectrum of MCC (top) and A-MCC (bottom) .......................................... 86
3.2 Initial viscosity of silica filled rubber composites and A-MCC partially filled
rubber composites ................................................................................................. 87
3.3 Mooney viscosity of silica filled rubber composites and A-MCC partially
filled rubber composites........................................................................................ 88
3.4 Tensile strength of all unaged and heat-aged rubber composites ......................... 92
3.5 Elongation-at-break of all unaged and heat-aged rubber composites ................... 93
3.6 Hardness of all unaged and heat-aged rubber composites .................................... 94
3.7 Tear strength of all rubber composites at room temperature and elevated
temperature ........................................................................................................... 95

Figure
Page
4.1 FT-IR spectrum of MCC (top) and AnKD-MCC (bottom) ................................ 108
4.2 Initial viscosities of all rubber composites.......................................................... 109
4.3 Mooney viscosities of all rubber composites...................................................... 110
4.4 Tensile strength of unaged and aged rubber composites .................................... 112
4.5 Elongation-at-break of unaged and aged rubber composites.............................. 113
4.6 Hardness of unaged and aged rubber composites ............................................... 114
4.7 Tear strength of all rubber composites at room temperature (Room temp) and
high temperature (Hot)........................................................................................ 115
5.1 A schematic of working mechanism of centrifugation ....................................... 126
5.2 Transmission electron microscope (TEM) image of NCC ................................. 129
5.3 The inverse relationship between relative centrifugal force (RCF) and volume
(V)* of NCC from Fraction 1 to Fraction 6........................................................ 131
5.4 The volume distribution of NCC after fractionation by differential RCF .......... 134
5.5 The length distribution of NCC whiskers after fractionation by differential
RCF ..................................................................................................................... 140
5.6 The aspect ratio distribution of NCC whiskers after fractionation by
differential RCF .................................................................................................. 145
6.1 The scheme of synthesizing compound I from DMPMA and ECH................... 159
6.2 FT-IR spectra of ECH (top) and compound I (bottom)...................................... 160
6.3 a) NCC suspension without stabilizer, b) K-NCC suspension, c) DMPMANCC suspension, d) I-NCC suspension.............................................................. 161
6.4 Chemical structure of Kyemene 450................................................................... 162
6.5 TEM images of a) NCC without stabilizer, b) K-NCC, c) DMPMA-NCC, d)
I-NCC ................................................................................................................. 164
6.6 The tensile strength of NCC-reinforced rubber composites without a
stabilizer.............................................................................................................. 165

Figure
Page
6.7 The elongation-at-break of NCC-reinforced rubber composites without a

stabilizer.............................................................................................................. 166
6.8 SEM images of a) freeze-dried unmodified NCC-reinforced rubber composite
film, b) freeze-dried K-NCC-reinforced rubber composite film, c)freeze-dried
DMPMA-NCC reinforced rubber composite film, d)freeze-dried I-NCCreinforced rubber composite film........................................................................ 168
LIST OF TABLES
Table
Page
2.1 Materials in this study........................................................................................... 43

2.2 Composition of rubber composites and compounding procedures....................... 45
2.3 Initial viscosity and Mooney viscosity (MV) for unaged and aged rubber
composites at 100C ............................................................................................. 56
2.4 Pre-vulcanization characteristics at 125C ........................................................... 58
3.1 Materials in this study........................................................................................... 80
3.2 Composition of rubber composites and compounding procedures....................... 83
3.3 Pre-vulcanization characteristics at 125 C .......................................................... 89
3.4 The scorch time (Ts-1) and cure time (Tc-90) of each batch at 160 C ................ 90
4.1 Materials in this study......................................................................................... 102
4.2 Composition of rubber composites and compounding procedure ...................... 104
4.3 Pre-vulcanization characteristics at 125 C ........................................................ 110
4.4 The scorch time (Ts-1) and rure time (Tc-90) of each batch at 160 C............... 111
5.1 Experimental design of NCC fractions by differential RCF at fixed centrifuge
time (10 min)....................................................................................................... 124
5.2 Comparison between the full volume range and the major volume range of
NCC whiskers at differential RCF...................................................................... 136
5.3 Comparison between the full length range and the major length range of NCC
whiskers at differential RCF ............................................................................... 142
6.1 Materials in NCC-reinforced rubber composites ................................................ 153
6.2 Other components in NCC-reinforced rubber composites.................................. 156
CHAPTER 1 GENERAL INTRODUCTION AND LITERATURE REVIEW

1.1 General introduction
Without reinforcing particulate fillers, many applications of rubbers cannot be
fulfilled. Commonly used fillers in rubbers include carbon black and silica. However,
their productions require tremendous amount of energy and their high densities have a
negative effect for the application of automobile tires. Furthermore, the disposal of
these rubber composites via combustion has an environmental issue because a large
amount of ash is generated.
Cellulose is the most abundant natural polymer. Commercial cellulose fibers
are commonly produced from cotton and wood. Native cellulose includes amorphous
and crystalline regions. Crystalline cellulose including microcrystalline cellulose and
nanocrystalline cellulose can thus be derived from the native cellulose fibers. Because
crystalline cellulose has high strength and high stiffness, it has a great potential to be
used as a reinforcing material in the thermoplastic or rubber matrix.
Cellulose-fiber-reinforced rubber composites have been investigated for the
applications in ropes, hose, belt, mats and insulation, but have not been investigated
for tire applications (Nunes and Visconte, 2000; Haghighat et al., 2005). This study
focuses on development of novel rubber composites filled with renewable and
inexpensive crystalline cellulose (micro or nano) for tire applications.
2
1.2 Literature review
1.2.1 Fillers from renewable sources
1.2.1a Cellulose
Cellulose is the
main component for all plants such as cotton and trees
(Kaplan, 1998). It plays an important role in the structural support of plant cell walls
because of its high mechanical properties (Bos et al., 2002). From the chemical point
of view, cellulose is a large and linear-chained polymer with many hydroxyl groups.
Its basic unit is anhydroglucopyranose (AGU) having three hydroxyl groups per AGU
except the terminal ends (Figure 1.1). The structural repeating unit of cellulose is
cellobiose with the two adjacent AGU units being rotated by 180 degree along the
cellulose chain axis.
One end of the cellulose chain has a reducing group, i.e.,
containing an aldehyde group; the other end does not contain any reducible group and
is called non-reducing end. The degree of polymerization (DP) is the number of
AGUs per cellulose chain and varies with the origin and treatment of the cellulose
sources. The values of DP are around 300 to 1700 for cellulose from wood pulp, 800
to 10,000 for cotton and bacterial celluloses, and 250 to 500 for regenerate cellulose
(Klemm et al., 2005).
Figure 1.1 Molecular structure of cellulose (Kamel et al., 2008)
Because of compact structures and strong intermolecular and intramolecular

hydrogen bonding among cellulose chains, cellulose is insoluble in water and
commonly used organic solvents. Cellulose can form highly crystalline structures,
thus making cellulose fibers strong and stiff. Cellulose can be used for a wide range
of applications such as composites, netting, coatings, packing, paper, etc. because of
its biodegradability and biocompatibility, abundance in nature and low cost (Conner,
1995; Kamel et al., 2008).
1.2.1b Microcrystalline cellulose (MCC)

Microcrystalline cellulose (such as Avicel) with DP value of less than 400
(Klemm et al., 2005). It can be prepared by treating different native cellulose sources
such as wood pulp, bamboo, viscous rayon and cotton with mineral acids (Battista and
Smith, 1962; Tiemstra, 1971; Wang and Feng, 2007; Sun et al., 2008). The native
cellulose has both amorphous and crystalline regions. The amorphous regions are
interacted first with solvents and chemical reagents, because of their loose structures.
The removal of the amorphous regions with an acid treatment of cellulose is the most
commonly used method for the production of MCC. The acid hydrolysis breaks the
(14) glycoside bond, thus decreasing the DP of the resulting MCC (Hakansson and
Ahlgren, 2005). There are two types of MCC, powder MCC and colloidal MCC.
Powder MCC is made by spray-drying of aqueous MCC suspension and has its
4
average particle size ranging from about 20-90 m. Colloidal MCC is MCC colloids
in water with the colloidal size of <0.2m in diameter (Gan and Whistler, 1990).
MCC has excellent mechanical properties and can potentially be used as
reinforcing fillers in polymer composites (W. Helbert, 1996; Qiu et al., 2003; Aji P.
Mathew, 2005; Chakraborty et al., 2005; Petersson and Oksman, 2006a; Petersson and
Oksman, 2006b). MCC as a reinforcing filler in polymer composites offers several
advantages over glass fibers and other inorganic fillers: renewability, nonfood sources,
low energy required for its production, low cost, low density, and high specific
strength and modulus (Azizi Samir et al., 2005).
Like other inorganic fillers such as glass fibers, MCC fillers have hydrophilic
surfaces and are not very compatible with hydrophobic plastics. Coupling agents or
compatibilizers are often required for improving the bonding between MCC and the
plastic matrix (Amash et al., 2002; John et al., 2007). Moreover, the processing
temperature of MCC-filled composites is restricted to about 200 C because MCC
starts to degrade near 230 C, whereas glass-fiber-reinforced composites can have a
much higher processing temperature (Ardizzone et al., 1999).
1.2.1c Nanocrystalline cellulose (NCC)

Nano-materials have many advantages in many high-tech applications. Most
of the nano-materials are prepared from inorganic materials (Rao and Cheetham,
2001; Cushing et al., 2004) and a few are reported to be obtained from natural
products such as cellulose (Beck-Candanedo et al., 2005).
The evolution of
nanocrystalline cellulose (NCC) from tree is shown in Figure 1.2. NCC can be
5
prepared by acid hydrolysis of cellulose under different conditions, i.e., time,
temperature, and ultrasound treatment (Dong et al., 1998). The process of producing
NCC is similar to that of preparing MCC. It also uses acid hydrolysis to break down
microfibrils into single crystals. NCC has a smaller DP value than MCC.
Figure 1.2 The evolution of nanocrystalline cellulose from trees (Jones et al., 2007)
Extensive research has been done in recent years about NCC from different
sources (Bhatnagar and Sain, 2005; Orts et al., 2005; Stenstad et al., 2008) because it
possesses higher strength than steel and higher stiffness than aluminum (Nishino and
Arimoto, 2007). It has been reported that NCC-reinforced plastic composite materials
had superior properties (Hajji et al., 1996; Lima and Borsali, 2004; Alemdar and Sain,
2008b, a). The geometrical features of NCC were found to play an important role in
the properties of the new nanocomposites (Terech et al., 1999; Samir et al., 2004).
6
The size of NCC prepared by the reported methods was not uniform and had a wide
distribution, which could have negative effects on the properties of the new
nanocomposites.
1.2.2 Main fillers in rubber composites

Rubbers without fillers have limited end applications because of the lack of
strength. With addition of particulate fillers, strength could be increased by 10 times
(Hamed and Park, 1999). The properties of fillers such as size, shape, surface area and
surface activity control the effectiveness of the reinforcement (Lee, 2007).
The
interactions between fillers and rubbers are also one of the most important factors that
affect the strength of filled rubbers (O'Brien et al., 1977; Serizawa et al., 1983).
1.2.2a Carbon black

Carbon black is the most widely used reinforcing filler in the rubber industry.
Carbon black is prepared by incomplete combustion or by thermal cracking of
hydrocarbons. Carbon black from incomplete burning of natural gas is acidic on the
surface. Carbon blacks can also be produced by thermal cracking of hydrocarbons in
the absence of oxygen and have relatively low specific surface area (6-15 m2/g)
(Studebaker, 1965).
Carbon black particles typically have their sized ranging from 20 to 300 nm
(Studebaker, 1965). There are three morphological forms of carbon black existing in
rubber composites: particle, aggregate, and agglomerate (Figure 1.3). The sizes of
these morphological forms has the following order: particle<aggregate<agglomerate.
7
Single carbon black particles are the fewest in rubber composites. Aggregates have
their sizes ranging from 100 to 500 nm measured by an electron microscopy (Byers,
1987). They do not break during rubber compounding. Agglomerate consists of a
group of aggregates. It requires a tremendous amount of energy to break down the
agglomerate during rubber compounding because of the high cohesive forces among
carbon black particles.
Figure 1.3 Morphology of carbon black (Norman, 1990)
Reinforcement of rubber by carbon black depends on many variables: surface

area, structure, surface activity, dispersion, and loading. Surface area and surface
activity of carbon black play an important role in its interaction with rubber chains.
The high surface area means the small size of the carbon black particles in the same
weight unit. It is also known that the higher the surface area the harder the even
dispersion of carbon black into the rubber matrix.
The surface area is usually
8
measured by different methods such as Brunner, Emmett, and Teller (BET) N2
adsorption, liquid cetyltrimethyl ammonium bromide (CTAB) adsorption, and iodine
number (Jansen and Kraus, 1971). The interactions between rubber and carbon black
can be through either physical adsorption or chemical bonding. Researchers used to
believe there was a chemical bonding between carbon black and rubber (Bueche,
1960). New studies showed carbon black particles with these functional groups did
not give significant improvement in reinforcement (Le Bras and Papirer, 1978).
Physical adsorption seemed to be a more important factor in reinforcement than the
chemical bonding.
1.2.2b Silica
Silica is another important reinforcing filler in the rubber industry. There are
two types of silica: precipitated silica and fumed silica with different manufacturing
methods. Precipitated silica is manufactured by a controlled precipitation from the
reactions of sodium silicate with acid or alkaline earth metal salts. It has a size
ranging from 10 to 100 nm (Kraus, 1965). Fumed silica with its size of 7-15 nm is
produced at a high temperature by a reaction of silicon tetrachloride with water vapor
(Garrett, 1992).
Hydroxyl groups on the surface of silica cause strong filler-filler interactions
and water adsorption via hydrogen bonding (Ou et al., 1994), thus silica usually exists
as aggregates and agglomerates (Figure 1.4).
The strong hydrogen bonding in
aggregates and agglomerates causes a serious problem in rubber composites, e.g., poor
dispersion. The problem could be solved by adding silane coupling agents into rubber
9
composites. The details are elaborated in the section of Silane coupling agents for
silica-filled-rubber composites.
Figure 1.4 Morphology of silica (Tscheschel et al.)
1.2.3 Rubbers
1.2.3a Butadiene rubber (BR)
Butadiene rubber (Figure 1.5) was originally manufactured from a sodium
catalyst, but this type of BR had limited applications. Today, most of BR is obtained
by solution polymerization with a variety of catalysts. Over 90% of the total BR is
used in tires, because BR has superior properties for tire applications, such as excellent
wear resistance, exceptional balance between wet-grip and rolling resistance, high
elasticity and flexibility, and good process ability (White, 1995). BR is also used in
golf balls, footwear, conveyor belts and flooring for high elasticity and improved
flexibility, tear and abrasion resistance (White, 1995).
10
Figure 1.5 Chemical structures for butadiene rubber (Barlow, 1993a)
1.2.3b Styrene butadiene rubber (SBR)

Styrene butadiene rubber (Figure 1.6) was developed during the World War II
because of the shortage of natural rubber. There are two types of SBR from two
different manufacturing methods: emulsion SBR (E-SBR) and solution SBR (S-SBR).
Emulsion SBR was first discovered through an emulsion polymerization in an aqueous
medium containing various special soaps. The solution SBR is produced by anionic
polymerization of styrene and butadiene and can have a different ratio of styrene and
butadiene. SBR is used for a wide variety of applications, such as tires, footwear,
conveyor belts, vibration-damping systems, hoses, flooring, and adhesives. E-SBR
provides a good balance of wear resistance and wet grip in combination with an
excellent process ability; S-SBR provides an excellent balance between wet grip,
rolling resistance, and dry handling for high-performance tires (Hofmann, 1989b).
11
Figure 1.6 Chemical structure for SBR (Barlow, 1993b)
1.2.4 Vulcanized rubbers

1.2.4a Vulcanization
Vulcanization was discovered in 1841 accidentally by Charles Goodyear who
heated natural rubber that contained sulfur. One year later, Thomas Hancock used the
same process in England. Vulcanization, crosslinking, and cure are basically referred
to the same process. During vulcanization, the free rubber chains are crosslinked
together to form a large three dimensional elastic network via polysulfide bonds, as
shown in Figure 1.7 (Coran, 1978c).
Figure 1.7 The vulcanization process in rubber (Coran, 1978c)
12
Nowadays, the type of curatives for vulcanization depends primarily on the
type of rubbers: unsaturated or saturated. For unsaturated rubbers, such as natural
rubber, styrene butadiene rubber, and butadiene rubber, sulfur is commonly used.
Saturated rubbers such as fluorocarbon rubber and silicon rubber cannot be vulcanized
by sulfur.
The most common curatives for saturated rubbers are peroxides,
quinonedioximes, metal oxides, amines, and isocyanates (Hofmann, 1989a).
1.2.4b Sulfur vulcanization

Various mechanisms have been studied to explain the process of the sulfur
vulcanization without accelerators. One of the proposed mechanisms, free radical
mechanism, is illustrated in Figure 1. 8 (Coran, 1978b). Sulfur is in a ring (S8)
structure. During the vulcanization, sulfur rings firstly generate radical polysulfides at
a high temperature. One radical polysulfide removes hydrogen from an allylic site and
gives a chain radical. Another polysulfide reacts with the chain radical and forms a
new pendent polysulfide radical. This radical can react with another free polymer
chain to form a crosslink. The propagation takes place as the radical reaction happens
between rubber chains via proton transfer, and then a giant rubber network is formed
with polysulfides as bridges.
13
Figure 1.8 The schematic for free radical mechanism of sulfur vulcanization without
accelerators (Coran, 1978b)
However, when sulfur is used alone in vulcanization, the cure rate is slow and
the cure time can be 3-5 h. The addition of accelerators is desirable to reduce the cure
time to as few as 2-5 min (Coran, 1978b). Therefore, sulfur along with accelerators is
used as curatives for rubber composites for increasing the crosslinking efficiency and
the cure rate.
There are different types of accelerators, such as thiazoles,
14
bithiocarbannates, guanidines, and sulfenamides (Figure 1.9). In most of cases the
curatives include two accelerators because they can be activated by each other, thus
increasing the cure rate.
Thiazoles
Dithiocarbamates
Guanidines
Sulfenamides
Figure 1.9 Different accelerators for vulcanization
The general reaction mechanism of sulfur vulcanization with an accelerator is

illustrated as follows, using 2-mercaptobenzo-thiazole (MBT) accelerator as an
example (Figure 1.10). First, the accelerator reacts with polysulfur (Sx) to form MBTSx-MBT structure by an initiator. Second, these polysulfides can react with rubber to
15
form rubber-Sx-MBT structure. Finally, rubber polysulfides react either directly or
through an intermediate to form rubber-Sx-rubber networks (Coran, 1978e).
Figure 1.10 The mechanism of sulfur vulcanization with accelerators (Coran, 1978e)
Almost all organic accelerators require the simultaneous use of inorganic and
organic activators to develop their full effectiveness. The main purpose of activator in
rubber composites is to support the vulcanization, especially in the sulfur curing
systems.
The inorganic activators include zinc oxide and magnesium oxide; the
organic ones include stearic, palmitic, lauric acid, and their zinc salts. The efficiency
of the polysulfide cross-links during vulcanization can be controlled by the complex
formed by activators (zinc and carboxylic acid), sulfur, and accelerators. A typical
16
vulcanization system includes, sulfur (0.5-4 phr), Diphenylguanidine (DPG) & Ncyclohexyl-2-benzothiazolesulfenamide (CBS) (0.5-2 phr), zinc oxide (2-10 phr), and
stearic acid (1-4 phr) (Coran, 1978a).
1.2.4c Characterization of the vulcanization process

Before vulcanization, there are many preparation steps, such as mixing,
milling, and molding. It is necessary to have sufficient resistance for pre-mature cure
of the rubber composites. The resistance of pre-mature cure is commonly measured
by t5, the time required for increasing the viscosity by five units at a given temperature.
The test temperature is usually a little higher than a typical processing temperature.
The t5 is usually measured with a Mooney viscometer. The t5 is commonly used as the
indicator of the processing safety for rubber materials.
The rate and extent of vulcanization are commonly measured by a Curemeter.
An uncured rubber material is put into a heating chamber under certain curing
conditions (fixed temperature, fixed frequency, and fixed amplitude). The torque is
recorded as a function of time (Figure 1.11). There are several curing parameters
recorded during the test by Curemeter. The torque at 90% cure (M90) is calculated by
Equation 1.1. The cure time (Tc90) is the time to reach M90.
M x = M L + 90%( M H M L )
Eq. 1.1
MH: maximum torque, ML: minimum torque.

Generally, there are three types of curing curves: marching, plateau, and
reversion (Figure 1.11).
In a marching curve, more polysulfide crosslinks are
17
continually formed, which results in the torque increase. In a plateau curve, the
crosslinking reaction is complete and the network is mature. In a reversion curve;
there is a drop of torque because the overheating during the test breaks down the
rubber network.
Figure 1.11 Vulcanization of rubber composites by Curemeter (Coran, 1978f)
1.2.5 Rubber composites

Rubber composites are composite materials consisting of rubbers (such as
natural rubber, butadiene rubber, styrene butadiene rubber, etc.), fillers (such as
carbon black, silica, etc.), curatives, and small amounts of process and property
modifiers. Rubbers are reinforced by fillers so that the resulting rubber composites
have adequate strengths for most of applications. Carbon black and silica are two
most commonly used fillers because they lead to strong mechanical properties of the
18
rubber composites. The property requirements of the end-products decide whether
carbon black, silica, or both are used in a rubber formulation. The properties required
for most applications include modulus, tensile strength, weariness, tear strength, and
dynamic properties. The maximum reinforcement of rubbers involves both physical
and chemical interactions between fillers and rubbers (Edwards, 1990). Physical
interactions include van der Waals forces and hydrogen bonding.
Chemical
interactions are referred to the covalent bonding between fillers and the rubber matrix.
The properties of rubber composites are not only dependent upon fillers, but
also affected by many other factors such as the crosslinking density, the types of
crosslinks, the sorts of rubbers, etc (Coran, 1978d). The effect of the crosslinking
density is shown in Figure 1.12. After vulcanization, rubber chains form a large
network. The vulcanized rubber composites are insoluble in organic solvent and have
high viscosity. Tear strength, tensile strength, fatigue life, and toughness increase and
then decrease with increasing the crosslinking density. Elastic recovery and stiffness
increase with increasing the crosslinking density. However, hysteresis, permanent set,
and friction decrease with increasing the crosslinking density.
19
Figure 1.12 The effects of vulcanization on properties of vulcanized rubber

composites (Coran, 1978d)
1.2.6 Adhesion between fillers and rubber matrix

Chemical compatibility between fillers and rubber matrix can be expected to
play an important role in the dispersion of the fillers in the matrix and in the strong
adhesion between the two phases.
Different fillers and rubbers require different
coupling agents. For example, silane coupling agents work very well for silica-filled
rubber composites. They also work well for other fillers such as lignocellulosic fibers,
clays, and carbon nanotubes (Bledzki and Gassan, 1996; Singh et al., 1996; Dai and
Huang, 1999; Shanmugharaj et al., 2007).
Depending on the fillers used, many
coupling agents have been studied (Brinke et al., 2003; Qi et al., 2004; Ismail et al.,
2005). The details are discussed in the following sections.
20
1.2.6a Silane coupling agents for silica-filled-rubber composites
Silane coupling agents are typically bi-functional organosilanes such as
bis(triethoxylsiylpropyl)-tetrasulfide (TESPT), one functional group being able to
form covalent bonding with silica and another being able to form covalent bonding
with rubber. Most commonly used silane coupling agents have a general formula of
(RO)3SiRY where the (RO)3Si group reacts with hydroxyl groups of the silica filler
to form a siloxane bond (Si-O-Si) and the R group (typically SH or polysulfide)
reacts with rubber to form covalent sulfide bonds (Figure 1.13). The reactions shown
in Figure 1.13a occur at a lower temperature than those shown in Figure 1.13b.
Production of filler-reinforced rubber products typically involves two steps. The first
step is to thoroughly mix rubber, fillers and other additives. The rubber mixture from
the first step has to be molded into different shapes of products. The second step is to
make the rubber mixture into desirable shapes of final products and then cure the
products. The silane coupling agents are typically added in the first step. The mixing
temperature in the first step has to be sufficiently high so that the reactions shown in
Figure 1.13a can occur at a high reaction rate, but has to be low enough to prevent the
reactions shown in Figure 1.13b from occurring to a great extent because these
reactions cause pre-mature cure of the rubber composites, i.e., reduce the flowability
of the rubber mixture. The mixing temperature is typically around 100 C and the
curing temperature is typically around 160 C. Increasing the mixing temperature can
shorten the reaction time for those reactions shown in Figure 1.13a, but also facilitate
those reactions shown in Figure 1.13b (Brinke et al., 2003). Therefore, the mixing
temperature and the mixing time have to be optimized for each rubber composite
21
system to maximize the reactions shown in Figure 1.13a and control the flowability
of rubber composites, i.e., the reactions shown in Figure 1.13b at an acceptable level.
Figure 1.13a) The working mechanism of a silane coupling agent for silica-reinforced
rubber composites (Reuvekamp et al., 2002)
Figure 1.13b) Scorch reaction between the silica filler and the rubber matrix (Brinke et
al., 2003)
22
1.2.6b Treatments for lignocellulosic materials with silane coupling agents
Lignocellulosic materials are mainly composed of cellulose, hemicelluloses,
and lignin. Silane coupling agents can be used to graft a wide range of functional
groups onto the surfaces of lignocellulosic materials. There have been a number of
studies about the modification of lignocellulosic materials with silane coupling agents
for improving their properties as fillers in plastic composites (Bledzki and Gassan,
1996; Singh et al., 1996; Matuana et al., 1998; Gassan et al., 2000; Pothan et al.,
2007; Wang and Sain, 2007). The possible mechanism of silane coupling reactions
has been studied (Castellano et al., 2004). It was found that SiOR groups did react
with phenolic hydroxyl groups in lignin, but did not react with hydroxyl groups of
cellulose and hemicelluloses in the absence of water (Castellano et al., 2004). Water
partially hydrolyzed the silanol (SiOR) group at the temperature of above 80 C, thus
facilitating its reaction with the hydroxyl groups (Castellano et al., 2004).
1.2.7 Surface modifications for microcrystalline cellulose

Microcrystalline cellulose (MCC) is incompatible with many polymers such as
plastics and polymer latex for the production of composites because of its hydrophilic
surface. Another drawback of MCC as a filler is that it requires a lower processing
temperature (below 200 C) than inorganic fillers such as carbon black, glass fibers,
and clays. Studies have been focused on making MCC less hydrophilic, thus being
more compatible with hydrophobic polymer matrices (Joly et al., 1996; Hubbe et al.,
2007). The hydroxyl groups on MCC surfaces have been modified via a number of
methods such as ionization (Gospodinova et al., 2002; Habibi et al., 2006), silanation
23
(Lu et al., 2008), and esterification (Pasquini et al., 2006). It has been demonstrated
that the surface modification did not damage the crystalline structure of MCC (Gouss
et al., 2004). The modified MCC thus still serves as good reinforcing fillers (Chauve
et al., 2005).
1.2.7a Ionization
MCC has been imparted with either negative or positive charges.
The
hydroxyl groups on MCC surfaces will be esterified with sulfuric acid or phosphoric
acid to form MCC sulfate or MCC phosphate that carries negative charges if MCC is
treated with these two acids or produced from hydrolysis of cellulose with these two
acids(Gospodinova et al., 2002; Lima and Borsali, 2004)0. A microwave treatment
was found to considerably increase the degree of phosphorylation of MCC
(Gospodinova et al., 2002). Positive charges were successfully introduced onto MCC
surfaces by reacting MCC with (3-chloro-2-hydroxypropyl)-trimethyl-ammonium
chloride (Hubbe et al., 2007).
The formation of carboxylic acids on the surface of MCC can make it more
hydrophilic (Habibi et al., 2006). The carboxylation of MCC was accomplished via
the oxidation of the primary hydroxyl groups of MCC with TEMPO-mediated
oxidation (Marchessault et al., 2006). It was demonstrated that the oxidation did not
change the crystal structure of MCC. Carboxylated MCC carried negative charges on
the surfaces and strong electrostatic repulsion among carboxylated MCC particles
facilitated the dispersion of carboxylated MCC particles into a polymer matrix (Saito
et al., 2007).
24
1.2.7b Silanation
Silane coupling agents such as 3-aminopropyltriethoxysilane and 3glycidoxypropyltrimethoxysilane have been successfully used for modification of
MCC surfaces (Lu et al., 2008). The strong adhesion between the treated MCC and
the epoxy polymer matrix resulted in good mechanical properties of the composite
materials. The mechanism for the silane coupling agent in MCC-epoxy composites
could be proposed in Figure 1.14. Triethoxysilane was firstly hydrolyzed to form SiOH that further reacted with OH groups of MCC. The amino groups on the MCC
surfaces reacted with epoxy, thus forming covalent linkages between MCC and epoxy
resins.
25
Figure 1.14 The working mechanism of a silane coupling agent in MCC-reinforced

epoxy composites (Belgacem and Gandini, 2005)
26
1.2.7c Esterification
Dodecanoyl chloride and octadecanoyl chloride have been used to graft
hydrophobic long hydrocarbon chains onto the surface MCC (Pasquini et al., 2006). It
was found that MCC was surface-grafted with long aliphatic chain and also changed
its hydrophilicity to hydrophobicity. With non-polar polymer matrices, these modified
MCCs can provide a good interfacial compatibility. Polymeric methylene diphenyl
diisocyanate (PMDI) has been used for modification of MCC. It was demonstrated
that PMDI-modification improved the compatibility between MCC and polystyrene
(Figure 1.15) (Girons et al., 2007). The delocalized -electrons of the benzene rings
in PMDI and polystyrene interacted with each other, thus improving the adhesion
between the modified MCC and the polystyrene matrix.
Figure 1.15 PMDI as a coupling agent for MCC-PS composites
27
Treatment of MCC surfaces with maleic-anhydride (MA)-modified polymers

has been studied (Joly et al., 1996; Palaniyandi, 2004; Kumar and Singh, 2007). It
was believed that maleic anhydride was able to form ester linkages with the hydroxyl
groups of MCC. Commonly used MA-grafted polymers include maleic-anhydridegrafted polypropylene (MAPP), maleic-anhydride-grafted polyethylene (MAPE) and
maleic-anhydride-grafted ethylene-propylene copolymer (MAEP). MAPP enhanced
tensile and flexural properties and impact resistances of the resulting MCC-PP
composites (Joly et al., 1996); MAPE improved tensile properties and flexural
modulus of the resulting MCC-HDPE composites (Palaniyandi, 2004); MAEP also
increased
tensile
properties
of
the
resulting
MCC-poly(ethylene-propylene)
composites (Kumar and Singh, 2007). The mechanism of covalent reactions between
MA-modified polymers and MCC surfaces is shown in Figure 1.16.
28
Figure 1.16 MA-polymer as a coupling agent for MCC-polymer composites
29
Acryloyl chloride was used for the surface esterification of MCC to form
acrylated MCC (Bojani et al., 1996). The acrylated MCC was co-polymerized with 4vinylpridine or 1-vinylmidazole to form superior MCC-reinforced composite materials
(Figure 1.17).
Figure 1.17 Acryloyl chloride as a coupling agent in polymer composites (Bojani et

al., 1996)
A sizing agent, alkyl ketene dimmer (AKD), was used for modification of
MCC and AKD-modified MCC was found to reinforce high density polyethylene
better than unmodified MCC (Palaniyandi, 2004).
AKD has a four-member
heterogeneous ring and two long hydrocarbon side chains. When the side chains are
unsaturated, it is named alkenyl ketene dimer (AnKD). The ring can be open to react
with OH groups of MCC surfaces and form -keto esters (Figure 1.18). The side
reaction of hydrolysis of AKD with water is not desirable. AKD is degraded to betaketo acid or ketone during the hydrolysis.
30
Figure 1.18 AKD open ring reactions (Karademir, 2002)
31
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39
CHAPTER 2 PARTIAL REPLACEMENT OF SILICA WITH
MICROCRYSTALLINE CELLULOSE FOR A NEW RUBBER COMPOSITE
Wen Bai and Kaichang Li*

Department of Wood Science & Engineering, Oregon State University
Corvallis, OR 97331
Composites Part A: Applied Science and Manufacturing

Elsevier Ltd.
The Boulevard, Langford Lane, Kidlington, Oxford OX51GB, UK
2009, 40, 1597-1605
40
2.1 Abstract
Carbon black and silica are the major reinforcing fillers used in rubber
industry.
They are derived from non-renewable materials and are expensive.
Cellulose is abundant, renewable, inexpensive, and readily available. In this study,

microcrystalline cellulose (MCC) was investigated to partially replace silica in rubber
composites. The partial replacement of silica with MCC significantly reduced the
energy required for thorough dispersion of fillers in rubber matrix and lowered the
internal temperature during the compounding process.
Moreover, the partial
replacement of silica with MCC reduced Mooney viscosity, apparent shear stress, and
apparent shear viscosity of the rubber composites, which facilitated the manufacturing
process of the rubber composites. The replacement of up to 18% silica with MCC did
not negatively affect the mechanical properties of the unaged and aged rubber
composites such as tensile strength and the modulus at 100%, 200%, and 300%
elongation.
The partial replacement of silica with MCC also improved the heat
resistance of the rubber composites, did not significantly change the tan of rubber
composites containing up to 11.8% of MCC at low temperature and decreased the
tan of all rubber composites at high temperature. However, addition of MCC slightly
decreased tear strength and hot tear strength of the resulting rubber composites.
2.2 Keywords
A. Microcrystalline cellulose (MCC); rubber composites; B. Mooney viscosity;
mechanical properties; dynamic mechanical properties
41
2.3 Introduction
In rubber industry especially in the rubber tire application, the currently used
fillers mainly include carbon black and silica. Carbon black is derived from fossil oil.
Silica is derived from minerals. Although silica is not a petrochemical-based product,
it consumes a lot of energy for its production. They both have high density, which has
negative impacts on the fuel efficiency of automobiles.
Therefore, the tire
manufacturers are seeking for new reinforcing fillers that are inexpensive, readily
available, light in weight, and renewable.
Cellulose is the most abundant natural polymer. Cellulose makes up 40 to 44
percent of wood (Bowyer et al., 2003). Commercial cellulose fibers are mainly from
cotton and wood. Short cellulose fibers have been studied as reinforcing fillers in
rubber composites in the past 25 years (Derringer, 1971; Ismail et al., 1997; Haghighat
et al., 2005; Joseph et al., 2006). Cellulose-fiber-reinforced rubber composites are
mainly used for making ropes, hose, belt, mats and insulation, and have yet to be used
in the tire application (Nunes and Visconte, 2000; Haghighat et al., 2005).
Cellulose contains both amorphous and crystalline regions.
Crystalline
cellulose is much stronger and stiffer than amorphous cellulose and cellulose itself,
and is supposed to be a better reinforcing filler than cellulose.
Microcrystalline
cellulose (MCC) is crystalline cellulose and is typically derived from the acid
hydrolysis of cellulose (Toschkov et al., 1976).
production of MCC.
This is a low cost process for
The acid hydrolysis preferentially removes the amorphous
regions of cellulose. When compared with glass fibers, silica and carbon black, MCC
42
as a reinforcing filler in composites has many advantages: low cost, low density,
easy to process, little abrasion to equipment, renewability, and biodegradability (Vigo
and Kinzig, 1992). There have been some studies on MCC as a reinforcing filler in
plastic composites in the past few years (Kubat and Klason, 1983; Reinsch and Kelley,
1997; Laka et al., 2003). However, little has been reported about using MCC as a
reinforcing filler in rubber composites.
In this study, MCC was used as a third filler to partially replace silica in
styrene butadiene rubber (SBR) and poly-butadiene rubber (BR) composites. The
effects of MCC loadings in rubber composites on energy consumptions during
compounding, rheological properties, mechanical properties, heat resistance, and
dynamic mechanical properties were studied in detail.
2.4 Experimental methods

2.4.1 Materials
Table 2.1 shows the materials used in this study, including code, trade name,
manufacturer, and location of the manufacturer. The following two types of rubbers
were used: styrene butadiene rubber (SBR) and polybutadiene rubber (PB). Three
different fillers were carbon black (CB), silica, and microcrystalline cellulose (MCC).
The coupling agent was bis(3-triethyoxysilylpropyl)disulfide. Two types of activators
were zinc oxide and stearic acid. The antiozonant was N-(1,3-dimethyl)-N-phenyl-pphenylenediamine (6PPD). The processing oil was a product with a trade name of
Sundex790. There were two kinds of accelerators: diphenylguanidine (DPG) and N-
43
cyclohexyl-2-benzothiazolesulfonamide (CBS). The vulcanizer was sulfur (S). The
curing agents included DPG, CBS and S.
Table 2.1 Materials in this study
Code
Trade name
Manufacturer
Firestone Polymers,
Rubber
SBR
Duradene 751
LLC
PB
Taktene 220
Lanxess Corp.
Side Richardson
Filler
CB
N220
Carbon Company
Silica Ultrasil@GR7000 Degussa Corp.
MCC Avicel PH 101
FMC Inc.
Coupling
Struktol Company
a
Silane SCA985
agent
of America
Struktol Company
Process aid PA
JB46F
of America
Activator
ZnO
Zinc oxide
Horsehead Corp.
Textile Rubber &
StAc Stearic acid
Chemical Co.
Western reserve
Antiozonant 6ppd 6PPDb
chemical Corp.
Processing
Sun
sundex 790
Sun Oil Company
oil
Flexsys America
Accelerator DPG Perkacit DPGc
LP
Flexsys America
CBS
Santocure CBSd
LP
Rubbermakers
Vulcanizer S
R.E. Carroll Inc.
sulfur
a Bis(3-triethoxysilyipropyl)disulfide.
b N-(1,3-dimethyl)N'-phenyl-p-phenylenediamine.
c Diphenylguanidine.
d N-cyclohexyl-2-benzothiazolesulfenamide.
Location
Akron, OH
Orange, TX
Akron, OH
Akron, OH
Philadelphia, PA
Stow, OH
Stow, OH
Monaca, PA
Nurnberg,
Germany
Stow, OH
Aartselaar,
Belgium
Akron, OH
Akron, OH
Akron, OH
44
2.4.2 Compounding recipe and procedure
A Banbury 1600 internal mixer (Farrel Corp., Ansonia, CT) was used for
compounding a rubber mixture, which was called master batch. The temperature of
the mixer was set and maintained at 65 C. There were five batches compounded
according to the recipes and procedures in Table 2.2. The weights of all ingredients in
the recipes were in units of per hundred rubber (phr). Batch 1 was the control which
did not contain MCC. The percentages of silica replaced by MCC were 5.6%, 11.8%,
17.6%, and 23.5%, corresponding to Batch 2, Batch 3, Batch 4, and Batch 5. There
were two passes to complete the compounding. After each pass, the master batches
were made into sheets with the thickness of 2-4 mm by an open rubber mill (Stewart
Bolling Co., Cleveland, OH).
45
Table 2.2 Composition of rubber composites and compounding procedures
Ingredient
Percent
1st passa
SBR
PB
CB
Silica
Silane
PA
ZnO
StAc
6ppd
Sun
MCC
2nd passb
DPG
CBS
S
Total
Batch 1
0MCC
phr
80.45
19.45
7.78
58.3
3.89
2.33
1.94
1.56
1.56
3.89
0
1.07
1.30
0.92
184.44
Batch 2
Batch 3
Batch 4
Batch 5
5.6MCC 11.8MCC 17.6MCC 23.5MCC
phr
phr
phr
phr
80.45
80.45
80.45
80.45
19.45
19.45
19.45
19.45
7.78
7.78
7.78
7.78
54.41
50.7
46.7
42.7
3.89
3.89
3.89
3.89
2.33
2.33
2.33
2.33
1.94
1.94
1.94
1.94
1.56
1.56
1.56
1.56
1.56
1.56
1.56
1.56
3.89
3.89
3.89
3.89
3.89
7.70
11.6
15.6
1.07
1.30
0.92
184.44
1.07
1.30
0.92
184.44
1.07
1.30
0.92
184.44
1.07
1.30
0.92
184.44
a Compounding procedure of 1st pass (master batch 1/MB1): 100 rpm and 0.207 MPa (30 psi)
1. Added rubber and mixed it for 30 s.
2. Added half silica, half MCC and silane, and then mixed them for 45 s.
3. Added the left silica, the left MCC and Sun, and then mixed them for 50 s.
4. Added CB, PA, ZnO, StAc, 6ppd, and then mixed them for 25 s.
5. Swept, auto ram lifted, and mixed for another 350 s.
6. Discharged at 55 rpm and 0.207 MPa (30 psi).
b Compounding procedure of 2nd pass (master batch 2/MB2): 77 rpm and 0.207 MPa (30 psi)
1. Loaded MB1, curatives, and MB1.
2. Mixed for 30 s and sweep.
3. Discharged either at 120 s or 100C.
46
2.4.3 Evaluation of viscoelastic properties of un-vulcanized rubber composites
2.4.3a Characterizations of Mooney viscosity and pre-vulcanization
Mooney viscosity and scorch tests were both carried out with Monsanto
Mooney Viscometer 2000 (TechPro Inc., Cuyahoga Falls, OH). Mooney viscosities
were measured with a large rotor at an oscillating rate of 0.2 rad/s. Initial viscosity
was recorded immediately after preheating a rubber composite specimen for 1 min at
100 C. Mooney viscosity at 100 C was recorded after pre-heating the specimen for
1 min and the total testing time was 4 min according to ASTM D1646. The initial
viscosities and Mooney viscosities of aged rubber composites were obtained after unvulcanized rubber composites were stored at room temperature for one week and two
weeks, respectively. The scorch test was carried out in accordance with ASTMD1646 as well. The testing temperature was 125 C and the total testing time was 60
min. The temperature was set at 125C because the processing temperature in rubber
manufacturing could ascend by incident. The times required for increasing Mooney
viscosity above its minimum viscosity by 5, 10, and 35 units were designated as t5, t10,
and t35. The total volume of two pieces of specimens for each test was around 253
cm3. Two pieces of specimens were used since they filled up the cavity of the test
chamber better than a single piece of specimen.
2.4.3b Evaluation of apparent shear stress and apparent shear viscosity

Apparent shear stress and apparent shear viscosity of the rubber composites
were obtained with a Capillary Rheometer, Rheo-testing 1000 (Goettfert, Germany) in
accordance with ASTM D5099.
The diameter of the die was 1.5 mm and the
47
length/diameter ratio of the die was 15. The entrance angle was 90 degrees. The
instrument was warmed up for 30 min at 100 C. The cycle of apparent extrusion
speed was from 1000 s-1, 500 s-1, 230 s-1, 115 s-1, 57.5 s-1, 23.0 s-1, to 11.5 s-1. The
apparent shear stresses and apparent shear viscosities at all apparent shear velocities
were obtained after 3 min pre-heating and the total testing time was 30 min.
2.4.3c Determination of curing characteristics

The vulcanizing characteristics of each rubber composite were determined with
an oscillating disk cure meter, Rheo-tech (TechPro Inc., Cuyahoga Falls, OH) in
accordance with ASTM D 2084. The curing temperature for SBR and PB rubber was
160 C. The oscillating frequency was 1.70.1 Hz with amplitude of 3.0. The
volume of a test specimen was between 3 and 5 cm3. The total testing time was 30
min. Scorch time (Ts-2) and cure time (Tc-90) were measured.
2.4.4 Evaluation of mechanical properties of vulcanized rubber composites

2.4.4a Evaluation of tensile strength of unaged and heat-aged rubber composites
The tensile stresses of rubber composites were measured with an Instron 5500
R, model 4201 (Instron, Canton, MA) in accordance with ASTM D624.
The
crosshead speed was 50 cm/min and the original gauge of the extensometer was 25
mm. The thickness and width of dumbbell specimens were about 2.00 mm and 6.25
mm, respectively.
Tensile strength and the modulus at 100%, 200%, and 300%
elongation were calculated from the following equations:
48
Tensile strength=
stress @ break
original _ cross _ sec tion _ area
Eq. 2.1
Modulus at 100% elongation=
stress @100%elongation
Eq. 2.2
stress @ 200%elongation
Eq. 2.3
stress @ 300%elongation
Eq. 2.4
The heat-aging of dumbbell specimens was carried out in accordance with

ASTM D573. The specimens were placed in a 100 C oven for 70 h. The hardness
(type A) of test specimens was measured by a Durometer type A (Instrument & MFG
Co. Inc., New York) in accordance with ASTM D2240. The thickness of test
specimens for hardness test was about 6.0 mm.
2.4.4b Evaluation of tear strength of rubber composites

The tear strength was measured in accordance with ASTM D412. The die
cutter for preparing tear-test specimens was Die C.
The thickness of tear-test
specimens was around 2.00 mm. The tear strength of hot rubber composites was
obtained after tear-test specimens were boiled in hot water for one hour.
specimens were tested when they were still hot.
The
49
2.4.4c Evaluation of heat resistance and heat blowout time
Heat buildup and heat blowout tests were performed with a Firestone
Flexometer (Firestone Tire & Rubber Co., Akron, OH) in accordance with ASTM
D623. The specimen was placed between two plates. One of the plates had an
oscillating speed of 13.3 Hz. For heat buildup test, the pressure was fixed at 0.8 MPa
and the test time was 45 min. The inside temperature of the rubber composites was
recorded after 45 min and used as an indicator for the heat-generating rate of rubber
composites. For the heat blowout test, the pressure was fixed at 1.7 MPa and the
moving amplitude of the oscillating plate was 8.2 mm. The time was recorded when
the deformation reached to 8.2 mm. The dimensions of Firestone specimen were: base
54.028.6 mm, top 50.825.4 mm, and altitude 38.1 mm. The cure time for Firestone
specimens was four times of that for tensile specimens.
2.4.4d Determination of dynamic mechanical properties

Dynamic mechanical properties were determined with a Mechanical energy
resolver (MER) MER-1100B (Imass Inc., Accord, MA) in compression and tension on
a cylindrical specimen. The frequency of the MER test was 1 Hz with a constant
dynamic force of 0.7 kg-RMS (RMS: root mean square). The MER test was done at
two different temperatures of 23 C and 100 C. The diameter and length of MER
specimens were about 17.8 mm and 25.0 mm, respectively. The cure time for MER
specimens was doubled of that for tensile specimens.
50
2.4.5 Statistical analysis of experimental data
All experimental data with replicates were analyzed with a standard twosample t-test using S-PLUS statistical software (Version 8.0, Insightful Corp., Seattle,
WA, USA). All comparisons were based on a 95% confidence interval.
2.5 Results and discussion

2.5.1 Compositions of rubber composites and compounding procedures
Table 2.2 shows the compositions of rubber composites from Batch 1 to Batch
5 and the compounding procedures for all batches. Batch 1 was the control rubber
composites that did not contain any MCC filler. The percentages of silica filler that
was replaced by the MCC filler were as follows: 5.6% in Batch 2, 11.8% (almost
double of the Batch 2) in Batch 3, 17.65 (almost triple of the Batch 2) in Batch 4, and
23.5% (close to quadruple of the Batch 2) in Batch 5. The weight percentages of other
components in rubber composites were the same for all batches. The compounding
procedures included two passes. In the first pass all the materials except the curatives
of the rubber composites were included. The total mixing time in the first pass was
500 s. A high shear and a long mixing time were used in the first pass for allowing the
even dispersion of all fillers and other additives in the rubber matrix. The rubber
composites obtained from the first pass were defined as Master Batch 1 (MB1). The
curatives (DPG, CBS and S) could not be added in the first pass because the internal
temperature could be high enough to cause the pre-cure of rubber composites. As a
result, a second pass was used where the curatives were added to the rubber
composites. The rubber composites obtained from the second pass were defined as
51
Master Batch 2 (MB2). For preventing the pre-cure of rubber composites, MB2
was discharged either at 120 s of the mixing time or at 100 C, whichever came first.
2.5.2 Compounding of the rubber composites in an internal rubber mill

Figure 2.1 shows the power required for the thorough mixing of the rubber
composites in an internal rubber mill. Because all the components in the first pass
were added into the mill during the first 240 s, the power required for the thorough
mixing was determined after 240 s (Figure 2.1). When the amount of silica replaced
by MCC increased, the power required for compounding the rubber composites
decreased.
These results appeared to indicate that it took less energy to evenly
disperse MCC into the rubber matrix than to evenly disperse the same amount of
silica. The densities of MCC, silica, and carbon black are around 1.42 (Sun, 2005),
2.20 (Perriot et al., 2006), and 1.81 (Gillen et al., 1999) g/cm3 , respectively. MCC is
lighter, i.e., bulkier than silica. MCC particles had less tendency of aggregation
among themselves than silica particles and carbon black particles. A part of energy
required for the thorough mixing was used to break down the silica or carbon black
aggregates. During the compounding, some MCC particles might be inserted between
silica particles, which would reduce the re-aggregation of silica particles and facilitate
the dispersion of silica particles into the rubber matrix, thus reducing the energy
required for evenly dispersing the fillers into rubber matrix.
52
Batch 1
Batch 2
Batch 3
Power (KW)
Batch 4
Batch 5
3
250
275
300
325
350
375
400
425
450
475
500
Time (s)
Figure 2.1 Energy consumptions of Batch 1, Batch 2, Batch 3, Batch 4, and Batch 5
during internal rubber mill processing
Figure 2.2 shows the temperature profiles of five batches during the
compounding in the first pass. The temperature in all five batches linearly decreased
as the mixing proceeded. The temperature was an indicator of the heat generated
during the compounding.
Frictions among fillers generated heat.
When the
compounding proceeded, more fillers were dispersed into the rubber matrix and less
frictions among fillers would occur, which might explain why the temperature linearly
decreased along the mixing time (Figure 2.2). As the compounding proceeded, some
filler particles would collide with each other to form aggregates again. When the
aggregates were broken down, frictions occurred and heat was generated. The higher
aggregation tendency of silica and carbon black particles might explain why the
temperature in Batch 1 decreased at a slower rate than that in other batches. From
Batch 2 to Batch 5, the amount of silica replaced by MCC increased, and the
temperature profile was also down-shifted in an almost parallel fashion. The reduction
53
of filler-filler interactions by MCC might account for this temperature down-shift.
Heat dissipation could be one of the factors that temperature dropped down during the
process because the temperature of the mixer was maintained at 65 C and was lower
than that of the rubber mixture.
Batch 1
Batch 2
Batch 3
180
Temperature (C)
Batch 4
Batch 5
170
160
150
250
275
300
325
350
375
400
425
450
475
500
Time (s)
Figure 2.2 Temperature profiles of Batch 1, Batch 2, Batch 3, Batch 4, and Batch 5
during internal rubber mill processing
A previous study has shown that the reaction of silane coupling agent with
silica occurs at the temperature above 150 C (Wagner, 1976).
The mixing
temperature for each batch in this study was above 150 C (Figure 2.2), which
indicated that the coupling reaction between the silane coupling agent and silica would
occur.
2.5.3 Mooney viscosity of the rubber composites

Table 2.3 shows the initial viscosities and Mooney viscosities of unaged and
aged rubber composites from each batch. The test temperature was set at 100 C
54
because most industry processes such as milling, extrusion, and calendaring
occurred around this temperature. The numbers in the first three columns were the
results of unaged rubber composites from each batch. The initial viscosities of the
unaged rubber composites decreased from Batch 1 to Batch 2, increased from Batch 2
to Batch 3, and then decreased again from Batch 3 to Batch 5. Low initial viscosity
resulted from less filler-filler interactions and better dispersion of fillers in the rubber
matrix. The Mooney viscosity for unaged rubber composites decreased with increase
in MCC content from Batch 1 to Batch 5. The viscosity difference () between the
Mooney viscosity and the initial viscosity is indicative of how easy the rubber
composite is processed to form different products. The smaller the difference the
easier the process. The viscosity difference for unaged rubber composites slightly
increased from Batch 1 to Batch 3. The viscosity differences for Batch 3 and Batch 4
were the same. The viscosity difference slightly decreased from Batch 4 to Batch 5.
The range of the viscosity differences for all batches was small. There will be little
problems of processing the rubber composites from all batches.
The next three
columns show the initial viscosity, the Mooney viscosity, and the viscosity differences
() for those rubber composites that have been aged for one week (Table 2.3). The
one-week aging significantly increased the initial viscosity and the Mooney viscosity
for all batches (Table 2.3). Both the initial viscosity and the Mooney viscosity for
one-week-aged rubber composites gradually decreased from Batch 1 to Batch 5.
In
other words, the initial viscosity and the Mooney viscosity both decreased along with
increasing the MCC content in the rubber composites. The viscosity difference
55
between the Mooney viscosity and the initial viscosity slightly increased from
Batch 1 to Batch 2 and then gradually decreased from Batch 2 to Batch 5, which
implied that addition of MCC facilitated the process of aged rubber composites into
different products. For those rubber composites that had been aged for two weeks, the
initial viscosity, the Mooney viscosity, and the viscosity difference between the
Mooney viscosity and the initial viscosity all decreased when the MCC content
increased from Batch 1 to Batch 5 (Table 2.3). These results demonstrated that the
replacement of silica by MCC facilitated the processes of aged rubber composites.
For the rubber composites from each batch, the initial viscosity and the Mooney
viscosity both increased when the aging time was increased (Table 2.3). During
storage, i.e., aging, fillers tend to migrate and aggregate, which results in the viscosity
increase. After the rubber composites were aged for either one week or two weeks,
the net gain of the initial viscosity and the net gain of the Mooney viscosity for each
Batch decreased along with the increase in the MCC content from Batch 1 to Batch 5.
We speculate that the following reasons may contribute the decrease in the net gains
of the viscosities: 1) MCC has lower tendency to aggregate than silica and carbon
black. The net gains of the viscosities would be smaller for the rubber composites
with a higher MCC content even if all fillers have the same migration rates. 2) MCC
slows down the migration of other two fillers, silica and carbon black. 3) MCC
interferes the aggregation of silica and carbon black.
Table 2.3 Initial viscosity and Mooney viscosity (MV) for unaged and aged rubber composites at 100C
Batch 1
Batch 2
Batch 3
Batch 4
Batch 5
Unaged
Initial
viscositya
99.3
97.7
98.8
93.8
89.6
MVb
76.4
72.5
68.4
63.5
62.3
-22.9
-25.2
-30.4
-30.3
-27.3
One-week aged
Initial
MV
viscosity
119.6
80.9
116.8
76.6
105.7
70.8
98.5
65.9
93.4
63.2
-38.7
-40.2
-34.9
-32.6
-30.2
IV1c MV1c
20.3
19.1
6.9
4.7
3.8
4.5
4.1
2.4
2.4
0.9
Two-week aged
Initial
MV
viscosity
127.6
83.3
119.7
78.1
112.1
71.9
100.7
66.6
94.9
64
IV2c
MV2c
-44.3
-41.6
-40.2
-34.1
-30.9
28.3
22.0
13.3
6.9
5.3
6.9
5.6
3.5
3.1
1.7
a. Initial viscosity: the immediate reading of viscosity after one min pre-heating.
b MV: Mooney viscosity after one min pre-heating and four min testing time.
c =MV-Initial viscosity, IV1=Initial viscosity(one-week aged)- Initial viscosity(unaged), IV2= Initial viscosity(two-week aged)- Initial
viscosity(unaged), MV1=MV(one-week aged)-MV(unaged), MV2=MV(two-week aged)-MV(unaged).
56
57
2.5.4 Pre-vulcanization characteristics of the rubber composites
Table 2.4 shows the t5, t10 and t35 of all rubber composites. The t5 gradually
decreased when the MCC content increased from Batch 1 to Batch 4 and then slightly
increased from Batch 4 to Batch 5. The t10 was longer than 60 min because the
viscosity did not increase by 10 units when the test was done at 60 min. The t10
decreased from Batch 3 to Batch 4 and then remained roughly the same from Batch 4
to Batch 5. The t35 for the Batches 1-3 was longer than 60 min because the viscosity
did not increase by 35 units when the test was done at 60 min. The t35 for Batch 4 and
Batch 5 was not significantly different. Generally speaking, the t5, t10 and t35 indicate
the pre-vulcanization characteristics during processing. If the t5, t10 and t35 are too
low, the rubber composites are vulcanized too fast, which means that the viscosity
increases too fast to allow the rubber composites to take a shape of the resulting
products. Therefore, the t5, t10 and t35 have to be sufficiently high. The Batch 1 is a
typical recipe for rubber tire application.
The pre-vulcanization characteristics of a
new rubber composite are considered desirable if its t5, t10 and t35 are close to those of
the Batch 1. The results from Table 2.4 suggested that MCC decreased the t5, t10 and
t35 to some extent. As shown in Table 3, MCC decreased the initial viscosity and the
Mooney viscosity of unaged and aged rubber composites. In other words, the rubber
composites containing MCC have a lower viscosity than the Batch 1 before any
process. When compared with the Batch 1, the lower initial viscosity will offset the
faster increase in the viscosity (i.e., the lower t5, t10 and t35) during a vulcanization
process. Therefore the lower t5, t10 and t35 of the rubber composites containing MCC
would not negatively affect their vulcanization processes.
58
Table 2.4 Pre-vulcanization characteristics at 125C
Batch 1
Batch 2
Batch 3
Batch 4
Batch 5
t5 (min)a
57.1
54.6
52.0
43.5
45.2
t10 (min)b
-d
58.8
48.2
49.7
t35 (min)c
55.4
56.2
a: t5: The time required for increasing the viscosity above the minimum viscosity by 5 units
b: t10: The time required for increasing the viscosity above the minimum viscosity by 10 units
c: t35: The time required for increasing the viscosity above the minimum viscosity by 35 units
d: (-): Data were not available because the viscosity did not increase by 10 units or 35 units when the
test was done at 60 min.
2.5.5 Rheological properties of the rubber composites

The rheological properties of the rubber composites were obtained with the
capillary rheometer at two apparent shear velocities of 500 s-1 and 1000 s-1 because
milling, extrusion and calendaring of rubber composites are usually carried out at 500
s-1 and the injection molding at 1000 s-1. The apparent shear stress of each batch at
1000 s-1 was higher than that at 500 s-1, which is consistent with the fact that a high
force had to be applied to the rubber composites to achieve a high flow rate (Figure
2.3).
The apparent shear stress decreased from Batch 1 to Batch 4, and then
maintained almost the same from Batch 4 to Batch 5. These results revealed that
MCC reduced the force required for achieving the same flow rate.
59
Apparent shear stress
ap (Pa)
3.310 5
3.010
500 s-1
1000 s-1
2.810 5
2.510 5
2.310 5
2.010 5
)
C
C
)
M
(2
3.
5%
5
at
ch
B
at
ch
(1
1.
8%
(1
7.
6%
C
C
C
C
)
C
C
M
B
at
ch
2
B
at
ch
at
ch
(5
.6
%
(c
on
tr
ol
)
1.810 5
Figure 2.3 The apparent shear stresses in each batch at two different apparent shear
velocities 500 s-1 and 1000 s-1
With the increase in the MCC replacement from Batch 1 to Batch 4, the
apparent dynamic shear viscosity decreased at both apparent shear velocities (Figure
2.4).
These results indicated that the MCC facilitated the process of the rubber
composites and reduced the energy consumption for the process.
The apparent
dynamic shear viscosity for Batch 4 was almost the same as that for Batch 5, which
the MCC effect on the reduction of the energy reduction flattened out when the MCC
replacement was 17.6% or higher (Figure 2.4).
500
500 s-1
1000 s-1
400
300
)
M
C
C
)
C
C
M
C
C
B
at
ch
(1
7.
6%
M
B
at
ch
3
at
ch
B
(1
1.
8%
(5
.6
%
2
(2
3.
5%
)
C
C
M
nt
r
(c
o
1
B
at
ch
B
at
ch
200
ol
)
Apparent dynamic shear

viscosity ap (PaS)
60
Figure 2.4. The apparent shear viscosities in each batch at two different apparent shear
velocities of 500 s-1 and 1000 s-1
2.5.6 Cure Characteristics of the rubber composites

The scorch time (Ts-2) for all five batches were about 6 min. This implied that
the addition of MCC in rubber composites did not have significant influence on the
time of initiating curing reactions (Figure 2.5). Tc-90 is usually used as the cure time,
i.e., the time required for full cure of the rubber composites. The cure time decreased
from Batch 1 to Batch 2, remained the same from Batch 2 to Batch 3, decreased again
from Batch 3 to Batch 4, and then kept almost the same from Batch 4 to Batch 5
(Figure 2.5). As discussed previously, MCC might facilitate the dispersion of silica.
A good dispersion of silica (i.e., low aggregation of silica) means that more silanecoupling-agent-coated silica surfaces are available for vulcanization, thereby reducing
61
the cure time. It is still poorly understood that the cure time did not linearly decrease
along with increasing the MCC content.
Because the Tc-90 was lower than 14 min
for all batches, the cure time of making tensile specimens for all the batches was set to
be 14 min.
15.0
T s-2
T c-90
Time (min)
12.5
10.0
7.5
C
)
M
C
C
)
(2
3.
5%
at
ch
(1
7.
6%
M
C
C
)
B
at
ch
(1
1.
8%
M
C
M
C
B
at
ch
2
B
at
ch
B
at
ch
(5
.6
%
(c
on
tr
o
l)
C
)
5.0
Figure 2.5 The scorch time (Ts-2) and cure time (Tc-90) of each batch at 160C. Ts-2:
the time required for increasing the torque above its minimum by 2 units. Tc-90: the
time required for reaching 90% of the maximum torque.
2.5.7 Tensile properties of unaged and heat-aged rubber composites

The tensile strength significantly increased from Batch 1 to Batch 2 (Figure
2.6). The tensile strengths of rubber composites from Batch 3, Batch 4, and Batch 5
were comparable with that of control rubber composites from Batch 1 (Figure 2.6).
For those heat-aged rubber composites, the tensile strength gradually decreased from
Batch 1 to Batch 3 and then remained the same from Batch 3 to Batch 5 (Figure 2.6).
62
There are two opposite effects that can affect the tensile strengths. First, a good
dispersion of fillers can improve the interactions between fillers and rubber matrix,
thus improving the tensile strength (Ishiaku et al., 2000; Haghighat et al., 2005).
Second, MCC has a lower Youngs modulus than silica (Eichhorn and Young, 2001).
MCC-rubber composites are inherently not as strong as silica-rubber composites,
which mean that silica cannot be completely replaced by MCC. Results from Figure
2.6 demonstrated that tensile strengths of the rubber composites containing MCC were
stronger than or comparable to the rubber composites without MCC (Batch 1) when
the MCC content was below 23.5%. It is still poorly understood that the treatment of
the rubber composites at 100 C for 70 h slightly reduced the tensile strength of the
rubber composites containing MCC.
63
Unaged
Tensile strength (MPa)
Aged
20
15
10
C
C
)
M
(2
3.
5%
M
Ba
tc
h
4
Ba
tc
h
(1
7.
6%
M
(1
1.
8%
M
Ba
tc
h
C
C
)
C
C
)
C
C
l)
Ba
tc
h
(5
.6
%
(c
on
tro
1
Ba
tc
h
Figure 2.6. The tensile strength of unaged and aged rubber composites. Each data
point is the mean of three replicates, and the error bar represents one standard
deviation.
Figure 2.7 shows the effects of MCC replacement in rubber composites on

modulus at 100%, 200%, and 300% elongations. The modulus at 100% elongation of
unaged rubber composites from Batch 2, Batch 3, Batch 4, and Batch 5 were higher
than that of unaged control rubber composites from Batch 1. The modulus at 100%
elongation of unaged rubber composites gradually increased as the amount of MCC
replacement increased from Batch 2 to Batch 5. The modulus at 200% elongation of
unaged rubber composites from Batch 2, Batch 3, Batch 4, and Batch 5 was higher
than that of unaged control rubber composites from Batch 1. The modulus at 200%
elongation of unaged rubber composites slightly increased as the percentage of MCC
64
replacement was increased from 0% to 11.8 % (i.e., from Batch 1 to Batch 3), and then
remained statistically the same from 11.8% to 23.5% of MCC replacement, i.e., from
Batch 3 to Batch 5 (Figure 2.7). The modulus at 300% elongation of unaged rubber
composites from Batch 2, Batch 3, Batch 4, and Batch 5 was higher than that of
unaged control rubber composites from Batch 1. The modulus at 300% elongation of
unaged rubber composites slightly increased as the percentage of MCC replacement
was increased from 0% to 11.8 %, i.e., from Batch 1 to Batch 3, remained statistically
the same from 11.8% to 17.6% of MCC replacement, i.e., from Batch 3 to Batch 4,
and then decreased from 17.6% to 23.5% of MCC replacement, i.e., from Batch 4 to
Batch 5. The modulus at 100%, 200%, and 300% elongation for all aged specimens
increased when compared to the corresponding modulus at 100%, 200% and 300%
elongation for all unaged ones. The modulus of aged specimens at 100% elongation
with MCC was larger than that without MCC. The modulus of aged specimens at
200% elongation for Batch 1 had no difference from those for Batch 2 and Batch 4.
The modulus of aged specimens at 200% elongation for Batch 1 was larger than those
for Batch 3 and Batch 5.
Moreover, the modulus at 300% elongation of aged
specimens from Batch 2 was comparable to Batch 1. However, the modulus at 300%
elongation of aged specimens from Batch 3, Batch 4, and Batch 5 were lower than
Batch 1. The following mechanisms may explain why the modulus changed after
aging.
After vulcanization, the crosslinks in rubber composites were mostly
polysulfide bonds.
Polysulfide bonds were more flexible, i.e., less stiff than
monosulfide bonds. As heat aging proceeded, some polysulfide bonds were broken
65
down to monosulfide bonds, which resulted in the increase in the modulus (Haghighat
et al., 2005).
Unaged @ 100%
Unaged @ 200%
Unaged @ 300%
Aged @ 100%
12.5
Aged @ 200%
Modulus (MPa)
10.0
Aged @ 300%
7.5
5.0
2.5
)
C
C
)
(2
3.
5%
C
C
5
Ba
tc
h
Ba
tc
h
3
Ba
tc
h
(1
1.
8%
(1
7.
6%
C
C
M
(5
.6
%
Ba
tc
h
1
Ba
tc
h
C
C
(c
on
tro
l)
0.0
Figure 2.7 The modulus at 100%, 200% , and 300% elongation of unaged rubber
composites and the modulus at 100%, 200%, and 300% elongation of aged rubber
composites. Each data point was the mean of three replicates, and the error bar
represents one standard deviation.
Figure 2.8 shows the effects of MCC replacement in rubber composites on

elongation-at-break.
The elongation-at-break of unaged rubber composites from
Batch 2 was not significantly different from that of unaged control rubber composites
from Batch 1. The elongation-at-break of unaged rubber composites from Batch 3,
Batch 4, and Batch 5 were slightly shorter than that of unaged control rubber
66
composites from Batch 1 (Figure 2.8). The elongation-at-break of unaged rubber
composites from Batch 3 was almost the same as that from Batch 4 and Batch 5. The
elongation-at-break for each aged specimen was shorter than the elongation-at-break
for each unaged one. Polysulfide bonds are more stretchable than monosulfide bond.
Because some polysulfide bonds were transformed into monosulfide bonds as the
heat-aging proceeded, the elongation-at-break of the heat-aged composites became
shorter than that of the unaged ones (Haghighat et al., 2005).
Unaged
Elongation at break (%)
Aged
800
600
400
200
C
C
)
M
(2
3.
5%
M
Ba
tc
h
(1
7.
6%
M
Ba
tc
h
(1
1.
8%
M
Ba
tc
h
C
C
)
C
C
)
C
C
l)
2
(5
.6
%
(c
on
tro
1
Ba
tc
h
Ba
tc
h
Figure 2.8 The elongation-at-break of unaged and aged rubber composites. Each data
deviation.
67
The hardness of aged rubber composites was higher than that of corresponding
unaged composites from the same batch (Figure 2.9). The hardness of unaged rubber
composites from Batch 1 to Batch 3 was almost the same, and then increased from
Batch 3 to Batch 5. The hardness of aged rubber composites from Batches 1-4 was
about the same and was higher than that from Batch 5.
80
Unaged
Hardness A
Aged
70
60
C
)
M
C
C
)
(2
3.
5%
at
ch
(1
7.
6%
M
C
C
)
B
at
ch
(1
1.
8%
M
C
M
C
B
at
ch
2
B
at
ch
B
at
ch
(5
.6
%
(c
on
tr
o
l)
C
)
50
Figure 2.9 Hardness (type A) of unaged and aged rubber composites. The data point is
the median values of five measurements.
2.5.8 Tear strengths of the rubber composites and hot rubber composites
The tear strength of rubber composites from Batch 2, Batch 3, Batch 4, and
Batch 5 was lower than that from Batch 1, respectively (Figure 2.10). The tear
strengths of rubber composites were about the same from Batch 2 and Batch 3,
decreased from Batch 3 to Batch 4, and remained the same from Batch 4 to Batch 5.
Rubber composites without MCC filler had a higher homogeneity than those
68
containing MCC, thus MCC filled rubber composites had low tear strength. The tear
strength of hot rubber composites remained the same from Batch 1 to Batch 3. The
tear strength of hot rubber composites decreased from Batch 3 to Batch 4 and then
remained the same from Batch 4 to Batch 5 (Figure 2.10).
Tear
Hot tear
Tear Strength (N/mm)
60
50
40
30
20
10
C
C
)
C
C
)
(2
3.
5%
5
Ba
tc
h
Ba
tc
h
(1
7.
6%
(1
1.
8%
C
C
)
C
C
)
M
Ba
tc
h
2
Ba
tc
h
Ba
tc
h
(5
.6
%
(c
on
tro
l)
Figure 2.10 The tear strength of rubber composites and hot rubber composites. Each
data point is the mean of three replicates, and the error bar represents one standard
deviation.
2.5.9 Heat build up and heat blow out time of the rubber composites
When rubber composites underwent a long-term dynamic distortion, the heat
built up inside the composites (i.e., the temperature increased).
The inside
temperature after 45 min dynamic distortion and the time after the rubber composites
deformed to 8.2 mm were recorded and are shown in Figure 2.11. The temperature
69
significantly decreased when the MCC content was increased from Batch 1 to Batch 5
(Figure 2.11). However, the blowout time slowly increased from Batch 1 to Batch 3
and then rapidly increased from Batch 3 to Batch 5. The heat capacity of cellulose
(1.3 kJ*kg-1*K-1) is larger than that of silica (0.7 kJ*kg-1*K-1) (Ball et al., 1999).
MCC could serve as heat sink and significantly delayed the blowout of the rubber
composites, which were very desirable features for tire application. There was smoke
coming out of blown out test specimens, which suggested that MCC was degraded to
some extent. This is consistent with the fact that MCC is less heat-resistant than silica
and carbon black.
The previous study on MCC with themorgravity analysis (TGA)
revealed that there was little weight loss when the temperature was below 200 C
(Ardizzone et al., 1999).
The temperature in some pocket areas of the rubber
composites might exceed the degradation temperature (200 C) during the Firestone
heat blowout test, which resulted in the smoke. The degradation of MCC requires
energy, thus dissipating heat. A combination of the high heat capacity and a partial
degradation of MCC may account for the low inside temperature and long blowout
time. How the partial degradation may affect the actual usable life of rubber tires
warrants further investigation.
180
temperature
170
time
100
80
160
60
150
40
140
0
M
C
at
ch
(2
3.
5%
M
C
C
)
B
at
ch
3
at
ch
(1
7.
6%
(1
1.
8%
M
C
M
C
(5
.6
%
2
B
l)
tr
o
(c
on
1
B
at
ch
B
at
ch
C
)
120
C
)
20
C
)
130
Time (min)
Temperature (C)
70
Figure 2.11 The inside temperature of rubber composites from the heat buildup test
and the blowout time of rubber composites from heat blowout test
2.5.10 Dynamic mechanical properties of the rubber composites

The tan was obtained from each rubber composite at a low temperature (23
C) and a high temperature (100 C). For test specimens from the same batch, the
tan at the low temperature was higher than that at the high temperature (Figure 2.12).
At the low temperature, the tan values of Batch 2 and Batch 3 were statistically the
same as that of Batch 1. At the low temperature, the tan decreased from Batch 3 to
Batch 4 and then remained the same from Batch 4 to Batch 5.
At the high
temperature, the tan decreased from Batch 1 to Batch 2, remained the same from
Batch 2 to Batch 3 and then rapidly decreased from Batch 3 to Batch 5 (Figure 2.12).
A high tan of a rubber composites means low slippery between rubber tires and road,
71
i.e., a high rolling resistance and low gas mileage. The tan from the low temperature
has implications on the rubber tire application in the raining season when the
temperature is low and road is wet. In the raining season, the high rolling resistance
between tires and the road is desirable. Therefore, the higher the tan obtained from
the low temperature the better.
Rubber composites with up to 11.8% of MCC
replacement had the tan, i.e., the traction, comparable to control rubber composites at
low temperature. Further increase in the MCC content in rubber composites decreased
the tan, i.e., the wet traction at low temperature. The tan from the high temperature
has implications on the rubber tire application in the summer when the temperature is
high, road is less slippery than in the raining season, and the fuel efficiency of
automobiles becomes an important consideration. In summer, the low tan of rubber
tires, i.e., the low rolling resistance between rubber tires and road is preferred for
obtaining a high fuel efficiency and good mileages of automobiles.
The tan
decreased from Batch 1 to Batch 2, flattened out from Batch 2 to Batch 3 and then
rapidly decreased from Batch 3 to Batch 5, which implies that the partial replacement
of silica by MCC in rubber composites would decrease the rolling resistance and
increase the fuel efficiency of automobiles if the rubber tires are made with the rubber
composites containing MCC.
72
0.22
23C
0.20
100C
Tan
0.18
0.16
0.14
C
)
M
C
C
)
(2
3.
5%
at
ch
(1
7.
6%
M
C
C
)
B
at
ch
(1
1.
8%
M
C
M
C
B
at
ch
2
B
at
ch
B
at
ch
(5
.6
%
(c
on
tr
o
l)
C
)
0.12
Figure 2.12 Viscoelastic property (tan) of each batch at 23C and 100C. Each data
deviation.
2.6 Conclusions
The partial replacement of silica with MCC significantly reduced the energy
required for thorough mixing of rubber, fillers, and other additives. MCC significantly
reduced the initial viscosity and the Mooney viscosity of un-vulcanized rubber
composites, thus facilitating the formation of rubber composites with different shapes
prior to vulcanization. Moreover, the addition of MCC reduced the difference in
viscosities between unaged and aged rubber composites, thus facilitating the handling
and process of the rubber composites. The rubber composites with MCC replacement
had a higher pre-vulcanization rate than those without MCC. The low initial viscosity
and low Mooney viscosity of rubber composites containing MCC would offset the
73
negative impacts of a higher pre-vulcanization rate on the process. MCC decreased
the shear stress and shear viscosities, which further demonstrated that MCC facilitated
the processes such as milling, calendaring, extrusion, and injection molding of rubber
composites. The tensile strengths and the modulus at 100%, 200%, 300% elongation
of rubber composites containing up to 17.6% of MCC were higher than those without
MCC.
MCC increased the heat resistance of rubber composites.
The partial
replacement of silica with MCC slightly decreased the tear strength of the rubber
composites and hot rubber composites. The partial replacement of silica with MCC
did not decrease the tan at the MCC replacement of up to 11.8% at low temperature
such as in the raining season, and decreased the tan at high temperature such as in the
summer time.
The automobile tires made from rubber composites containing up to
11.8% MCC would have the same traction on road in the winter as those without
MCC and would give the automobiles a higher fuel efficiency in the summer than
those without MCC.
2.7 Acknowledgments
Financial support for this research was provided by Schill+Seilacher Struktol
AG, Hamburg, Germany and Struktol Company of America, Stow, OH. The authors
greatly appreciated the experimental support from Mr. P. Danilowicz, Mr. Z. Brdarski,
Mrs. B. Eikelberry, and Mr. K. Tracy at Struktol Company of America.
74
2.8 References
features and water sorption capability. Cellulose 6, 57-69.
Ball, R., McIntosh, A.C., Brindley, J., 1999. The role of char-forming processes in the
thermal decomposition of cellulose. Phys. Chem. Chem. Phys. 1, 5035-5043.
Bowyer, J.L., Shmulsky, R., Haygreen, J.G., 2003. Composition and Structure of
Wood Cells. In: Bowyer, J.L., Shmulsky, R., Haygreen, J.G. (Eds.), Forest
Products and Wood Science: An Introduction. Iowa State Press, Ames, Iowa,
pp. 47-64.
Derringer, G.C., 1971. Short fiber-elastomer composites. J Elastoplast 3, 230-248.
Eichhorn, S.J., Young, R.J., 2001. The Young's modulus of a microcrystalline
cellulose. Cellulose 8, 197-207.
Gillen, K.T., Celina, M., Clough, R.L., 1999. Density measurements as a condition
monitoring approach for following the aging of nuclear power plant cable
materials. Radiation Physics and Chemistry 56, 429-447.
96, 2203-2211.
Ishiaku, U.S., Chong, C.S., Ismail, H., 2000. Cure characteristics and vulcanizate
properties of a natural rubber compound extended with convoluted rubber
powder. Polym Test 19, 507-521.
Ismail, H., Rosnah, N., Rozman, H.D., 1997. Curing characteristics and mechanical
properties of short oil palm fiber reinforced rubber composites. Polymer 38,
4059-4064.
Joseph, S., Joseph, K., Thomas, S., 2006. Green composites from natural rubber and
oil palm fiber: physical and mechanical properties. Int J Polym Mater 55, 925945.
Kubat, J., Klason, T.C.F., 1983. Composites from cellulose or lignocellulosic
materials and plastics. In. (Swed), Application: WO, p. 12 pp.
Laka, M., Chernyavskaya, S., Maskavs, M., 2003. Cellulose-Containing Fillers for
Polymer Composites. Mech Compos Mater 39, 183-188.
75
Nunes, R.C.R., Visconte, L.L.Y., 2000. Natural fibers/elastomeric composites. Nat
Polym Agrofibers Based Compos, 135-157.
Perriot, A., Vandembroucq, D., Barthel, E., Martinez, V., Grosvalet, L., Martinet, C.,
Champagnon, B., 2006. Raman Microspectroscopic Characterization of
Amorphous Silica Plastic Behavior. Journal of the American Ceramic Society
89, 596-601.
Reinsch, V.E., Kelley, S.S., 1997. Crystallization of poly(hydroxybutyrate-cohydroxyvalerate) in wood fiber-reinforced composites. J Appl Polym Sci 64,
1785-1796.
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Vigo, T.L., Kinzig, B.J., 1992. Composite Applications: The Role of Matrix, Fiber,
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76
CHAPTER 3 EFFECT OF ACRYLATED MICROCRYSTALLINE
CELLULOSE ON THE PROPERTIES OF SILICA-FILLED RUBBER
COMPOSITES

Corvallis, OR 97331
77
3.1 Abstract
Microcrystalline cellulose (MCC) was modified with acryloyl chloride to form
acrylated microcrystalline cellulose (A-MCC). A-MCC was investigated as a partial
replacement of silica filler in rubber composites in this study. A-MCC lowered initial
viscosity and Moony viscosity of the resulting rubber composites, thus facilitating the
process of the rubber composites. A-MCC improved the pre-vulcanization resistance
and lowered initial cure rate. Rubber composites containing A-MCC required the
same curing time as those containing silica only. Rubber composites containing AMCC were softer, more stretchable, and stronger than those containing silica only. AMCC enhanced the properties of heat-aged rubber composites, did not compromise the
tear strength of rubber composites at room temperature, and improved the tear strength
of rubber composites at high temperature.
3.2 Key words

acrylated microcrystalline cellulose, surface modification; rubber composites;
Mooney viscosity; mechanical properties
3.3 Introduction
Most of rubber products require fillers to achieve their desired properties
(Medalia and Kraus, 1994). The currently used fillers in the rubber tire application
mainly include carbon black and silica. Carbon black is derived from natural gas or
fossil oil. Silica is made from either the acidification of sodium silicate solutions
followed by a dehydration process or the reaction of silicon tetrachloride with water
78
vapor. Both fillers have high density, which has negative effect on the fuel efficiency
of automobiles. Furthermore, the production of carbon black and silica requires a
tremendous amount of energy. Therefore, the tire manufacturers are seeking for new
fillers that come from inexpensive, readily available, light-weighed and renewable
materials (Jong, 2006; Haghighat et al., 2007).
Cellulose is the most abundant renewable material. Short cellulose fibers have
been used as fillers in rubber composites (Derringer, 1971; Ismail et al., 1997;
Haghighat et al., 2005; Joseph et al., 2006). However the cellulose-filled rubber
composites are only used for making ropes, hose, belt, mats and insulation, and have
yet to be used in the tire tread application (Nunes and Visconte, 2000; Haghighat et
al., 2005). Cellulose contains amorphous and crystalline regions. Cellulose chains in
amorphous cellulose are loosely packed and can be easily accessible by chemicals for
various reactions such as acid hydrolysis, whereas those in crystalline cellulose are
tightly packed and are not easily accessible by chemicals. Crystalline cellulose is
much stronger and stiffer than amorphous cellulose and cellulose itself. Crystalline
cellulose with the size in micrometer range is called microcrystalline cellulose (MCC).
MCC can be readily produced from the acid hydrolysis of cellulose.
The acid
hydrolysis preferentially removes the amorphous regions of cellulose. MCC as a

reinforcing filler in composites has many advantages over glass fibers, silica and
carbon black: low cost, low density, easy to process, little abrasion to equipment,
renewability, and biodegradability (Vigo and Kinzig, 1992). Our recent study showed
that the partial replacement of silica with MCC in rubber composites provided a
79
number of benefits such as reduction of the energy required for thorough dispersion of
fillers in rubber matrix, reduction of Mooney viscosity, shear stress, and shear
viscosity of the rubber composites, improvement of the heat buildup resistance and the
potential of reducing the rolling resistance of the resulting rubber composites (Bai and
Li).
The partial replacement of silica with MCC did not negatively affect the
mechanical properties of the unaged and aged rubber composites, such as tensile
strength and modulus at 100%, 200%, and 300% elongation (Bai and Li). However,
addition of MCC slightly decreased tear strength and hot tear strength of the resulting
rubber composites (Bai and Li). It is believed that interfacial adhesion between fillers
and rubber matrix plays an important role in the tear strength and other mechanical
properties. In this study, acrylated MCC (A-MCC) was prepared and investigated as a
filler for the partial replacement of silica, hoping that the acrylate groups on the MCC
surface would form covalent linkages with rubber matrix, thus improving the tear
strength and other mechanical properties while retaining all those benefits that MCC
generated.
3.4 Experimental
3.4.1 Materials and equipment
Acetonitrile and diethyl ether were purchased from J.T. Baker Chemical Co.
(Philipsburg, NJ). Potassium-t-butoxide (KTB) and acryloyl chloride were purchased
from Alfa Aesar (Ward Hill, MA). Ethanol and acetone were purchased from VWR
International, LLC. (West Chester, PA). Table 3.1 shows the materials used for
80
rubber compounding, including codes, trade names, manufacturers, and locations of
manufacturers.
Table 3.1Materials in this study
Code
Rubber
SBR
Filler
Silica
MCC
A-MCC
Coupling
agent
Activator
Silane
ZnO
StAc
Processing
oil
Oil
Accelerator DPG
CBS
Vulcanizer
Trade name
Manufacturer
Buna VSL
Lanxess Corp.
5025-1
Ultrasil7000
Degussa Corp.
GR
Avicel PH 101 FMC Inc.
Synthesized from the lab
Struktol Company
Si69a
of America
Zinc oxide
Horsehead Corp.
Textile Rubber &
Stearic acid
Chemical Co.
Shell Catenex
Shell UK Oil
Oil SNR
Products Ltd.
Weber & Schaer
b
Perkacit DPG
GmbH & Co. KG
MLPC
Ekaland CBSc
International
Rubbermakers
R.E. Carroll Inc.
sulfur
a Bis(3-triethoxysilylpropyl)tetrasulfide.
b Diphenylguanidine.
c N-cyclohexyl-2-benzothiazolesulfenamide.
Location
Orange, TX
Akron, OH
Philadelphia, PA
Stow, OH
Monaca, PA
Nurnberg,
Germany
Manchester, UK
Hamburg,
Germany
Rion des Landes,
France
Akron, OH
81
FT-IR spectra were recorded on a NEXUS 470 FT-IR spectrometer (Thermo
Nicolet Corp., Madison, WI). Rubber composites were prepared with a rubber mill
(Reliable Rubber & Plastics Machinery Co., North Bergen, NJ) and a Brabender
(C.W. Brabender Instrument, Inc., South Hackensack, NJ). The curing of the rubber
composites was performed on a Carver Press (Carver, Inc., Wabash, IN). Viscosity of
rubber composites were measured with Monsanto Rheometer 100 (TechPro Inc.,
Cuyahoga Falls, OH). Strengths and elongation of rubber composites were measured
with Instron 5582 (Instron Corp., Norwood, MA).
The hardness of the rubber
composites was measured with Shore Instruments Durometer type A (Instron Corp.,
Norwood, MA).
3.4.2 Surface-modification of microcrystalline cellulose (MCC) with acryloyl chloride

The surface-modification of MCC was performed in accordance with a
literature procedure (Bojanic et al., 1996). MCC (20 g) was stirred in acetonitrile (100
mL). A suspension of KTB (12.45 g) in acetonitrile (100 mL) was added into the
MCC suspension, and the mixture was stirred at room temperature for 4 h. Acryloyl
chloride (30.1 g) in acetonitrile (100 mL) was added dropwise into the mixture at
room temperature over 30 min. The reaction mixture was stirred and refluxed for
another 10 h. The reaction mixture was filtered, washed sequentially with deionized
water, ethanol, and diethyl ether, and then dried under vacuum at 50 C to generate
acrylated MCC (A-MCC).
82
3.4.3 Compounding recipes and procedures
An open rubber mill was used to compound rubber mixtures. There were five
batches compounded according to the recipes and procedures in Table 3.2. The
control had silica as the sole filler. The percentages of silica replaced by A-MCC
were 6.25%, 12.5%, 18.75%, and 25.0%, corresponding to A-MCC-I, A-MCC-II, AMCC-III, and A-MCC-IV. The other components except silane coupling agent Si69
in the rubber composites had the same amount in all batches containing A-MCC. The
usage of Si69 was 18.8 g for the control, 17.6 g for A-MCC-I, 16.4 g for A-MCC-II,
15.23 g for A-MCC-III, and 14.06 g for A-MCC-IV. The usage of the Si69 was
proportional to the content of silica filler. The compounding procedure included two
passes. The first pass had all the materials for rubber composites, except the curatives.
The high shear in the first pass allowed even dispersion of all fillers and other
additives. The resulting rubber composites were compounded in Brabender at 152157 C for six min so that Si69 could react with silica.
The resulting rubber
composites then underwent the second pass where the curatives such as DPG, CBS,
and sulfur were included. The compounding temperature of the second pass was at 50
C for preventing pre-cure of rubber composites. After the second pass, all batches
were made into sheets with the thickness of 2-4 mm by the open rubber mill.
83
Table 3.2 Composition of rubber composites and compounding procedures
st
Control
A-MCC-I
A-MCC-II
A-MCC-III
A-MCC-IV
309.0
240.0
309.0
225
309.0
210
309.0
195
309.0
180
15
30
45
60
18.8
15.0
7.5
3.0
17.6
15.0
7.5
3.0
16.4
15.0
7.5
3.0
15.2
15.0
7.5
3.0
14.1
15.0
7.5
3.0
6.0
5.1
4.2
6.0
5.1
4.2
6.0
5.1
4.2
6.0
5.1
4.2
6.0
5.1
4.2
1 Pass
SBR(g)
Silica(g)
AMCC(g)
Si69(g)
Oil(g)
ZnO(g)
StAC(g)
2nd Passb
DPG(g)
CBS(g)
S(g)
a Compounding procedure of the 1st pass (master batch 1/MB1): open rubber mill at 65 C, 17.2 rpm
(front roll) and 13.0 rpm (rear roll)
1. Added rubber until it evenly coated on the front roll of the open rubber mill.
2. Added silica, A-MCC, Oil and Si69 in the open rubber mill, and then mixed them until fillers evenly
dispersed into rubber matrix.
3. Mixed rubber compounds in Brabender at 152-157 C for 6 min.
4. Added ZnO, StAc and then mixed them until they evenly dispersed in the open rubber mill.
b Compounding procedure of 2nd pass (master batch 2/MB2): open rubber mill at 50 C, 17.2 rpm
1. Loaded MB1, DPG, CBS, and S.
2. Mixed until all gradients were evenly dispersed in rubber.
84
3.4.4a Determination of Mooney viscosity and characterization of pre-vulcanization
Mooney viscosity and pre-vulcanization data were both measured with
Monsanto Mooney Viscometer according to ASTM D1646. Mooney viscosities were
measured with a large rotor at an oscillating rate of 0.2 rad/s. Initial viscosity was
recorded immediately after preheating the rubber composites for one min at 100 C.
Mooney viscosity at 100 C was recorded after one min of pre-heating and four min of
testing.
There were three replicates in each data point.
For pre-vulcanization
characterization, t5 (the time required for increasing Mooney viscosity above the
minimum viscosity by 5 units) was measured at the testing temperature of 125 C and
the total testing time of 60 min. The testing temperature was set at 125 C because the
processing temperature in rubber manufacturing could ascend by incident.
The
volume of two pieces of specimens for each test was around 253 cm3. Two pieces of
specimens were used because they filled up the cavity of the test chamber better than a
single piece of specimen.
3.4.4b Determination of vulcanizing characteristics

Monsanto Rheometer in accordance with ASTM D 2084.
The vulcanizing
temperature for SBR rubber was 160 C. The oscillating frequency was 1.70.1 Hz
with amplitude of 3.0. The volume of a specimen was between 3 and 5 cm3. The
total testing time was 40 min.
measured.
Scorch time (Ts-1) and cure time (Tc-90) were
85

3.4.5a Evaluation of tensile Strength of unaged and heat-aged rubber composites
The tensile properties were measured by an Instron in accordance with ASTM
D624.
The crosshead speed was 50 cm/min and the original gauge of the
extensometer was 25 mm. The thickness and width of dumbbell specimens were
about 3.00 mm and 6.25 mm, respectively. Tensile strength, which is defined as the
following equation, was obtained.
Tensile strength=
stress @ break
Eq. 3.1

(type A) of specimens was measured by a Durometer type A in accordance with
ASTM D2240. The thickness of specimens for the hardness test was about 6.0 mm.

The tear test was done in accordance with ASTM D412. The die cutter for the
tear test was Die C. The thickness of tear specimens was around 3.00 mm. The tear
strength of hot rubber composites was obtained after tear-test specimens were boiled
in hot water for one hour. The specimens were tested when they were still hot.
86
All experimental data with replicates were analyzed with a standard two-tail ttest using S-PLUS statistical software (Version 8.0, Insightful Corp., Seattle, WA,
USA). All comparisons were based on a 95% confidence interval.

3.5.1 Verification of surface modification of MCC
When compared with the FTIR spectrum of MCC, the spectrum of A-MCC
had two extra peaks at 1725 cm-1 (the C=O group of the acrylate) and at 805 cm-1(the
C-H vibration peak of C=CH2 in the acrylate), which verified that acrylate groups had
been successfully grafted onto the MCC surface (Fig. 3.1).
140
130
120
110
100
80
2202.92
%Transmittance
90
70
60
805.93
50
1725.55
40
30
20
10
4000
3500
3000
2500
2000
1500
Wavenumbers (cm-1)
Figure 3.1 FT-IR spectrum of MCC (top) and A-MCC (bottom)
1000
87
3.5.2 Mooney viscosity of rubber composites
The test temperature for determining Mooney viscosity was set at 100 C since
temperatures of processes such as milling, extrusion, and calendaring occurred around
this temperature. The initial viscosity of A-MCC-I, A-MCC-II, A-MCC-III, and AMCC-IV specimens was lower than that of the control specimens (Fig. 3.2). The
initial viscosity gradually decreased with increasing the usage of A-MCC. Low initial
viscosity means low filler-filler interactions and good dispersion of fillers in a rubber
matrix. With the decrease of silica loading in A-MCC specimens, the chance of
forming silica aggregates was reduced. A-MCC was bulky and was coated with
acrylate groups on the surface; therefore, it had low tendency to form aggregates. AMCC could also disrupt the hydrogen bonds between silica particles, thus reducing the
filler-filler interaction.
Initial viscosity
150
125
100
75
50
Control
II
III
IV
Figure 3.2 Initial viscosity of silica filled rubber composites and A-MCC partially
filled rubber composites. Each data point is the mean of three replicates, and the error
bar represents one standard deviation.
88
The Mooney viscosity of A-MCC-I, A-MCC-II, A-MCC-III, and A-MCC-IV
specimens was lower than that of control specimens (Fig. 3.3). The Mooney viscosity
remained the same when the A-MCC usage was raised from 6.25% to 12.50%, i.e.,
from A-MCC-I to A-MCC-II, and then decreased when the A-MCC usage was further
increased from 12.5% to 25.00%, i.e., from A-MCC-II to A-MCC-IV (Fig. 3.3). The
acrylate groups on the MCC surface reduced the number of OH groups, thus reducing
the hydrogen bonding among fillers.
A-MCC might be located between silica
particles, thus preventing the silica particles from aggregating, which might explained
why A-MCC was able to reduce the Mooney viscosity of A-MCC specimens.
Mooney viscosity
100
90
80
70
60
50
Control
II
III
IV
Figure 3.3 Mooney viscosity of silica filled rubber composites and A-MCC partially
filled rubber composites. Each data point is the mean of three replicates, and the error
bar represents one standard deviation
3.5.3 Pre-vulcanization characteristics of rubber composites

The t5 is a pre-vulcanization characteristic during rubber processing. The high
value of the t5 indicates the high resistance to pre-cure of rubber composites. The t5 of
A-MCC-filled rubber composites were all above 50 min and were larger than that of
89
the control specimen (Table 3.3). It indicated that the addition of A-MCC increased
the resistance to pre-cure of rubber composites. Hydroxyl groups on A-MCC surfaces
were partially masked by the acrylate groups and were not fully available for forming
covalent linkages with the silane coupling agent. Therefore, A-MCC-filled rubber
composites might have a lower amount of covalently bonded silane coupling agent on
the fillers than the control. The sulfur curative might react with rubber matrix and the
acrylate groups on the surface of A-MCC to form covalent linkages between A-MCC
and the rubber matrix. This two-step reaction is supposed to be slower than the onestep reaction between the sulfur-containing groups on the silica surfaces and rubber
matrix. The net results of the low coupling agent content on fillers and the slow twostep reactions might explain why A-MCC-filled rubber composites had a longer t5
than the control.
Table 3.3 Pre-vulcanization characteristics at 125 C
Samples
t5a (min)
Control
48.2
A-MCC-I
55.2
A-MCC-II
>60
A-MCC-III
>60
A-MCC-IV
>60
a: t5: The time required for increasing viscosity above the minimum viscosity by 5 units.
b: The total testing time: 60 min. When t5 is larger than 60 min, it means viscosity increase is less than
5 units in 60 min.
3.5.4 Curing characteristics of the rubber composites

The scorch time (Ts-1) of A-MCC specimens was larger than that of the
control (Table 3.4). Ts-1 gradually increased when the A-MCC content was raised
from 6.25% to 25%, i.e., from A-MCC-I to A-MCC-IV (Table IV). Ts-1 could be
used as an indicator for the initial curing rate. Si69 reacted with fillers, thus the filler
surfaces were coated with mercapto groups (SH) or di-sulfur bonds (S-S), which were
90
the active sites for crosslinking. A-MCC specimens had less Si69 coupling agent than
the control, thus the initial cure rate was slow. Tc-90 is usually used for the curing
time. When compared with the control, A-MCC did not significantly change the
curing time (Table IV). It was possible that the two-step reactions among the sulfur
curative, rubber matrix and the acrylate groups on A-MCC were fast enough at the
curing temperature of 160 C to offset the slow curing rate that resulted from the
possible lower amount of silane coupling agent covalently bonded on fillers in the
rubber composites containing both A-MCC and silica than those containing silica
only.
Table 3.4 The scorch time (Ts-1) and cure time (Tc-90) of each batch at 160 C
samples
Control
Ts-1 (min) 3.63
Tc-90 (min) 30.08
A-MCC-I
3.70
30.91
A-MCC-II
4.06
30.13
A-MCC-III
4.63
30.78
A-MCC-IV
4.98
32.76
a: Ts-1: The time required for increasing viscosity above the minimum viscosity by one unit.
b: Tc-90: The time required for 90% viscosity increase out of total increase.
3.5.5 Tensile properties of unaged and oven-aged rubber composites

Unaged A-MCC specimens except A-MCC-IV had a higher tensile strength
that the control (Fig. 3.4). The tensile strength decreased when the A-MCC usage was
raised from 6.25% to 12.50%, remained the same when the A-MCC usage was further
increased from 12.5% to 18.75%, and then further decreased when the A-MCC usage
was further increased from 18.75% to 25.00%. A good dispersion of fillers can
improve the interactions between fillers and rubber matrix, thus improving the tensile
strength.(Ishiaku et al., 2000; Haghighat et al., 2005) Another filler, i.e., A-MCC in
rubber composites could improve the dispersion of silica filler via interfering the
91
hydrogen bonds between silica particles. The tensile strength of heat-aged A-MCC-I
was the same as that of the aged control (Fig. 3.4). The tensile strength of heat-aged
rubber composites containing A-MCC increased when A-MCC content was raised
from 6.25% to 12.5%, i.e., from A-MCC-I to A-MCC-II.
However, the tensile
strength of heat-aged A-MCC composites gradually decreased when the A-MCC

content was further raised from 12.5% to 25%, i.e., from A-MCC-II to A-MCC-IV
(Fig. 3.4). The aged control specimens had a higher tensile strength than the unaged
control specimens. The aged A-MCC specimens had a lower tensile strength than the
unaged A-MCC specimens except A-MCC-II, i.e., aged A-MCC-I <unaged A-MCC-I,
aged A-MCC-III <unaged A-MCC-III, and aged A-MCC-IV <unaged A-MCC-IV
(Fig. 3.4). For the control specimens, the increase of tensile strength after the aging
might resulted from the conversion of polysulfide bonds to monosulfide bonds
because the conversion would make the rubber composites stronger and less flexible.
For the A-MCC specimens, polysulfide bonds were still converted to monosulfide
bonds, but the rubber-S-CH2-CH2C(=O)-O-MCC linkage on the MCC surfaces might
be converted to rubber-SH plus CH2=CH2C(=O)-O-MCC during the heat-aging via a
reversed Michael Addition reaction, thus weakening the adhesion between rubber and
MCC and subsequently lowering the tensile strength. The Michael Addition reaction is
a reversible reaction. The conversion of polysulfide bonds to monosulfide bonds and
the reversed Michael Addition reaction had the opposite effect on the tensile strength.
92
Unaged
Aged
18
16
14
12
Control
II
III
IV
Figure 3.4 Tensile strength of all unaged and heat-aged rubber composites. Each data
point is the mean of five replicates, and the error bar represents one standard
deviation.
The elongation-at-break of unaged A-MCC specimens was longer than that of

the control and increased with the increase of A-MCC usage in rubber composites
(Fig. 3.5). The elongation-at-break is affected by the flexibility of the rubber polymer
chains.
The higher the crosslinking density the less flexible the rubber polymer
chains.
It indicated that A-MCC-filled rubber composites had low crosslinking
density. The elongation-at-break of aged A-MCC specimens was also longer than that
of the aged control (Fig. 3.5). For the aged A-MCC specimens, the elongation-atbreak increased when A-MCC usage increased from 6.25% to 12.5%, remained the
same when A-MCC usage increased from 12.5% to 18.75%, and then further
increased when A-MCC usage increased from 18.75% to 25.00%. When compared
with unaged rubber specimens, heat-aged rubber composites had lower elongation-atbreak (Fig. 3.5). Polysulfide bonds are more flexible than monosulfide bond. The
93
heat aging process converted the polysulfide bonds to monosulfide bonds, which could
explain why the heat-aging decreased the elongation-at-break.
Unaged
Aged
350
300
250
200
150
100
Control
II
III
IV
Figure 3.5 Elongation-at-break of all unaged and heat-aged rubber composites. Each
data point is the mean of five replicates, and the error bar represents one standard
deviation.
3.5.6 Hardness of the unaged and oven-aged rubber composites

The hardness of unaged A-MCC-I specimens was almost the same as that of
the unaged control, and the other A-MCC specimens was lower than the unaged
control (Fig. 3.6). The hardness of unaged rubber composites decreased from AMCC-I to A-MCC-II, increased from A-MCC-II to A-MCC-III, and then decreased
from A-MCC-III to A-MCC-IV. The hardness of all heat-aged rubber composite
specimens was higher than that of the unaged ones (Fig. 3.6). After vulcanization, the
crosslinks in rubber composites were mostly polysulfide bonds. Polysulfide bonds
were more flexible, i.e., less stiff than monosulfide bonds.
As heat aging, the
polysulfide crosslinks were converted to monosulfide crosslinks (Haghighat et al.,
94
2005). The net gain of hardness between unaged and aged control specimens was
larger than that between unaged and aged A-MCC specimens (Fig. 3.6). As discussed
previously, the heat-aging might lead to the reversed Michael Addition reaction, thus
lowering the hardness.
Unaged
Aged
85
Hardness
80
75
70
65
60
Control
II
III
IV
Figure 3.6 Hardness of all unaged and heat-aged rubber composites. Each data point
is the mean of five replicates, and the error bar represents one standard deviation.
3.5.7 Tear strength and hot tear strength of the rubber composites
Tear strength can be used as an indicator for the cutting chip property when the
rubber composites is used for tread compounds in passenger car tires. At room
temperature, A-MCC-I and A-MCC-II had the same tear strength as the control. AMCC-III had slightly higher tear strength than the control; and A-MCC-IV had lower
tear strength than the control (Fig. 3.7) at room temperature. Tear strength of the hot
A-MCC-I was the same as that of the hot control. The tear strengths of hot A-MCCII, A-MCC-III and A-MCC-IV were comparable with each other, but were much
higher than those of hot control and A-MCC-I (Fig.3 7). These results indicated that
95
addition of A-MCC filler in rubber composites significantly increased the resistance to
high temperature deterioration.
Room temp
Hot
Tear strength (N/mm)
32
28
24
20
Control
II
III
IV
Figure 3.7 Tear strength of all rubber composites at room temperature and elevated
temperature. Each data point is the mean of three replicates, and the error bar
represents one standard deviation.
3.6 Conclusions
A-MCC was successfully prepared. The replacement of up to 25% of silica
with A-MCC facilitated the rubber process through lowering initial viscosity and
Moony viscosity. The initial viscosity and Moony viscosity decreased along with
increasing A-MCC usage.
Rubber composites containing A-MCC had higher
resistance to pre-vulcanization and lower initial cure rate than those without any AMCC. The addition of A-MCC had little effect on the curing time. The addition of AMCC enhanced the tensile strength of rubber composites by up to 18.75% and made
the resulting rubber composites more stretchable and softer. The replacement of up to
18.75% of silica with A-MCC did not negatively affect the tear strength of rubber
96
composites at room temperature, but significantly improved the tear strength at an
elevated temperature.
3.7 Acknowledgments
Financial support for this research was partially provided by Schill+Seilacher
97
3.8 References
Bai, W., Li, K., Partial Replacement of Silica with Microcrystalline Cellulose in
Rubber Composites. Composites Part A: Applied Science and Manufacturing
In Press, Accepted Manuscript.
Bojanic, V., Jovanovic, S., Tabakovic, R., Tabakovic, I., 1996. Synthesis and
electrochemistry of the grafted copolymers of cellulose with 4-vinylpyridine,
1-vinylimidazole, 1-vinyl-2-pyrrolidinone, and 9-vinylcarbazole. J. Appl.
Polym. Sci. 60, 1719-1725.
Derringer, G.C., 1971. Short fiber-elastomer composites. J Elastoplast 3, 230.
Haghighat, M., Khorasani, S.N., Zadhoush, A., 2007. Filler-rubber interactions in
alpha_cellulose-filled styrene butadiene rubber composites. Polymer
alpha -cellulose-filled styrene-butadiene rubber composites. J. Appl. Polym.
Sci. 96, 2203-2211.
4059.
Jong, L., 2006. Effect of soy protein concentrate in elastomer composites. Composites
Part A: Applied Science and Manufacturing 37, 438-446.
Medalia, A.I., Kraus, G., 1994. Reinforcement of elastomers by particulate filles. In:
Mark, J.E., Erman, B., Eirich, F.R. (Eds.), Science and technology of rubber.
Academic Press, San Diego, pp. 387-418.
Polym Agrofibers Based Compos, 135.
98
CHAPTER 4 EFFECT OF ALKENYL-KETENE-DIMMER-MODIFIED
MICROCRYSTALLINE CELLULOSE ON THE PROPERTIES OF SILICAFILLED RUBBER COMPOSITES

Corvallis, OR 97331
99
4.1 Abstract
Microcrystalline cellulose (MCC) was modified with alkenyl ketene dimmer
(AnKD), an inexpensive and readily available sizing agent. AnKD-modified-MCC
(AnKD-MCC) was used to partially replace silica in rubber composites. The partial
replacement of silica with AnKD-MCC lowered initial viscosity and Moony viscosity,
thus facilitating the rubber processing. AnKD-MCC shortened cure time, lowered the
resistance to pre-vulcanization and slowed down the initial cure rate of the resulting
rubber composites. AnKD-MCC improved the hardness, stretchability, and strength
of the resulting rubber composites.
The addition of AnKD-MCC did not have
negative effects on the tensile properties of heat-aged rubber composites and tear
strength of rubber composites at room temperature, but improved the tear strength at
high temperature.
4.2 Key words

Alkenyl-ketene-dimmer-modified-microcrystalline cellulose (AnKD-MCC);
surface modification; rubber composites; Mooney viscosity; mechanical properties
4.3 Introduction
Rubber composites have excellent mechanical and elastic properties and are
widely used in various applications from automobile tires to seals, valves, and gaskets
(Evans, 1980). However, the disposal of used rubber composites by incineration
generates a large amount of ash and could causes environmental pollution. Therefore,
there are growing demands for environmentally friendly rubber composites.
100
Especially, the rubber composites used for green tires have drawn great interest
among the tire manufacturers for the reduction of the energy consumption and carbon
dioxide emission during tire production (You-Ping et al., 2004).
Cellulose is the most abundant renewable material. It plays an important role
in the structural support of plant cell walls because of its high mechanical properties.
There is a growing interest in development of eco-composites such as cellulosereinforced plastic composites that focus on the better utilization of short cellulose
fibers (Derringer, 1971; Ismail et al., 1997; Haghighat et al., 2005; Joseph et al.,
2006). The cellulose-fiber-filled rubber composites have been developed and used for
making ropes, hose, belt, mats and insulation, but have yet to be used in the tire tread
applications (Nunes and Visconte, 2000; Haghighat et al., 2005). Crystalline cellulose
with the size in micrometer range is called microcrystalline cellulose (MCC). MCC as
a reinforcing filler in composites has many advantages over glass fibers, silica and
carbon black: low cost, low density, easiness to process, little abrasion to equipment,
renewability, and biodegradability (Vigo and Kinzig, 1992).
There are two main components in rubber composites: fillers and rubber
matrix. The interfacial adhesion between the fillers and the rubber matrix is typically
weak, which leads to low strength and unusable properties of the rubber composites.
A coupling agent to the rubber composites or the modification of the filler surfaces is
required to impart the rubber composites desirable properties of various applications.
It has recently been reported that the partial replacement of silica with renewable
MCC provided a number of benefits for the resulting rubber composites (Bai and Li).
101
However, the addition of MCC slightly decreased tear strength and hot tear strength of
the resulting rubber composites, which was believed to result from insufficient
interfacial adhesion between MCC and the rubber matrix (Bai and Li). For improving
the interfacial adhesion, MCC was modified with alkenyl ketene dimmer (AnKD), an
inexpensive and readily available sizing agent. The AnKD-MCC was investigated as
a filler for the partial replacement of silica in rubber composites in this study.
4.4 Experiment
4.4.1 Materials and equipment
Dimethylformamide (DMF) was purchased from EMD Chemical Inc.
(Gibbstown, NJ). Molecular sieves (1-2 mm beads) were purchased from Alfa Aesar
(Ward Hill, MA). N-methylmorpholine was from Acros Organics (Geel, Belgium).
AnKD with a commercial name of Precis900 was from Hercules Inc. (Wilmington,
DE). Methanol was from Mallinckrondt Baker, Inc. (Philipsburg, NJ). Toluene was
from VWR International (West Chester, PA). Table 4.1 shows the materials used for
rubber compounding, including codes, trade names, names and locations of
manufacturers.
102
Table 4.1 Materials in this study
Code
Rubber
SBR
Filler
Silica
MCC
AnKDMCC
Coupling
agent
Activator
Processing
oil
Trade name
Buna VSL
5025-1
Ultrasil7000
GR
Avicel PH 101
Location
Lanxess Corp.
Orange, TX
Degussa Corp.
Akron, OH
FMC Inc.
Philadelphia, PA
Synthesized from the lab
Silane
Si69a
ZnO
Zinc oxide
StAc
Stearic acid
Oil
Shell Catenex
Oil SNR
Accelerator DPG
Perkacit DPGb
CBS
Ekaland CBSc
Rubbermakers
sulfur
Vulcanizer
Manufacturer
Struktol Company
of America
Horsehead Corp.
Textile Rubber &
Chemical Co.
Shell UK Oil
Products Ltd.
Weber & Schaer
GmbH & Co. KG
MLPC
International
R.E. Carroll Inc.
Stow, OH
Monaca, PA
Nurnberg,
Germany
Manchester, UK
Hamburg,
Germany
Rion des Landes,
France
Akron, OH
103
FTIR spectra were recorded on a NEXUS 470 FT-IR spectrometer (Thermo
Nicolet Corp., Madison, WI). Rubber composites were prepared with a rubber mill
(Reliable Rubber & Plastics Machinery Co., North Bergen, NJ) and a Brabender
(C.W. Brabender Instrument, Inc., South Hackensack, NJ). The curing of the rubber
composites was performed on a Carver Press (Carver, Inc., Wabash, IN). Viscosity of
rubber composites was measured with Monsanto Rheometer 100 (TechPro Inc.,
Cuyahoga Falls, OH). Strengths and elongation-at-break of rubber composites were
measured with Instron 5582 (Instron Corp., Norwood, MA). The hardness of the
rubber composites was measured with Shore Instruments Durometer type A (Instron
Corp., Norwood, MA).
4.4.2 Surface modification of MCC with AnKD

The surface-modification of MCC was performed according to a literature
procedure (Nahm, 1986). DMF was dried over 4 molecular sieves at 5:1 weight
ratio.
MCC was dried in a 103 C oven for 24 h.
MCC (15 g) and N-
methylmorpholine (0.75 g) were added to the dry DMF (75 mL). The resulting
mixture was stirred at 90-95 C for 1 h followed by adding AnKD (20.6 g). The
reaction mixture was stirred at 90-95 C for another 16 h and then cooled down to 20
C. The reaction mixture was filtered, and washed with DMF and methanol. The
crude product was purified in Soxhlet extraction with toluene over 24 h, and then dried
under vacuum at 85 C to generate AnKD-MCC.
104
Table 4.2 Composition of rubber composites and compounding procedure
1st Passa
SBR(g)
Silica(g)
AnKDMCC(g)
Si69(g)
Oil(g)
ZnO(g)
StAC(g)
2nd Passb
DPG(g)
CBS(g)
S(g)
Control
AnKDMCC-I
206.0
160.0
206.0
150.0
AnKDMCC-II
AnKDMCC-III
AnKDMCC-IV
206.0
140.0
206.0
130.0
206.0
120.0
10.0
20.0
30.0
40.0
12.5
10.0
5.0
2.0
11.7
10.0
5.0
2.0
10.9
10.0
5.0
2.0
10.2
10.0
5.0
2.0
9.4
10.0
5.0
2.0
4.0
3.4
2.8
4.0
3.4
2.8
4.0
3.4
2.8
4.0
3.4
2.8
4.0
3.4
2.8
a Compounding procedure of 1st pass (master batch 1/MB1): open rubber mill at 65 C, 17.2 rpm (front
roll) and 13.0 rpm (rear roll)
1. Added rubber until it evenly coated on the front roll of the open rubber mill.
2. Added silica, AnKD-MCC, Oil and Si69 in the open rubber mill, and then mixed them until fillers
evenly dispersed into rubber matrix.
3. Mixed rubber compounds in Brabender at 152-157 C for 6 min.
4. Added ZnO, StAc and then mixed them until they evenly dispersed in the open rubber mill.
b Compounding procedure of 2nd pass (master batch 2/MB2): open rubber mill at 50 C, 17.2 rpm
1. Loaded MB1, DPG, CBS, and S.
2. Mixed until all gradients were evenly dispersed in rubber.
105
4.4.3 Compounding recipes and procedures
An open rubber mill was used to compound rubber mixtures. There were five
batches compounded according to the recipes and procedures in Table 4.2. The
control had silica as the sole filler. The percentages of silica replaced by AnKD-MCC
were 6.25%, 12.5%, 18.75%, and 25.0%, corresponding to AnKD-MCC-I, AnKDMCC-II, AnKD-MCC-III, and AnKD-MCC-IV. The amount of other components
except silane coupling agent Si69 in the rubber composites remained the same in
batches containing AnKD-MCC. The usage of Si69 was proportionally reduced as the
amount of AnKD increased, i.e., 12.5 g for the control, 11.7 g for AnKD-MCC-I, 10.9
g for AnKD-MCC-II, 10.2 g for AnKD-MCC-III, and 9.4 g for AnKD-MCC-IV. The
compounding procedures included two passes. The first pass had all the materials for
rubber composites, except the curatives. The resulting rubber composites were further
compounded in Brabender at 152-157 C for six min so that Si69 could react with
silica. The resulting rubber composites then underwent the second pass where the
curatives such as DPG, CBS, and sulfur were included.
The compounding
temperature of the second pass was at 50 C for preventing pre-cure of rubber

composites.
After the second pass, all batches were made into sheets with the
thickness of 2-4 mm by the open rubber mill.

4.4.4a Determination of Mooney viscosity and characterization of pre-vulcanization
Mooney viscosity and pre-vulcanization characteristics were both determined
with Monsanto Mooney Viscometer according to ASTM D1646. Mooney viscosities
106
were measured with a large rotor at an oscillating rate of 0.2 rad/s. Initial viscosity
was recorded immediately after preheating the rubber composites for one min at 100
C. Mooney viscosity at 100 C was recorded after one min of pre-heating and four
min of testing. There were three replicates in each data point. For pre-vulcanization
characteristics, t5 (the time required for increasing Mooney viscosity above the
minimum viscosity by 5 units) was measured at the testing temperature of 125 C and
the total testing time of 60 min. The testing temperature was set at 125 C because the
processing temperature in rubber manufacturing could ascend by incident.
The
volume of two pieces of specimens for each test was around 253 cm3. Two pieces of
specimens were used because they filled up the cavity of the test chamber better than a
single piece of specimen.
4.4.4b Determination of vulcanizing characteristics

Monsanto Rheometer in accordance with ASTM D 2084.
The vulcanizing
temperature for SBR rubber was 160 C. The oscillating frequency was 1.70.1 Hz
with amplitude of 3.0. The volume of a specimen was between 3 and 5 cm3. The
total testing time was 40 min.
measured.
Scorch time (Ts-1) and cure time (Tc-90) were
107
4.4.5a Evaluation of tensile Strength of unaged and heat-aged rubber composites
D624.
about 3.00 mm and 6.25 mm, respectively. Tensile strength, which is defined as the
following equation, was obtained.
Tensile strength=
stress @ break
Eq. 4.1

(type A) of specimens was measured by a Durometer type A in accordance with
ASTM D2240. The thickness of specimens for the hardness test was about 6.0 mm.

The tear test was done in accordance with ASTM D412. The die cutter for the
tear test was Die C. The thickness of tear specimens was around 3.00 mm. The tear
strength of hot rubber composites was obtained after tear-test specimens were boiled
in hot water for one hour. The specimens were tested when they were still hot.
108
All experimental data with replicates were analyzed with a standard two-tail ttest using S-PLUS statistical software (Version 8.0, Insightful Corp., Seattle, WA,
USA). All comparisons were based on a 95% confidence interval.

4.5.1 Verification of surface modification of MCC
When compared with FTIR spectrum of MCC, the AnKD-MCC spectrum had
two extra peaks at 1750 cm-1 (the C=O group of ester) and at 1710 cm-1(the C=O
group of ketone), which verified that AnKD had been successfully grafted onto the
surfaces of MCC (Fig. 4.1).
140
130
120
110
90
80
1749.92
60
50
1656.16
70
1709.74
%Transmittance
100
40
30
20
4000
3500
3000
2500
2000
1500
Wavenumbers (cm-1)
Figure 4.1 FT-IR spectrum of MCC (top) and AnKD-MCC (bottom)
1000
109
4.5.2 Mooney viscosity of rubber composites
The test temperature for determining Mooney viscosity was set at 100 C since
temperatures of processes such as milling, extrusion, and calendaring occurred around
this temperature. The initial viscosity of specimens containing AnKD-MCC was
lower than that of the control, and gradually decreased along with the increase in
AnKD-MCC content (Fig. 4.2). Mooney viscosity of specimens containing AnKDMCC was lower than that of the control, and also gradually decreased along with the
increase in AnKD-MCC content (Fig. 4.3). Low initial viscosity and low Mooney
viscosity mean low filler-filler interactions and good dispersion of fillers in a rubber
matrix. The amount of silica agglomerates decreased when the silica loading in
specimens containing AnKD-MCC decreased. AnKD-MCC had little tendency to
form aggregates because it was coated with long unsaturated hydrocarbon chains on
the surface.
AnKD-MCC could also disrupted hydrogen bonds between silica
particles, thus reducing the filler-filler interactions.
Initial viscosity
150
125
100
75
Control
II
III
IV
Figure 4.2 Initial viscosities of all rubber composites. Each data point is the mean of
three replicates, and the error bar represents one standard deviation.
Mooney viscosity
110
90
80
70
60
Control
II
III
IV
Figure 4.3 Mooney viscosities of all rubber composites. Each data point is the mean
of three replicates, and the error bar represents one standard deviation.
4.5.3 Pre-vulcanization characteristics of rubber composites

The t5 is indicative of the pre-vulcanization characteristics of rubber
composites during processing. The lower the t5 the faster the crosslinking reactions in
rubber composites, i.e., the lower the resistance to pre-cure of rubber composites. All
t5 values of rubber specimens containing AnKD-MCC were smaller than that of
control specimen (Table 4.3). The t5 gradually decreased with increasing the AnKDMCC content, which implied that AnKD-MCC decreased the resistance to pre-mature
curing.
It appeared that the unsaturated hydrocarbon chains on MCC surfaces were
easier to form cross-links with rubber matrix than the silane coupling agent on the
silica surfaces at 125 C (the test temperature).
Table 4.3 Pre-vulcanization characteristics at 125 C
Samples
Control
t5 (min)
48.2
AnKDMCC-I
39.0
AnKDMCC-II
36.7
AnKDMCC-III
36.3
t5: The time required for increasing viscosity above the minimum viscosity by 5 units.
AnKDMCC-IV
22.2
111
4.5.4 Cure characteristics of the rubber composites
The scorch times (Ts-1) of all specimens containing AnKD-MCC except
AnKD-MCC-IV were higher than that of the control (Table 4.4). The Ts-1 decreased
when the AnKD-MCC content increased. Tc-90 is usually used for the cure time. The
cure time of AnKD-MCC specimens was shorter than that of the control specimen
(Table 4.4). The curing time decreased along with increasing the AnKD-MCC content
(Table 4.4). These results are consistent with the explanation that the unsaturated
hydrocarbon chains on AnKD-MCC surfaces were more reactive for forming crosslinks with rubber matrix than the silane coupling agent on silica surfaces.
Table 4.4 The scorch time (Ts-1) and rure time (Tc-90) of each batch at 160 C
samples
Control
Ts-1 (min) 3.63

Tc-90 (min) 30.08
AnKDMCC-I
4.20
27.0
AnKDMCC-II
4.10
25.8
AnKDMCC-III
3.90
24.7
AnKDMCC-IV
3.40
24.0
a: Ts-1: The time required for increasing viscosity above the minimum viscosity by one unit.
b: Tc-90: The time required for 90% viscosity increase out of total increase.
4.5.5 Tensile test and heat-aged tensile test

The tensile strength for unaged specimens containing AnKD-MCC was
comparable to that of the unaged control, except that AnKD-MCC-III had slightly
higher tensile strength than the control (Fig. 4.4). The aged AnKD-MCC-I had a
higher tensile strength than the aged control. The tensile strength of the aged AnKDMCC-II, AnKD-MCC-III, and AnKD-MCC-IV was comparable to that of the aged
control. It was still poorly understood that the tensile strength of aged specimens
containing AnKD-MCC fluctuated.
112
Unaged
Aged
20.0
17.5
15.0
12.5
10.0
Control
II
III
IV
Figure 4.4 Tensile strength of unaged and aged rubber composites. Each data point is
the mean of three replicates, and the error bar represents one standard deviation.
The elongation-at-break for the specimens containing AnKD-MCC was longer

that of the control (Fig. 4.5). The elongation-at-break gradually increased when the
AnKD-MCC content was raised (Fig. 4.5).
The elongation-at-break for aged
specimens containing AnKD-MCC was longer that of the aged control (Fig. 4.5). The
elongation-at-breaks for the aged AnKD-MCC-I, AnKD-MCC-II, and AnKD-MCCIII was the same and was lower than that for the aged AnKD-MCC-IV (Fig. 4.5). The
unsaturated hydrocarbon chains in AnKD are longer and more stretchable than the
hydrocarbon chain of Si69 (the silane coupling agent), which may account for the
increased elongation-at-break for all specimens containing AnKD.
113
Unaged
Aged
400
300
200
100
0
Control
II
III
IV
Figure 4.5 Elongation-at-break of unaged and aged rubber composites. Each data
deviation.
4.5.6 Hardness of the unaged and aged rubber composites

The hardness for the unaged AnKD-MCC-I was higher that of the unaged
control (Fig. 4.6). The hardness of the unaged AnKD-MCC-II, AnKD-MCC-III and
AnKD-IV was the same and was comparable to that of the unaged control (Fig. 4.6).
The hardness of all aged specimens containing AnKD-MCC was slightly lower than
that of the aged control (Fig. 4.6), which may be explained by the fact that
hydrocarbon chains of AnKD are longer and more flexible than that of Si69. The
hardness of the aged AnKD-MCC-I and AnKD-MCC-II was statistically the same,
and then slowly decreased from the aged AnKD-MCC-II to the aged AnKD-MCC-IV
(Fig. 4.6). Except AnKD-MCC-IV, the aging appeared to increase the hardness of
each specimen, i.e., aged control> unaged control, aged AnKD-MCC-I> unaged
AnKD-MCC-I, aged AnKD-MCC-II> unaged AnKD-MCC-II, and aged AnKD-
MCC-III> unaged AnKD-MCC-III (Fig. 4.6).
114
The heat-aging tends to convert
polysulfide bonds to monosulfide bonds in rubber, thus resulting in a higher hardness.

Unaged
Aged
Hardness
90
80
70
60
50
Control
II
III
IV
Figure 4.6 Hardness of unaged and aged rubber composites. Each data point is the
mean of five replicates, and the error bar represents one standard deviation.
4.5.7 Tear strength and hot tear strength of the rubber composites
At room temperature, the tear strength of AnKD-MCC-I, AnKD-MCC-II, and
AnKD-MCC-III specimens was slightly lower than that of the control, while the tear
strength of AnKD-MCC-IV was higher than that of the control (Fig. 4.7). At high
temperature (100 C), the tear strength of AnKD-MCC-I, AnKD-MCC-II, and AnKDMCC-IV was higher than the hot control, and the tear strength of AnKD-MCC-III was
comparable to that of the hot control (Fig. 4.7). We speculated that not all the silane
coupling agent formed a covalent bond with silica filler during compounding, thus the
interaction between silica filler and the rubber matrix was not as strong as that of
AnKD-MCC filler and the rubber matrix. The tear strength at high temperature can be
used as an indicator for the cutting chip property when the rubber composites are used
115
for tire tread. The results clearly indicated that the addition of AnKD-MCC filler in
rubber composites significantly improved the tear strength of the hot rubber
composites, thus improving the cutting chip properties for the tire applications.
Room temp
Hot
Tear strength (N/mm)
32
28
24
20
Control
II
III
IV
samples
Figure 4.7 Tear strength of all rubber composites at room temperature (Room temp)
and high temperature (Hot). Each data point is the mean of three replicates, and the
error bar represents one standard deviation.
4.6 Conclusions
The unsaturated hydrocarbon chains had been grafted on the surface of MCC
via a reaction with a sizing agent, AnKD, and N-methylmorpholine as a catalyst. The
partial replacement of silica with AnKD-MCC facilitated the rubber processing
through lowering initial viscosity and Moony viscosity. The initial viscosities and
Mooney viscosities of AnKD-MCC-filled rubber composites were lower than those of
the control containing only silica, and also decreased with increasing the AnKD-MCC
content. The rubber composites containing AnKD-MCC had lower resistance to pre-
116
vulcanization than the control. The rubber composites containing AnKD-MCC had
the same initiate curing rate as the control, but required shorter curing time. AnKDMCC-filled rubber composites were more stretchable than the control. The tensile
strengths of AnKD-MCC-filled rubber composites were as strong as those of the
control at room temperature. The addition of AnKD-MCC did not have negative
effect on the tensile properties of aged rubber composites. AnKD-MCC improved the
tear strength of rubber composites at high temperature.
4.7 Acknowledgment
Financial support for this research was partially provided by Schill+Seilacher
117
4.8 References
Derringer, G.C., 1971. Short fiber-elastomer composites. J Elastoplast 3, 230.
Evans, C.W., 1980. Developments in rubber and rubber composites. Applied Science
Publishers, London.
alpha -cellulose-filled styrene-butadiene rubber composites. J. Appl. Polym.
Sci. 96, 2203-2211.
4059.
Nahm, S.H., 1986. Direct evidence for covalent bonding between ketene dimer sizing
agents and cellulose. J. Wood Chem. Technol. 6, 89-112.
Polym Agrofibers Based Compos, 135-157.
You-Ping, W., Mei-Qin, J., Qing, Q., Yi-Qing, W., Li-Qun, Z., 2004. Preparation,
Structure, and Properties of Starch/Rubber Composites Prepared by CoCoagulating Rubber Latex and Starch Paste. Macromolecular Rapid
Communications 25, 565-570.
118
CHAPTER 5 A TECHNIQUE FOR PRODUCTION OF
NANOCRYSTALLINE CELLULOSE WITH A NARROW SIZE
DISTRIBUTION
Wen Bai1, James Holbery2 and Kaichang Li1,*

1
Wood Science & Engineering Department, Oregon State University

Corvallis, OR 97331
Energy and Environment Directorate, Pacific Northwest National Laboratory

Richland, WA 99352
Cellulose
P.O. Box 990
3300 AZ Dordrecht
The Netherlands
2009, 16, 455-465
119
5.1 Abstract
Nanocrystalline cellulose (NCC) was prepared by sulfuric acid hydrolysis of
microcrystalline cellulose (MCC). A differential centrifugation technique was studied
to obtain NCC whiskers with a narrow size distribution. It was shown that the volume
of NCC in different fractions had an inverse relationship with relative centrifugal force
(RCF). The length of NCC whiskers was also fractionized by differential RCF. The
aspect ratio of NCC in different fractions had a relatively narrow range.
This
technique provides an easy way of producing NCC whiskers with a narrow size
distribution.
5.2 Keywords
nanocrystalline cellulose (NCC), microcrystalline cellulose (MCC), differential
centrifugation, narrow size distribution, transmission electron microscope (TEM)
5.3 Introduction
Cellulose is the most abundant natural polymer and contains both amorphous
and crystalline structures.
Nanocrystalline cellulose (NCC), also called cellulose
nanocrystals, is typically a rigid rod-shaped monocrystalline cellulose domain

(whisker) with 1 nm to 100 nm in diameter and tens to hundreds of nanometers in
length (Ruiz et al., 2000; De Souza Lima and Borsali, 2004). NCC has a highly
crystalline structure, a very large aspect ratio (around 70), and a high surface area (ca.
150 m2/g) (Ruiz et al., 2000). Extensive studies have shown that NCC can be used for
many applications such as regenerative medicine (Fleming et al., 2001), optical
120
application (Revol et al., 1998), automotive application (Hill, 1997; Dahlke et al.,
1998), composite materials and so on. NCC has a very high tensile strength, a very
high Youngs modulus and should be a very good reinforcing filler for various
composite materials (Sakurada et al., 1962; Ruiz et al., 2000; Samir et al., 2005).
Several studies have shown that NCC serves as a reinforcing filler to dramatically
increase the strength of reinforced thermoset and thermoplastic materials (Helbert et
al., 1996; Grunert and Winter, 2000; Winter and Bhattacharya, 2003; Roman and
Winter, 2006). The geometrical features of NCC are important factors that determine
the strength of NCC-reinforced composite materials (Terech et al., 1999; Samir et al.,
2004a, b).
Previous studies show that NCC can be produced from acid hydrolysis of
various natural cellulose fibers such as cotton, cellulose fibers from lignocellulosic
materials, and a marine animal tunicate (Dong et al., 1998; Grunert and Winter, 2000;
Heux et al., 2000; Edgar and Gray, 2002; Grunert and Winter, 2002).
Microcrystalline cellulose (MCC) from lignocellulosic materials such as wood is
abundant, inexpensive and readily available. Therefore, NCC is commonly produced
from the hydrolysis of MCC with a strong acid such as sulfuric acid (Bondeson et al.,
2006).
The acid hydrolysis removes the amorphous cellulose to form highly
crystalline cellulose, and also reduces the size of MCC. NCC from acid hydrolysis of
MCC typically has a wide range in size. Geometrical characteristics of NCC depend
on the hydrolysis conditions such as temperature and time (Dong et al., 1998), and the
original source of cellulose fibers: bacterial cellulose (Grunert and Winter, 2000;
121
Grunert and Winter, 2002), cotton filter paper (Dong et al., 1998; Edgar and Gray,
2002), chitin (Goodrich and Winter, 2007), and tunicates (Heux et al., 2000). The size
of NCC from previous studies all has a wide range and little has been published on
how to produce NCC with a narrow distribution of size.
In this paper, we have developed a novel technique of differential
centrifugation to separate NCC suspensions into different fractions with each fraction
having a narrow size distribution.

5.4.1 Chemicals
MCC (Avicel pH-101, approximately 50 m) was purchased from FMC
BioPolymer (Philadelphia, PA, USA). Sulfuric acid (95-98 wt%) was purchased from
Fisher Scientific (Gibbstown, NJ, USA).
All water utilized throughout the
experimental procedures was deionized water. Uranyl Acetate and copper grids (200
mesh, covered with carbon film) were purchased from Ted Pella Incorporated
(Redding, CA, USA).
5.4.2 Preparation of NCC suspensions

NCC suspension was produced by following a literature procedure (Dong et
al., 1998). MCC powder (10.0 g) was hydrolyzed by sulfuric acid (87.5 mL, 64%
w/v) for five hours at 45 C with continuous stirring. The hydrolysis was quenched by
adding a large amount of water (500 mL) to the reaction mixture. The resulting
mixture was cooled to room temperature (25 C) and centrifuged (2383g or 3500
122
rpm) for 30 min at room temperature (Labofuge 400, Heraeus, Hanau, Germany). The
supernatant was decanted. Water (500 mL) was added to the precipitate and the
mixture was then sonicated for 10 min to form a new suspension. This
centrifugation/sonication process was repeated three times.
The newly generated
suspension was filtered with an ultra-filtration membrane (30,000 molecular weight

cutoff) using an Amicon Stirred Cell (Millipore Corporation, Bedford, MA, USA)
until the pH of the suspension reached a constant value.
The resultant NCC
suspension (around 0.2 wt%) was stored in a refrigerator at 3.0 C.
5.4.3 Transmission electron microscopy (TEM) graphs

An NCC suspension was placed on a copper grid (the drop size of the
suspension was around 2.5 mm in diameter) and dried at room temperature (25 C).
The sample was stained with uranyl acetate (around 5 wt%) for three min
(Zimmermann et al., 2006). TEM graphs were acquired with Philips CM-12 at 60 kV
(Philips, Eindhoven, The Netherlands).
5.4.4 Fractionation of NCC suspensions using a differential centrifugation technique

NCC suspensions were separated into six fractions using differential angle
velocity, i.e., relative centrifugal force (RCF) at a fixed centrifugal time (10 min). A
NCC suspension prepared per the previously described hydrolysis technique was
centrifuged at an angular velocity of 500 rpm for 10 min. The precipitate from this
centrifugation was discarded because the most whiskers of the precipitate had
diameters over 100 nm. The suspension from the previous centrifugation at 500 rpm
123
was centrifuged at 1000 rpm for 10 min. The precipitate from this centrifugation was
designated as Fraction #1. The suspension from the previous centrifugation at 1000
rpm was centrifuged at 1500 rpm for 10 min, and the resultant precipitate was
designated as Fraction #6. This sequential centrifugation process was repeated three
times. This fractionation experiment is shown in Table 5.1.
124
Table 5.1 Experimental design of NCC fractions by differential RCF at fixed
centrifuge time (10 min)
Fraction
RCF
(rpm)
No.
(g)
1
2
3
4
5
6
1000
1500
2000
2500
3000
3500
195
438
778
1216
1751
2383
Average
yield of
NCC * (%)
Standard
deviation
Relative weight
percentage **
(%)
6.68
2.15
3.00
2.50
1.46
5.23
0.54
0.34
0.14
0.42
0.11
0.13
31.79
10.21
14.27
11.90
6.94
24.89
* The average yield of NCC whiskers was based on the dry weight of MCC used in the hydrolysis.
Data were the means of three replicates.
** The relative weight percentage was defined as the weight of each fraction divided by the total weight
of six fractions.
125
5.4.5 Determination of the diameter, length, and volume of NCC
It has been shown that NCCs from tunicate have ribbon-like morphology
(Elazzouzi-Hafraoui et al., 2008). However, numerous evidences from microscopy
and light scattering techniques reveal that cellulose crystals have rodlike shape (De
Souza Lima and Borsali, 2004). Ribbon-like morphology was not observed for the
NCCs in our study. Therefore we assume that the NCCs have cylindrical shape in our
calculation of the NCC volumes.
Approximately 10 TEM graphs were acquired for each NCC fraction and
subsequently used to determine the diameter and length of each NCC crystals. At
least 80-100 measurements of the diameter and the length were made for each
fraction. Adobe Photoshop CS software was used to aid in the determination of the
NCC size. All data were analyzed by a statistical method (frequency distribution
analysis) with all data exhibiting moderately skewed distributions. The relationship
between the volume of NCC and RCF was determined via linear regression analysis.
The volume of each NCC particle is calculated from the diameter (d) and
length (L) of the NCC particle according to the Eq. 5.1.
V =
d 2 L
4
Eq. 5.1
The volume of a NCC particle for each fraction is reported as the average
volume that can be calculated by Eq. 5.2.
n
V =
V
i =1
Eq. 5.2
126
Vi : the volume of individual NCC particle, V : the average volume of NCC in
each fraction.
5.4.6 Mechanism of differential centrifugation

Equation 5.3 shows the relationship between angular velocity and RCF (Boyer,
1993).
RCF = 1.118 10 6 2 r
Eq. 5.3
Where r = radius (mm), = angular velocity (rpm).

NCC whiskers were uniformly dispersed in the suspension. The whiskers
traveled to the bottom of the tube with a velocity of v when the centrifugal force (Fc),
buoyant force (Fb) and frictional force (Ff) were on balance as shown in Figure 5.1
(Boyer, 1993).
meniscus
air
solution
bottom
Fb
Fc
Ff
r
Figure 5.1 A schematic of working mechanism of centrifugation. : angle velocity,
r: radius of centrifuge, Fc: centrifugal force, Fb: buoyant force, Ff: frictional force.
Fc = m 2 r
Eq. 5.4
127
Fb = m0 r
Eq. 5.5
F f = fv
Eq. 5.6
where m = the mass of NCC, = angular velocity, r = radius, mo = the mass of

the displaced water, f = frictional coefficient, = the velocity of NCC toward the
bottom of centrifugation tube.
The force balance on a NCC particle was explained in Eq. 5.7
m 2 r m0 2 r fv = 0
Eq. 5.7
m = pV
Eq. 5.8
m 0 = sV
Eq. 5.9
where s = solvent (water) density, p = NCC particle density, and V = the

volume of a NCC particle.
Eq.5.10 is derived from Eq. 5.7, Eq. 5.8 and Eq. 5.9. To get the relationship
between RCF and volume of NCC particle, Eq. 5.11 is derived from the combination
of Eq. 5.3 and Eq. 5.10.
V =
fv
r( p s )
2
Eq. 5.10
V =
1.118 10 6 fv
RCF ( p s )
Eq. 5.11
V=
Av
RCF
Eq. 5.12
log(V ) = log( Av) log( RCF )
Eq. 5.13
128
Where A =
1.118 10
( p s )
, A is a constant.
From Eq. 5.12 and Eq. 5.13, we can see that the volume (V) is proportional to
the velocity at a fixed RCF. In other words, at a fixed RCF as all centrifugation was
done, a bigger NCC would have a higher velocity, i.e., would reach the bottom of a
centrifugation tube first. For individual NCC particle, its precipitation speed to the
bottom of a centrifuge tube increases along with increase in RCF. For precipitating a
small NCC particle, either RCF or centrifugation time has to be increased. At a fixed
centrifugation time, NCC fractions with different volume distributions can be obtained
through a sequential change in RCF. This is the basic principle behind this work.

5.5.1 Verification of NCC size by TEM
TEM images of NCC fractions from the angle velocity of 1000-3500 rpm
revealed that all cellulose whiskers maintained diameters less than 100 nm.
representative TEM image of the cellulose whiskers is shown in Figure 5.2. However,
the diameters of some cellulose whiskers were larger than 100 nm when the hydrolysis
time was less than five hours. Therefore, the five-hour hydrolysis time was used for
generating NCC suspensions in this fractionation study. TEM images were used to
determine the sizes of NCC in the fractionation study.
129
Figure 5.2 Transmission electron microscope (TEM) image of NCC
5.5.2 Yields of NCC in different fractions
The yield of NCC in each fraction was calculated by the weight of NCC in
each fraction divided by the initial weight of MCC. The average yields of NCC from
Fraction 1 to Fraction 6 were 6.68%, 2.15%, 3.00%, 2.50%, 1.46%, and 5.23% (Table
5.1). The total yield of NCC in six fractions was about 21.02%. The high yields of
NCC were in Fraction 1 and Fraction 6 (Table 5.1). Fraction 1 accounted for 31.79%
of all NCCs. The high yield of NCC in Fraction 1 was probably due to a number of
large NCC.
The relative weight percentages of the Fractions 2-5 were 10.21%,
14.27%, 11.90% and 6.94%, respectively. The relative weight percentage of NCC in
the Fraction 6 was around 24.89%. It also indicated that the number of NCC with
small size in Fraction 6 was larger than that of any other fractions.
130
5.5.3 The relationship between RCF and the volume of NCC in each fraction
The inverse relationship between RCF and the volume (V) of NCC from the
Fraction 1 to the Fraction 6 is shown in Figure 3. The inverse relationship between
RCF and volume of NCC whiskers is consistent with the principle of differential
centrifugation described in the Method section. R2 was 0.88 from the simple linear
regression analysis, indicating a linear relationship between log(RCF) and log(V).
Each data point represented the average volume of NCC whiskers in each fraction
(Figure 5.3). The standard error of each data point was not shown because all the
volume distributions were not normal and moderately skewed. At the same centrifuge
time, the larger the centrifuge force, the smaller the precipitated NCC whiskers.
However, there was a break point at Fraction 3 (RCF=778). The average volume of
NCC in Fractions 3 was smaller than both Fraction 2 and Fraction 4. The exact reason
for this break point is not well understood. The break point at Fraction 3 led to a
relatively low value of R2 (0.88).
131
5.0
4.8
log(V)
4.6
4.4
4.2
4.0
3.8
2.2
2.4
2.6
2.8
3.0
3.2
3.4
3.6
log(RCF)
Figure 5.3 The inverse relationship between relative centrifugal force (RCF) and
volume (V)* of NCC from Fraction 1 to Fraction 6. * The values of volume at all data
points are the average volume of NCC in each fraction. The volume distribution of
each fraction is not a normal distribution, so that the standard deviation is not shown
in the Figure.
The volume distributions of the NCC whiskers from the six fractions are
shown in Figure 5.4. For the Fraction 1, about 3.80% of NCC whiskers was in the
volume range from 0 to 5103 nm3 (Figure 5.4a) The percentage of NCC whiskers
increased to 17.72% in the volume range from 6103 nm3 to 10103 nm3. It decreased
to 13.92% in the volume range from 11103 nm3 to 15103 nm3 and further decreased
to 10.13% in volume range from 16103 nm3 to 20103 nm3. The right tail (from
66103 nm3 to 105103 nm3) of the volume distribution for the Fraction 1 was
12.66%. For the Fraction 2, 11.58% of NCC whiskers fell within the volume range
132
from 0 to 510 nm . The percentage of NCC increased to 24.21% in the volume
3
range from 6103 nm3 to 10103 nm3. It decreased to 18.95% in the volume range
from 11103 nm3 to 15103 nm3 and further decreased to 8.43% in the volume range
from 16103 nm3 to 20103 nm3. The right tail (from 66103 nm3 to 105103 nm3) of
the volume distribution in the Fraction 2 was 6.32% (Figure 5.4a). For the Fraction 3,
28.89% of NCC was in the volume range from 0 to 5103 nm3. The percentage of
NCC was also 28.89% in the volume range from 6103 nm3 to 10103 nm3. It
decreased to 13.33% in the volume range from 11103 nm3 to 15103 nm3 and further
decreased to 11.11% in volume range from 16103 nm3 to 20103 nm3. The right tail
(from 66103 nm3 to 105103 nm3) of the volume distribution in fraction 3 was only
1.11% (Figure 5.4a). For the Fraction 4, 18.12% of NCC was in the volume range
from 0 to 5103 nm3. The percentage decreased to 16.87%, 15.62% and 9.38% in
volume ranges from 6103 nm3 to 10103 nm3, from 11103 nm3 to 15103 nm3, and
from 16103 nm3 to 20103 nm3, respectively. The right tail (from 66103 nm3 to
105103 nm3) of the volume distribution for the Fraction 4 was 4.38% (Figure 4b).
For the Fraction 5, 22.00% of NCC whiskers were in the volume range from 0 to
5103 nm3. The percentages of NCC in volume ranges from 6103 nm3 to 10103
nm3, from 11103 nm3 to 15103 nm3, and from 16103 nm3 to 20103 nm3
continuously decreased to 30.00%, 9.00% and 6.00%, respectively (Figure 5.4b). The
right tail (from 66103 nm3 to 105103 nm3) of the volume distribution for the
Fraction 5 was about 1.00%. For the Fraction 6, about 41.90% of NCC whiskers were
in volume range from 0 to 5103 nm3. The percentages decreased to 23.80%, 10.48%
133
and 4.76% in following three volume ranges from 610 nm to 1010 nm , from
3
11103 nm3 to 15103 nm3 and from 16103 nm3 to 20103 nm3, respectively. There
were no NCC whiskers in the right tail (from 66103 nm3 to 105103 nm3) of the
volume distribution for the Fraction 6. The volume of NCC whiskers in each fraction
had a distribution and was not a single value because NCC whiskers were uniformly
suspended in the water and the travelling distances to the bottom of the centrifuge tube
varied. Even though a small centrifuge force was applied to a NCC whisker with a
small volume, NCC might precipitate if it was close enough to the bottom of a
centrifuge tube. However, there is a general trend in the overall volume distribution.
The larger the applied centrifugal force was, the more NCC whiskers with smaller
volumes were precipitated.
134
Figure 5.4 The volume distribution of NCC after fractionation by differential RCF.
*Relative percentage= (Number of NCC whiskers in each bin of one fraction) / (total
number of NCC whiskers in one fraction)*100%. **Legends stand for differential
RCF in different fractions.
135
As seen in Table 5.2, the majority (80%) of NCC whiskers in each fraction had
their volume ranges: the Fraction 1, 0 to 80103 nm3; the Fraction 2, 0 to 45103 nm3;
the Fraction 3, 0 to 20103 nm3; the Fraction 4, 0 to 35103 nm3; the Fraction 5, 0 to
30103 nm3; and the Fraction 6, 0 to 20103 nm3, respectively. Compared with the
full volume ranges, the major (80% of NCC whiskers) volume ranges were relatively
narrow. For Fractions 3, 4 and 5, there was no significant difference in the volume
distributions under 95% confidence interval (p=0.062 from one-way ANOVA test for
multiple comparison using S-Plus software (Version 8.0, Insightful Corp., Seattle,
WA, USA)). It may be due to the small differences of RCF in these three fractions.
Overall, there was ample evidence that the majority of NCC whiskers in each fraction
shifted to a small volume and the volume range became narrow as RCF increased.
The results from the volume distributions (Figure 5.4) were also consistent with the
inverse relationship between RCF and the volume of NCC whiskers from Figure 5.3.
136
Table 5.2 Comparison between the full volume range and the major volume range of
NCC whiskers at differential RCF
Fraction
No.
1
2
3
4
5
6
(rpm)
1000
1500
2000
2500
3000
3500
RCF
(g)
195
438
778
1216
1751
2383
Full volume
range * (103 nm3)
0 to 105
0 to 100
0 to 90
0 to 100
0 to 80
0 to 60
Major volume
range ** (103 nm3)
0 to 80
0 to 45
0 to 20
0 to 35
0 to 30
0 to 20
* The volume range contained all NCC whiskers in one fraction.

** The major volume range was defined as the narrowest volume range containing 80% of NCC in one
fraction.
137
5.5.4 Length distributions of NCC by differential centrifugation method
The length distributions of NCC whiskers for Fractions 1-6 are shown in
Figure 5.5.
It was obvious that the length distribution became narrow as RCF
increased, i.e., the length of NCC whiskers in the Fraction 1 had the broadest
distribution and the length of NCC whiskers in the Fraction 6 had the narrowest
distribution. For the Fraction 1, no NCC whiskers had their lengths less than 40 nm.
Only about 1.26% of NCC whiskers had their lengths ranging from 41 to 60 nm, and
from 61 to 80 nm, respectively. The percentage increased to 8.86% when the length
range increased to from 81 to 100 nm. The major percentages of 16.46%, 13.92%, and
16.46% corresponded to the length ranges from 101 to 120 nm, 121 to 140 nm, and
141 to 160 nm, respectively. The percentages gradually decreased with the increase in
the length of NCC whiskers. The right tail (from 281 to 420 nm) of the length
distribution for the Fraction 1 was 15.19%. For the Fraction 2, no NCC whiskers had
their lengths less than 20 nm. NCC whiskers with the length range from 21 to 40 nm,
and from 41 to 60 nm each accounted for about 1.05%. The major percentages of
10.53%, 4.21%, 22.10%, 16.84%, 11.58%, and 10.52% corresponded to the length
ranges from 61 to 80 nm, 81 to 100 nm, 101 to 120 nm, 121 to 140 nm, 141 to 160
nm, and 161 to 180 nm, respectively. The percentage of NCC whiskers began to
decrease when the length was higher than 180 nm (Figure 5.5a). The right tail (from
281 to 420 nm) of the length distribution for the Fraction 2 was 2.10%. For the
Fraction 3, no NCC whiskers had its length range less than 60 nm. About 5.55% of
NCC whiskers had its length range from 61 to 80 nm. The major percentages of NCC
whiskers were 17.78%, 22.22%, 16.67%, and 11.11% corresponding to the length
138
ranges from 81 to 100 nm, 101 to 120 nm, 121 to 140 nm, and 141 to 160 nm,
respectively. The percentage decreased to 5.55% for the length range from 161 to 180
nm. The right tail (from 281 to 420 nm) of the length distribution for the Fraction 3
was only 1.11%. For the Fraction 4, no NCC whisker with its length less than 20 nm
could be found. Only 0.83% of NCC whiskers were in the length range from 21 to 40
nm. Another 0.83% of NCC whiskers were in the length range from 41 to 60 nm. The
percentage increased to 5.83% in the length range from 61 to 80 nm. The major
percentages of NCC whiskers were 10.83, 25.00, 17.92, 10.42, and 15.00%
corresponding to the length ranges from 81 to 100 nm, 101 to 120 nm, 121 to 140 nm,
141 to 160 nm, and 161 to 180 nm. The percentage then deceased to 4.58% in the
following length range of 181-220 nm. There were no NCC whiskers in the right tail
(from 281 to 420 nm) of the length distribution for the Fraction 4 (Figure 5.5b). For
the Fraction 5, no NCC whiskers with their lengths less than 40 nm could be found.
About 6.00% of NCC whiskers were in the length range from 41 to 60 nm. Another
6.00% of NCC whiskers were in the length range from 61 to 80 nm. The majority of
NCC whiskers fell into narrow length ranges from 81 to 100 nm (21.00%), 101 to 120
nm (15.00%), and 121 to 140 nm (20.00%). The percentage decreased to 8.00% in the
following length range of 141-160 nm. The right tail (from 281 to 420 nm) of the
length distribution for the Fraction 5 only accounted for about 1.00% of NCC
whiskers (Figure 5.5b). For the Fraction 6, no NCC whiskers with their lengths less
than 20 nm could be found. Only 0.95% of NCC whiskers had its length range from
21 to 40 nm. The major percentages of NCC whiskers were 21.90%, 21.90%, 14.28%
139
and 20.00%, corresponding to the length ranges from 41 to 60 nm, 61 to 80 nm, 81 to
100 nm, and 101 to 120 nm, respectively. The percentage of NCC whiskers decreased
to 6.67% in the following length range of 101-120 nm. No NCC whiskers in the right
tail (from 221 to 420 nm) could be found. From the overall length distributions of
NCC whiskers, the number of precipitated NCC whiskers with small lengths increased
as RCF increased.
140
Figure 5.5 The length distribution of NCC whiskers after fractionation by differential
RCF. *Relative percentage= (Number of NCC whiskers in each bin of one fraction) /
(total number of NCC whiskers in one fraction)*100%. **Legends stand for
differential RCF in different fractions.
141
Based on the same length range from 41 to 180 nm, the percentages of NCC
whiskers from the six fractions were 63% for the Fraction 1, 77% for the Fraction 2,
79% for the Fraction 3, 85% for the Fraction 4, 82% for the Fraction 5 and 96% for
the Fraction 6. Table 5.3 shows the narrowest length ranges containing 90% of NCC
whiskers in each fraction: 81 to 320 nm for the Fraction 1, 81 to 220 nm for the
Fraction 2, 81 to 200 nm for the Fraction 3, 61 to 200 nm for the Fraction 4, 41 to 200
nm for the Fraction 5, and 41 to 160 nm for the Fraction 6. There was a general trend
that the length of NCC whiskers decreased when the RCF was increased. The length
range also became narrow at the same time.
Although the full range of length
distribution of NCC in each fraction was broad as indicated in Table 5.3, the length
range containing most NCC whiskers in each fraction was much smaller than the full
length range. TEM graphs showed that NCC whiskers were rod-shaped (Figure 5.2).
The diameter of NCC whiskers was almost 10 times less than the length.
The
variations in the diameter of NCC whiskers were pretty small. This may explain why
this differential centrifugation technique can separate NCC whiskers into narrow
length ranges.
142
Table 5.3 Comparison between the full length range and the major length range of
NCC whiskers at differential RCF
Fraction
No.
1
2
3
4
5
6
(rpm)
1000
1500
2000
2500
3000
3500
RCF
(g)
195
438
778
1216
1751
2383
Full length
range * (nm)
40 to 420
30 to 360
60 to 340
20 to 280
40 to 280
20 to 220
Major length
range ** (nm)
81 to 320
81 to 220
81 to 200
61 to 220
41 to 200
41 to 160
* The length range contained all NCC whiskers in one fraction.

** The major length range was defined as the narrowest length range containing 90% of NCC whiskers
in one fraction.
143
5.5.5 Aspect ratio distribution of NCC whiskers by differential centrifugation
The aspect ratio of NCC whiskers is defined as L/d, which is length over
diameter. The aspect ratio distributions of NCC whiskers for the Fractions 1-6 are
shown in Figure 5.6. For the Fraction 1, about 82 % of NCC whiskers had the aspect
ratio between 5 and 16, more specifically, the aspect ratio range of 5 to 8 (21.52%), 9
to 12 (39.24%), and 13 to 16 (21.52%) with the most abundant aspect ratio range
being between 9 and 12. For the Fraction 2, about 87% of NCC whiskers had the
aspect ratio between 5 and 16, i.e., the aspect ratio range of 5 to 8 (22.1%), 9 to 12
(36.84%), and 13 to 16 (28.42%). The NCC whiskers with the aspect ratio range
between 9 and 12 were still more abundant than those with other aspect ratio ranges
(Figure 5.6). About 65% of NCC whiskers from the Fraction 2 had a very narrow
aspect ratio between 9 and 16. For the Fraction 3, about 80% of the NCC whiskers
had the aspect ratio between 5 and 20, i.e., the aspect ratio range of 5 to 8 (12.22%), 9
to 12 (22.22%), 13 to 16 (18.89%), and 17 to 20 (26.67%).
The aspect ratio
distribution for the Fraction 3 was slightly broader than that for the Fractions 1 and 2.
The NCC whiskers with the aspect ratio between 17 and 20 were more abundant than
those with other aspect ratio ranges. For the Fraction 4, over 86% of NCC whiskers
had the aspect ratio between 5 and 16, i.e., the aspect ratio range of 5 to 8 (24.38%), 9
to 12 (40.62%), and 13 to 16 (21.25%). The NCC whiskers with the aspect ratio of 9
to 12 were the most abundant. For the Fraction 5, about 78% of NCC whiskers had
the aspect ratio between 5 and 16, i.e., 5 to 8 (26.00%), 9 to 12 (33.00%), and 13 to 16
(19.00%). The most abundant NCC whiskers also had the aspect ratio between 9 and
12. For the Fraction 6, about 81% of NCC whiskers had the aspect ratio between 5
144
and 16, i.e., the aspect ratio range of 5 to 8 (32.38%), 9 to 12 (30.48%), and 13 to 16
(18.10%). In other word, about 63% of NCC whiskers had the aspect ratio between 5
and 12. The aspect ratio distributions for all six fractions were all similar with the
most abundant aspect ratio range being between 9 and 12. Except the Fraction 3, more
than 78% of NCC whiskers from all other five fractions had their aspect ratio between
5 and 16.
145
Figure 5.6 The aspect ratio distribution of NCC whiskers after fractionation by
differential RCF. * Relative percentage= (number of NCC whiskers in each bin of
one fraction) / (total number of NCC in one fraction)*100%. ** Legends stand for
differential RCF in different fractions.
146
5.6 Conclusions
Based on the initial MCC weight, the total yield of NCC whiskers from the
sulfuric acid hydrolysis was 21.0%.
NCC whiskers obtained from the five-hour
hydrolysis had their diameter less than 100 nm. NCC whiskers were successfully
fractionized based on their sizes by a new differential centrifugation technique. The
volume of NCC whiskers has an inverse relationship with RCF. The experimental
data were consistent with the model of differential centrifugation. The majority of
NCC whiskers shifted to small sizes and the volume range of NCC also decreased as
RCF increased. Furthermore, the length of NCC whiskers also decreased and the
length range containing 90% of NCC whiskers became narrow as RCF increased. The
aspect ratio distributions of NCC whiskers were in a relatively narrow range. This
differential centrifugation technique will allow us to prepare NCC whiskers with a
narrow size distribution for various scientific studies and applications.
5.7 Acknowledgements
Financial support for this research was provided by Schill + Seilacher
147
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149
CHAPTER 6 NANOCRYSTALLINE CELLULOSE REINFORCED RUBBER
COMPOSITES
Wen Bai and Kaichang Li

Wood Science & Engineering Department, Oregon State University
Corvallis, OR 97331
150
6.1 Abstract
Methacrylamidopropyl,dimethyl,glycidylammonium
chloride
(I)
was
successfully prepared with the reaction between epichlorohydrin and N-[3(dimethylamino)propyl]-methacrylamide (DMPMA).
Nanocrystalline cellulose
(NCC) was prepared from microcrystalline cellulose through an acid hydrolysis

process. The compound I, Kymene 450 (a commercially available polymer), and
DMPMA were used to modify NCCs. The chemical-modified NCCs appeared to have
a lower tendency to form aggregates in water than unmodified NCCs. However,
freeze-dried chemical-modified NCCs could not be re-dispersed in water again.
Unmodified NCCs were used to reinforce SBR rubber through a dry blending process.
However, the resulting NCC-reinforced rubber composites had poor tensile strength
and high elongation-at-break, which was due to the poor dispersion of NCCs in the
rubber matrix. For improving the dispersion of NCCs in a rubber matrix, SBR was
first dissolved in THF and then mixed with one of the following NCC samples:
unmodified NCCs, the compound-I-modified NCCs, DMPMA-modified NCCs, and
Kymene-450-modified NCCs. The resulting NCC-SBR mixtures were casted a film
by removing THF at room temperature in a fume hood. SEM images of these films
revealed that this method did not lead to a better dispersion of NCCs in the SBR
matrix than that from the drying blending process.
6.2 Introduction
Natural fibers are abundant in plants such as grasses, reeds, stalks, and wood.
Cellulose is one of the main chemical components in these fibers. Native cellulose
includes amorphous and crystalline regions.
151
The crystalline regions (cellulose
crystals) can be obtained by removal of the amorphous regions through acid

hydrolysis of cellulose. These crystals are called nanocrystalline cellulose (NCC) if
one of their dimensions is smaller than 100 nm.
NCC has superior mechanical
strength and highly ordered structure. The elastic modulus of NCC is around 138 GPa
(Takashi et al., 1995) and the aspect ratio of NCC ranges from 20 to 60 (Kamel,
2007). Therefore, the possibility of using NCC as a reinforcing filler in polymeric
materials has received tremendous interest. Several studies have showed that it is
important to uniformly mix the reinforcing fillers with the polymeric materials for
superior strengths of the resulting materials (Ljungberg et al., 2005; Ljungberg et al.,
2006; Mathew et al., 2006; Petersson et al., 2007; Wang and Sain, 2007). When
compared with inorganic fillers, NCC as a filler has the following advantages (Kamel,
2007):
Renewable nature
Wide variety of sources available throughout the world
Nonfood agricultural based economy
Low energy consumption
Low cost
Low density
High specific strength and modulus
Relatively reactive surface, which can be surface-modified
Disposal by combustion of NCC filled composites is easier compared
with inorganic fillers rubber composites.
Natural rubber (NR) is obtained from latex from rubber trees. Both NR and
synthetic styrene butadiene rubber (SBR) are irreplaceable materials in the
applications of tires and engine mounts. NR is mainly used in winter tires and in tires
152
for trucks (Gopalan Nair and Dufresne, 2003). Tires for passenger cars are usually
made of SBR (Gopalan Nair and Dufresne, 2003). The annual consumption of NR
and SBR is almost the same. The properties of NR or SBR can be tailored by the
addition of fillers. There is no reported research about NCC as a reinforcing filler in
rubber materials. In this study, NCC-reinforced rubber composites were prepared and
characterized.

6.3.1 Chemicals and equipment
Microcrystalline cellulose (MCC) (Avicel pH-101, approximately 50 m in

diameter) was purchased from FMC BioPolymer (Philadelphia, PA). Sulfuric acid
(95-98 wt%) was purchased from Fisher Scientific (Gibbstown, NJ). Kymene 450
(20% solids content) was provided by Hercules Inc. (Wilmington, DE).
N-[3-
(dimethylamino)propyl]-methacrylamide (DMPMA) and tetrahydrofuran (THF) were

purchased from Sigma-Aldrich Inc. (Milwaukee, WI). Epichlorohydrin (ECH) was
from Acros Organics (Geel, Belgium). Diethyl ether was from Mallinckrodt Baker,
Inc. (Philipsburg, NJ). Deionized (DI) water was used in all experiments. Thin layer
chromatography (TLC) plates, TLC Silica gel-60-F254, were from EMD Chemicals
Inc. (Gibbstown, NJ). Uranyl Acetate and copper grids (200 mesh, covered with
carbon film) were purchased from Ted Pella Incorporated (Redding, CA). Table 6.1
shows the materials used for rubber compounding, including codes, trade names,
names and locations of manufacturers.
153
Table 6.1 Materials in NCC-reinforced rubber composites
Code
Rubber
SBR
Filler
Silica
NCC
Coupling
agent
Activator
Silane
ZnO
StAc
Processing
oil
Oil
Accelerator DPG
CBS
Vulcanizer
Trade name
Manufacturer
Buna VSL 5025Lanxess Corp.
1
Ultrasil7000
Degussa Corp.
GR
Prepared from the lab
Struktol Company
Si69a
of America
Zinc oxide
Horsehead Corp.
Textile Rubber &
Stearic acid
Chemical Co.
Shell Catenex
Shell UK Oil
Oil SNR
Products Ltd.
Weber & Schaer
Perkacit DPGb
GmbH & Co. KG
MLPC
Ekaland CBSc
International
Rubbermakers
R.E. Carroll Inc.
sulfur
Location
Orange, TX
Akron, OH
Stow, OH
Monaca, PA
Nurnberg,
Germany
Manchester, UK
Hamburg,
Germany
Rion des Landes,
France
Akron, OH
154
FTIR spectra were recorded on a NEXUS 470 FT-IR spectrometer (Thermo
Nicolet Corp., Madison, WI). Heraeus Labofuge 400 centrifuge was from Thermo
Scientific Corp. (Hanau, Germany). Amicon stirred cell was from Millipore Corp.
(Bedford, MA). Transmission electron microscope (TEM) was Philips CM-12 from
Philips (Eindhoven, The Netherlands). Scanning electron microscope (SEM) was FEI
dual beam field emission SEM from FEI Company (Hillsboro, OR).
Rubber
composites were prepared with a rubber mill (Reliable Rubber & Plastics Machinery
Co., North Bergen, NJ) and a Brabender (C.W. Brabender Instrument, Inc., South
Hackensack, NJ). The curing of the rubber composites was performed on a Carver
Press (Carver, Inc., Wabash, IN).
Strengths and elongation at break of rubber
composites were measured with Instron 5582 (Instron Corp., Norwood, MA).
6.3.2 Preparation of methacrylamidopropyl,dimethyl,glycidylammonium chloride (I)
The synthesis of compound I was performed in accordance with a literature

procedure (McClure, 1970). ECH (20.7 mL, 261.6 mmol) was placed a three-necked
round bottom flask fitted with a condenser and an addition funnel. DMPMA (10.6
mL, 58.1 mmol) was dropwise added into ECH over 10 min at 8 C. The reaction
mixture was stirred for 20 h at room temperature. TLC was used for monitoring the
process of the reaction. At the end of the reaction, diethyl ether (20 mL) was added
into the reaction mixture and yellow solids precipitated. The yellow solids were
filtered, washed with diethyl ether, evaporated with a rotary evaporator and dried
under high vacuum to generate the product (I) (9.2g, 60.3%). The product was
characterized by FT-IR.
155
6.3.3 Preparation of NCC suspension
NCC suspension (aqueous medium) was produced by following a literature

procedure (Dong et al., 1998). MCC powder (10.0 g) was hydrolyzed by sulfuric acid
(87.5 mL, 64% w/v) for five hours at 45 C with continuous stirring. The hydrolysis
was quenched by adding a large amount of water (500 mL) to the reaction mixture.
The resulting mixture was cooled to room temperature (25 C) and centrifuged
(2383g or 3500 rpm) for 30 min at room temperature. The supernatant was decanted.
Water (500 mL) was added to the precipitate and the mixture was then sonicated for
10 min to form a new suspension. This centrifugation/sonication process was repeated
three times. The newly generated suspension was filtered with an ultra-filtration
membrane (30,000 molecular weight cutoff) using an Amicon stirred cell until the pH
of the suspension reached a constant value. The resultant NCC suspension (around 0.2
wt%) was stored in a refrigerator at 3.0 C.
6.3.4 Preparation of NCC suspension with a stabilizer and freeze-dried NCC
Three chemicals were used as a stabilizer for a NCC suspension, Kymene 450,
DMPMA, and compound I. Kymene 450 (0.80 g) was diluted to 3% solids content by
DI water (4.55 mL), followed by adding 0.5 N NaOH (1.12 mL) (0.14 dry g/dry g of
Kymene 450) and stirring for 15 min at room temperature for the activation. The
activated Kymeme 450 was mixed with NCC suspension with 1/1 NCC/Kymene 450
weight ratio at room temperature. The mixture was stirred at room temperature for
one h.
The resulting NCC/Kymene 450 mixture was freeze-dried to generated
156
Kymene 450-coated NCC (simplified as K-NCC). DMPMA (0.16 g) and compound I
(0.16 g) were also mixed with NCC suspension with weight ratio of 1:1 at room
temperature, respectively to generated DMPMA-treated NCC (simplified as DMPMANCC), and Compound I-treated NCC (simplified as I-NCC). DMPMA was directly
added into NCC suspension, so as compound I. The suspensions of unmodified NCC,
K-NCC, DMPMA-NCC, and I-NCC were freeze-dried after being stored for one
week.
6.3.5 Preparation of NCC-reinforced rubber composites by dry-blending
The freeze-dried unmodified NCC (0, 2.0, 5.0, 8.0, or 10.0 g) was compounded
with SBR (103 g) in an open rubber mill, corresponding to the five specimens:
Control, NCC-2phr, NCC-5phr, NCC-8phr, and NCC-10phr. The content of silica
filler was correspondingly reduced to 78.0, 75.0, 72.0, and 70.0 g. The amounts of
other components in NCC-reinforced rubber composites were shown in Table 6.2.
Table 6.2 Other components in NCC-reinforced rubber composites
Weight (g)
Si69
Oil
ZnO
StAc
Sulfur
CBS
DPG
6.25
5.0
2.5
1.0
1.4
1.7
2.0
The compounding procedure included two passes. The first pass had all the
materials for rubber composites, except the curatives (sulfur, CBS, and DPG). The
resulting NCC-rubber composites were compounded in Brabender at 152-157 C for
six min so that Si69 could react with silica. The resulting rubber composites then
157
underwent the second pass where the curatives such as DPG, CBS, and sulfur were
included.
The compounding temperature of the second pass was at 50 C for
preventing premature cure of rubber composites. After the second pass, all batches
were made into sheets with the thickness of 2-4 mm by the open rubber mill.
6.3.6 Preparation of NCC-reinforced rubber composite films in organic solvent
SBR (5.0 g) was dissolved in THF (27 mL). A freeze-dried unmodified NCC
(0.10 g) was mixed with the SBR solution. The mixture was placed in a Teflon mold
in a fume hood and air-dried at room temperature for 7 to 10 days to obtain the
unmodified-NCC-reinforced SBR films with their thickness ranging between 0.5 and 1
mm. The films of K-NCC-reinforced SBR, DMPMA-NCC-reinforced SBR, and INCC-reinforced SBR were prepared separately in accordance with the previously
described procedure for making unmodified-NCC-reinforced SBR films
6.3.7 Microscopic images of NCC suspensions and NCC-rubber composites
The dried unmodified NCC was re-dispersed into water, and the resulting
suspensions were then sonicated for 10 min.
The re-dispersed NCC aqueous
suspension was placed on a copper grid (the drop size of the suspension was around
2.5 mm in diameter) and dried at room temperature (25 C). The sample was stained
with uranyl acetate (around 5 wt%) for three min (Zimmermann et al., 2006). TEM
images were acquired with TEM at 60 kV. The TEM images of K-NCC, DMPMANCC, and I-MCC were obtained through the same procedure as described previously
for obtaining the TEM images of unmodified NCC.
158
The freeze-dried unmodified NCC-reinforced SBR films were frozen under
liquid nitrogen and cut into small pieces. The small pieces of films were placed on a
mount and coated with gold/palladium on a sputter coater.
SEM images were
obtained using 7 kV secondary electrons. The SEM images of the films of K-NCCreinforced SBR, DMPMA-NCC-reinforced SBR, and I-NCC-reinforced SBR were
obtained separately in accordance with previously described procedure of obtaining
SEM images of the unmodified NCC-reinforced SBR films.
6.3.8 Tensile properties of NCC-reinforced rubber composites

D624.
about 3.00 mm and 6.25 mm, respectively.
Tensile strength is defined as the
following equation.
Tensile strength=
stress @ break
Eq. 6.1

6.4.1 Synthesis of compound I
Synthesis of the compound I is shown in Figure 6.1. The tertiary amino group
in DMPMA first opened the epoxy ring in epichlorohydrin; the resulting oxygen anion
replaced the Cl group to form a new epoxy again (Figure 6.1). Both DMPMA and
159
epichlorohydrin had low solubility in water, whereas the compound I was completely
soluble in water because of the quaternary amino group.
Figure 6.1 The scheme of synthesizing compound I from DMPMA and ECH
The FT-IR spectrum of compound I showed characteristic peaks at 3256 cm-1

for secondary amine (N-H) 1653 cm-1 for amide (-CO-N-), and 928 cm-1 for the
vibration of epoxy ring (Figure 6.2). Compound I had the same characteristic peak at
928 cm-1 for an epoxy ring as epicholorohydrin (Figure 6.2).
160
100 *ech
90
%T
80
922.57
70
60
50
100 *epoxy
95
90
1653.00
75
70
65
60
4000
3500
928.07
80
3256.66
%T
85
3000
2500
2000
1500
1000
Wavenumbers (cm-1)
Figure 6.2 FT-IR spectra of ECH (top) and compound I (bottom)
6.4.2 Stability of NCC suspensions
The suspensions of unmodified NCC, K-NCC, DMPMA-NCC, and I-NCC

were stored at room temperature for one week (Figure 6.3). The unmodified NCC
suspension showed some NCC aggregates at the bottom of the suspension (Figure
6.3a). The surface of NCC from sulfuric acid hydrolysis had negative charges. The
negative changes were supposed to help NCC evenly dispersed in water. Probably
because a large amount of NCC surface area did not contain the negative charge, NCC
still tended to aggregate.
161
a
Figure 6.3 a) NCC suspension without stabilizer, b) K-NCC suspension, c) DMPMANCC suspension, d) I-NCC suspension
162
Kymene 450 is a commercially available polyamine-epichlorohydrin adduct
containing quaternary ammonium groups at pH = 3, as shown in Figure 6.4. The
quaternary ammonium groups in Kymene 450 had positive charges.
Therefore,
Kymene 450 was coated on the surfaces of the negatively charged NCC, thus
preventing NCC from aggregation. As shown in Figure 6.3b, there were two layers:
water (top) and K-NCC suspension (bottom). The uniformity of K-NCC was shown
in the bottom layer.
R1
N+ Cl
R2
Cl
OH
Figure 6.4 Chemical structure of Kyemene 450
After one-week of storage, the DMPMA-NCC suspension was shown in

Figure 6.3c. DMPMA contains a tertiary amino group that can interact with the
hydrogen sulfate group (-OSO3H), thus being absorbed onto NCC surfaces. The white
DMPMA-NCC layer was very uniform, which was a good indication of good
suspension. The I-NCC suspension is shown in Figure 6.3d. There are two layers:
one clear water layer and one uniform white I-NCC layer. The uniformity of the INCC layer was a good indication that NCC did not aggregate. Compound I also
contained a quaternary ammonium group that interacted with the negative charges on
the NCC surfaces, thus preventing I-NCC from aggregation.
163
6.4.3 Micro-images of re-dispersed NCC suspensions
Because NCC samples had to be freeze-dried before they could be mixed with
rubber through a drying blending process, TEM was used to investigate if the freezedrying could lead to aggregation of unmodified NCC, K-NCC, DMPMA-NCC and INCC. Both single crystals and some agglomerates existed in TEM images of all NCC
samples, which implied that the freeze-drying resulted in the aggregation of NCC
samples (Figure 6.5). In other words, the freeze-dried NCC samples were difficult to
be re-dispersed into an aqueous medium.
164
a
Figure 6.5 TEM images of a) NCC without stabilizer, b) K-NCC, c) DMPMA-NCC,

d) I-NCC
165
6.4.3 Tensile properties of NCC-reinforced rubber composites
The tensile strength for NCC-2phr specimen was comparable to that of the
control. The tensile strengths gradually decreased when the NCC usage was raised
from 2 phr to 10 phr, i.e., from NCC-2phr to NCC-10phr. (Figure 6.6). NCC has to be
well separated and evenly distributed in the polymeric materials for achieving good
reinforcing effect (Ljungberg et al., 2005; Ljungberg et al., 2006; Mathew et al., 2006;
Petersson et al., 2007; Wang and Sain, 2007). We speculated that the decrease in the
tensile strength along with increasing the NCC usage might be due to the uneven
dispersion of NCC and large agglomerates of NCC in rubber matrix. The higher the
NCC usage in the rubber matrix the higher tendency of NCC to form large
agglomerates, which is consistent with the results shown in Figure 6.6 that the tensile
strength of NCC-reinforced rubber composites decreased with increasing the usage of
NCC.
16
13
10
hr
r
-1
CC
N
CC
-8
0p
ph
r
ph
N
CC
-5
-2
CC
N
Co
nt
ph
ro
Figure 6.6 The tensile strength of NCC-reinforced rubber composites without a

stabilizer
166
The elongation-at-break of the NCC-2phr was longer than that of the control
and increased when the NCC usage was raised from 2 phr to 8 phr (Figure 6.7). The
elongation-at-break of NCC-8phr was comparable to that of NCC-10phr.
When the
NCC formed large agglomerates for the same amount of NCC and rubber, the contact
areas between NCC and the rubber matrix decreased, thus reducing the interfacial
adhesion and the reinforcing effects, which resulted in the high elongation-at-break.
450
400
350
300
250
200
150
C
on
tr
ol
N
C
C
-2
ph
r
N
C
C
-5
ph
r
N
C
C
-8
ph
r
N
C
C
-1
0p
hr
100
Figure 6.7 The elongation-at-break of NCC-reinforced rubber composites without a

stabilizer
6.4.4 Morphology of freeze-dried unmodified and modified NCC-reinforced rubber

composite films
Because the poor dispersion of NCCs in the SBR matrix was believed to lead
to the poor tensile strength of NCC-reinforced rubber composites prepared by a dryblending process, SBR was first dissolved in THF before being mixed with a freezedried NCC for improving the dispersion of NCCs in the SBR matrix. SEM images of
unmodified-NCC-SBR, K-NCC-SBR, DMPMA-NCC-SBR and I-NCC-SBR films are
167
shown in Figure 6.8. The diameters of NCCs were smaller than 100 nm. At the
magnification level shown in Figure 6.8, NCCs should not have been visible as big
white areas if they were evenly dispersed in the SBR matrix. However, all four NCCreinforced SBR samples showed big white areas in the SEM images, indicating the
agglomerates of NCCs. The results from SEM images implied that freeze-dried NCCs
could not be evenly dispersed in SBR even if a SBR solution in THF was used.
168
a
Figure 6.8 SEM images of a) freeze-dried unmodified NCC-reinforced rubber

composite film, b) freeze-dried K-NCC-reinforced rubber composite film, c)freezedried DMPMA-NCC reinforced rubber composite film, d)freeze-dried I-NCCreinforced rubber composite film
169
6.5 Conclusions
The compound I was successfully synthesized from epichlorohydrin and
DMPMA. Treatments of NCCs with Kymene 450, DMPMA, or the compound I
appeared to stabilize NCCs from aggregation.
However, freeze-dried K-NCC,
DMPMA-NCC, and I-NCC could not be well dispersed in water again. The NCCreinforced rubber composites made with a dry-blending process had poor tensile
properties and high elongation-at-break, which was probably due to the poor
dispersion of NCCs in the SBR matrix. However, that SBR was dissolved in THF
followed by mixing with a freeze-dried NCC sample also did not improve the
dispersion of NCCs in the SBR matrix. For future research, the mixing of a rubber
latex with an aqueous NCC suspension followed by drying may lead to better
dispersion of NCCs in a rubber matrix because freeze-drying appeared to result in
aggregation of NCCs.
6.6 Acknowledgement
Financial support for this research was provided by Schill+Seilacher Struktol
AG, Hamburg, Germany.
170
6.7 References
conditions on the formation of colloid crystals of cellulose. Cellulose (London)
5, 19-32.
Gopalan Nair, K., Dufresne, A., 2003. Crab Shell Chitin Whisker Reinforced Natural
Rubber Nanocomposites. 1. Processing and Swelling Behavior.
Kamel, S., 2007. Nanotechnology and its applications in lignocellulosic composites, a
mini review. eXPRESS Polymer Letters 1, 546-575.
Ljungberg, N., Bonini, C., Bortolussi, F., Boisson, C., Heux, L., Cavaille, 2005. New
Nanocomposite Materials Reinforced with Cellulose Whiskers in Atactic
Polypropylene: Effect of Surface and Dispersion Characteristics.
Ljungberg, N., Cavaill, J.Y., Heux, L., 2006. Nanocomposites of isotactic
polypropylene reinforced with rod-like cellulose whiskers. Polymer 47, 62856292.
Mathew, A.P., Chakraborty, R.T., Oksman, K., Sain, M., 2006. The strucutre and
mechanical properties of cellulose nanocomposites prepared by twin screw
extrusion. In. ACS Symp. Ser., pp. 114-131.
McClure, J.D., 1970. Glycidyltrimethylammonium chloride and related compounds.
The Journal of Organic Chemistry 35, 2059-2061.
Petersson, L., Kvien, I., Oksman, K., 2007. Structure and thermal properties of
poly(lactic acid)/cellulose whiskers nanocomposite materials. Composites
Science and Technology 67, 2535-2544.
Takashi, N., Kiyofumi, T., Katsuhiko, N., 1995. Elastic modulus of the crystalline
regions of cellulose polymorphs. Journal of Polymer Science Part B: Polymer
Physics 33, 1647-1651.
Wang, B., Sain, M., 2007. Dispersion of soybean stock-based nanofiber in a plastic
matrix. Polymer International 56, 538-546.
171
CHAPTER 7 GENERAL CONCLUSIONS

In summary, the crystalline portions of cellulose such as microcrystalline
cellulose (MCC) have been successfully used as fillers for rubber composites. MCC
was incorporated into rubber composites as the partial replacement of silica without
any new coupling agents. The partial replacement of silica provided the following
advantages for the rubber composites: 1) low energy consumption for compounding,
2) good processability, 3) strong tensile properties, 4) good heat resistance, and 5) the
potential of good fuel efficiency for tire applications.
The good interfacial bonding between fillers and a rubber matrix is essential
for generating the desired properties of rubber composites for most of the end
applications.
In our study, MCC was surface-modified with various chemicals.
Acryloyl chloride was first used to modify MCC to form acrylate on MCC surfaces.
The carbon-carbon double bond of acrylate groups could be opened during
vulcanization, thus forming covalent linkages between MCC and rubber matrix.
Alkenyl ketene dimmer (AnKD), a readily available sizing agent for paper, was also
used to modify MCC surfaces. The ketene functional group of AnKD could react with
hydroxyl groups of MCC and the carbon-carbon double bonds on the fatty acid chains
could form covalent linkages with the rubber matrix during vulcanization. The surface
modifications of MCC did not alter the integrity of MCC, but enhanced the chemical
activity of the MCC surfaces toward the rubber matrix. Both acrylated MCC an
AnKD-modified MCC provided better interfacial adhesion between MCC and the
rubber matrix than MCC alone. Thus, A-MCC and AnKD-MCC were superior to
MCC in terms of improving tear properties of rubber composites.
172
Nanocrystalline cellulose (NCC), a potential nano-size filler for rubber
composites, was prepared from the acid hydrolysis of MCC. Because the geometrical
features of NCC are important factors that determine the strength of NCC-reinforced
composites, a new technique of differential centrifugation was developed for the
production of NCC with a narrow size distribution. NCCs tend to aggregate because
their huge surface areas.
Methacrylamidopropyl,dimethyl,glycidylammonium
chloride (I) were successfully synthesized. The compound I, Kymene 450, and N-[3(dimethylamino)propyl]-methacrylamide (DMPMA) were used to modify NCC in
aqueous suspensions. The modifications indeed appeared to stabilize NCCs from
aggregation.
However, the freeze-drying of these chemical-modified NCC
suspensions appeared to lead to aggregation of NCCs. In other words, the freeze-dried

modified NCC samples could not be well re-dispersed in water again. Unmodified
NCC samples were investigated as nano-fillers for SBR rubber through a dry-blending
process. However, the resulting NCC-SBR composites had poor tensile strength and
high elongation-at-break, which was due to the poor dispersion of NCCs in the rubber
matrix. Dissolution of SBR in THF followed by mixing with a NCC sample also did
not improve the dispersion of NCCs in the rubber matrix. For future research, the
mixing of an aqueous NCC suspension with a rubber latex followed by drying may be
a better way of dispersing NCCs in a rubber matrix.
173
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AN ABSTRACT OF THE DISSERTATION OF

Rubber without reinforcement has limited applications.

differential centrifugation technique has been developed for separation of NCC

NCC had to be dried before it could be blended with rubbers.

Copyright by Wen Bai

New Application of Crystalline Cellulose in Rubber Composites

Presented November 3, 2009

Doctor of Philosophy dissertation of Wen Bai presented on November 3, 2009.

I understand that my dissertation will become part of the permanent collection of

First and foremost, I would like to express my sincere appreciation to my

Many thanks also go to the faculty and staff

members of Department of Wood Science and Engineering and School of Chemical,

TABLE OF CONTENTS (Continued)

TABLE OF CONTENTS (Continued)

TABLE OF CONTENTS (Continued)

TABLE OF CONTENTS (Continued)

TABLE OF CONTENTS (Continued)

1.1 Molecular structure of cellulose.............................................................................. 2

LIST OF FIGURES (Continued)

2.2 Temperature profiles of Batch 1, Batch 2, Batch 3, Batch 4, and Batch 5

LIST OF FIGURES (Continued)

LIST OF FIGURES (Continued)

6.7 The elongation-at-break of NCC-reinforced rubber composites without a

2.1 Materials in this study........................................................................................... 43

CHAPTER 1 GENERAL INTRODUCTION AND LITERATURE REVIEW

main component for all plants such as cotton and trees

One end of the cellulose chain has a reducing group, i.e.,

Figure 1.1 Molecular structure of cellulose (Kamel et al., 2008)

Because of compact structures and strong intermolecular and intramolecular

1.2.1b Microcrystalline cellulose (MCC)

1.2.1c Nanocrystalline cellulose (NCC)

1.2.2 Main fillers in rubber composites

1.2.2a Carbon black

Figure 1.3 Morphology of carbon black (Norman, 1990)

Reinforcement of rubber by carbon black depends on many variables: surface

The surface area is usually

The strong hydrogen bonding in

Figure 1.4 Morphology of silica (Tscheschel et al.)

Figure 1.5 Chemical structures for butadiene rubber (Barlow, 1993a)

1.2.3b Styrene butadiene rubber (SBR)

Figure 1.6 Chemical structure for SBR (Barlow, 1993b)

1.2.4 Vulcanized rubbers

Figure 1.7 The vulcanization process in rubber (Coran, 1978c)

The most common curatives for saturated rubbers are peroxides,

quinonedioximes, metal oxides, amines, and isocyanates (Hofmann, 1989a).

1.2.4b Sulfur vulcanization

There are different types of accelerators, such as thiazoles,

The general reaction mechanism of sulfur vulcanization with an accelerator is

1.2.4c Characterization of the vulcanization process

MH: maximum torque, ML: minimum torque.

In a marching curve, more polysulfide crosslinks are

Figure 1.11 Vulcanization of rubber composites by Curemeter (Coran, 1978f)

1.2.5 Rubber composites

Figure 1.12 The effects of vulcanization on properties of vulcanized rubber

1.2.6 Adhesion between fillers and rubber matrix

Different fillers and rubbers require different

Depending on the fillers used, many

1.2.7 Surface modifications for microcrystalline cellulose

Figure 1.14 The working mechanism of a silane coupling agent in MCC-reinforced

Figure 1.15 PMDI as a coupling agent for MCC-PS composites

Treatment of MCC surfaces with maleic-anhydride (MA)-modified polymers

Figure 1.16 MA-polymer as a coupling agent for MCC-polymer composites

Figure 1.17 Acryloyl chloride as a coupling agent in polymer composites (Bojani et