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DEPARTMENT OF CHEMISTRY

AND TECHNOLOGY OF POLYMERS


CRACOW UNIVERSITY OF TECHNOLOGY

Profile :
Department of Chemistry and Technology of Polymers
(hereafter called Department) is a part of Faculty of
Chemical Engineering and Technology at the Cracow
University of Technology. In the Department there are 3 full
professors, 1 associate professor, 9 adjuncts and 4 members
of staff.
Faculty members of the Department are involved in teaching
and research in the area of polymer chemistry and
technology, including materials science issues. At the postgraduate level 45 students are trained within the
specialisation technology of polymers, performing at the
final semester M.Sc. works under supervision of faculty
members at the Department.
Most of the research works is performed together with 12
Ph.D. students who are working towards their doctorates at
the Department, being funded by Ministry of National
Education and Science in Poland.
DEPARTMENT OF CHEMISTRY AND TECHNOLOGY OF POLYMERS
CRACOW UNIVERSITY OF TECHNOLOGY

Activities :
Education: the main teaching profile is technology and
engineering
of polymeric materials (polymers, copolymers, blends,
(nano)composites, plastics, hybrid materials, etc.) and their
application as innovative products in modern materials
engineering.
Research: synthesis, processing, characterisation and optimization
of properties of polymeric materials for advanced applications.
Design
of structure / properties relationships in polymer nanocomposites
to fabricate value-added products and technologies.
Cooperation: established links with Polish polymer industry to
develop jointly new products and technologies as well as to offer
training possibilities and research expertize.

DEPARTMENT OF CHEMISTRY AND TECHNOLOGY OF POLYMERS


CRACOW UNIVERSITY OF TECHNOLOGY

Expertise on following materials:

polymers
copolymers
blends
(nano)composites
hybrid materials

DEPARTMENT OF CHEMISTRY AND TECHNOLOGY OF POLYMERS


CRACOW UNIVERSITY OF TECHNOLOGY

Actual research domains concerning materials


technology /Competences :
Activities :
Research works performed at the Department focus on the
following areas:

Synthesis of novel polymers for special applications (e.g.


biodegradable polymers, polymers from renewable
resources, polymer nanohydrogels),
Preparation of polymer blends and nanomaterials for
thermal energy storage materials,
Polymer nanocomposites with enhanced thermal properties,
Recycling of polymers and plastics, particularly PVC wastes,
Flame retardancy of polymeric (nano)materials,
Application of novel techniques in polymer synthesis and
characterisation, e.g. MT-DSC, microwaves, thermovision.
DEPARTMENT OF CHEMISTRY AND TECHNOLOGY OF POLYMERS
CRACOW UNIVERSITY OF TECHNOLOGY

POM/MMT

DEPARTMENT OF CHEMISTRY AND TECHNOLOGY OF POLYMERS


CRACOW UNIVERSITY OF TECHNOLOGY

Polyoxymethylene (POM) - engineering


thermoplastic polymer
Properties:
high mechanical strength,
chemical resistance,
thermal resistance,
good electrical properties.

POM share in the worldwide


production of engineering
thermoplastics

Applications:
gears, conveyors,
elements of pumps, belt
fasteners, etc.

DEPARTMENT OF CHEMISTRY AND TECHNOLOGY OF POLYMERS


CRACOW UNIVERSITY OF TECHNOLOGY

Polymer/layered silicate nanocomposites


Advantages over classic composites
Improved material performance at low filler loading
(below 10 wt%, usually 3 -5 wt%) due to small
interparticle distances and the conversion of a large
fraction of the polymer matrix near their surfaces into an
interphase of different properties as well as to the
consequent change in morphology.
Enhancement of a variety of properties, e.g. mechanical
strength, thermal stability, chemical resistance, barrier
properties.
Elimination or reduction of processing problems, such as
substantial changes in rheological properties,
deterioration of surface appearance.

DEPARTMENT OF CHEMISTRY AND TECHNOLOGY OF POLYMERS


CRACOW UNIVERSITY OF TECHNOLOGY

Structures of ammonium compounds used


for MMT modification
CH3

CH3
R

Cl

CH3

Cl

R2

2R2M

1R3M

CH3

H2C

R1

CH3
CH2OH

CH2 CH2 OH
R

N
H2C

Cl

CH3

OH

CH2 N

CH2 CH2 OH

RM2Et

CH2OH

CH3
R

N
CH3

CH3

Cl

RA3M, where
R contains
amide group

DEPARTMENT OF CHEMISTRY AND TECHNOLOGY OF POLYMERS


CRACOW UNIVERSITY OF TECHNOLOGY

Cl
RB2Et

Structure of organo-modified MMT (oMMT)

XRD diffractograms of sodium MMT and o-MMT modified with


different amounts of ammonium modifier (50 and 100% of
cation exchange capacity of MMT).
More effective in dispersing the polymer matrix were o-MMT with
higher interlayer distances since organic compound facilitates
(i) changing the hydrophilic
exfoliation by
character of montmorillonite
into organophilic one thus
allowing
macromolecules
to
intercalate into MMT galleries,
and,
(ii) increasing the distance
between montmorillonite layers
and simultaneously weakening
electrostatic forces responsible
for MMT stack cohesion.
DEPARTMENT OF CHEMISTRY AND TECHNOLOGY OF POLYMERS
CRACOW UNIVERSITY OF TECHNOLOGY

Melt blending of MMT into POM matrix

Previous research on thermoplastic polymers indicated


that the degree of exfoliation/intercalation of MMT is
favoured by
Longer time of mixing
Higher speed of rotors
Higher melt viscosity (higher molecular weight of
polymer)
Since POM is susceptible to thermomechanical
degradation the optimization of processing
parameters is required.
DEPARTMENT OF CHEMISTRY AND TECHNOLOGY OF POLYMERS
CRACOW UNIVERSITY OF TECHNOLOGY

Nanocomposite structure characterization


2 peak at ca. 5.5
indicates the presence of
unintercalated stacks of
organomodified
MMT
layers. However, taking
into account the weak
intensity of these peaks,
partial
exfoliation
of
montmorillonite can be
considered.
WAXD diffractograms of:
a- pristine MMT,
b - organo-modified MMT (MMT-2M2R),
c - POM/MMT-2M2R nanocomposite.
DEPARTMENT OF CHEMISTRY AND TECHNOLOGY OF POLYMERS
CRACOW UNIVERSITY OF TECHNOLOGY

Model of structure of POM/MMT


nanocomposite

DEPARTMENT OF CHEMISTRY AND TECHNOLOGY OF POLYMERS


CRACOW UNIVERSITY OF TECHNOLOGY

Structure of nanocmposites

SEM microphotographs homogenic distribution of MMT


stacks and layers

POM

POM/Na+MMT

POM/MMT-2R2M.

DEPARTMENT OF CHEMISTRY AND TECHNOLOGY OF POLYMERS


CRACOW UNIVERSITY OF TECHNOLOGY

Core-shell structure of nanocomposite


injection moulding

SEM microphotographs of criofractured injection


moulding sample

247
m

DEPARTMENT OF CHEMISTRY AND TECHNOLOGY OF POLYMERS


CRACOW UNIVERSITY OF TECHNOLOGY

Influence of MMT on crystallization


process of POM

Sample

Enthalpy of melting
Hm
[J/g]

Crystallinity
degree
C%
[%]

Core
region

Shell
region

Core
region

Shell
region

POM

135.1

133.7

41.4

41.0

POM/Na+MMT
(microcomposit
e)

145.4

136.8

44.6

41.9

POM/MMT-2R2M
(nanocomposite
)

168.0

137.6

51.5

42.2

DEPARTMENT OF CHEMISTRY AND TECHNOLOGY OF POLYMERS


CRACOW UNIVERSITY OF TECHNOLOGY

POSS polyhedral oligomeric


silsesquioxanes

DEPARTMENT OF CHEMISTRY AND TECHNOLOGY OF POLYMERS


CRACOW UNIVERSITY OF TECHNOLOGY

POSS polyhedral oligomeric


silsesquioxanes
Within the latter class of materials increasing interest lies in
the usage of functional polyhedral oligomeric silsesquioxanes
(POSS) with a general formula (RSiO1.5)n having natural silicatype nanoparticles with a well defined structure and topology
as an inorganic phase. Cubic structural compounds (completely
and incompletely condensed silsesquioxanes) are commonly
illustrated as T6, T8, T10 and T12, based on the number of silicon
atoms present in cubic structure.
POSS nanostructured chemicals, with sizes of from 1 to 3 nm in
diameter, can be thought of as the smallest possible particles
of silica
Structures of POSS
occurring most often: a
T6, b T8, c T10, d i e
T12.

Cubane cage of POSS


(RSiO1,5)8
DEPARTMENT OF CHEMISTRY AND TECHNOLOGY OF POLYMERS
CRACOW UNIVERSITY OF TECHNOLOGY

R
X
O
S
i
S
i
O
O
O
R
R
iO
S
S
i
O
O
S
i
S
i
O
R
O
R
iRR
S
S
i
O

Polyhedral oligomeric silsesquioxanes


Characteristic and properties of POSS

Thermally and chemically


robust hybrid framework.
Precise three-dimensional
structure for molecular level
reinforcement of polymer
segments and coils.
1 - 3 nm (~0,5 nm)

POSS Properties:

One or more reactive


groups for grafting or
polymerization

Unreactive organic (R)


groups for solubilization
and compatibilization

They occur in the form of crystalline solids,


waxes and oils.
Soluble in organic solvents such as THF,
toluene, chloroform and hexane.
They have relatively low melting point.
Due to the presence of Si-O bonds are rigid
and resistant to nucleophilic and electrophilic
agents.
DEPARTMENT OF CHEMISTRY AND TECHNOLOGY OF POLYMERS
CRACOW UNIVERSITY OF TECHNOLOGY

Polymeric nanohybrid materials


Definitions

Hybrid materials mixtures of two or more materials with new


properties
created by new electron orbitals formed between each material, such
as covalent bond between polymer and silanol molecules in
inorganic/organic hybrids.

Hybrid composite

Hybrid polymer

The composite material


in which two or more
high-performance
reinforcements are
combined.

Understood as the
polymer where an organic
part is combined, on the
molecular level, with an
inorganic part.

DEPARTMENT OF CHEMISTRY AND TECHNOLOGY OF POLYMERS


CRACOW UNIVERSITY OF TECHNOLOGY

Nanohybrid materials
POSS/Polymer
Hybrid organic-inorganic materials based on incorporating of polyoctahedral
oligomeric silsesquioxanes (POSS) into polymeric matrices have received a
considerable attention.
A variety of POSS nanostructured chemicals contain one or more covalently
bonded reactive functionalities that are suitable for polymerization, grafting,
surface bonding, or other transformations.
Covalently bonded POSS nanocomposites exhibit:
improved thermal and mechanical stability,
improved elasticity,
increased the resistance to oxidation,
increased the resistance to UV radiation,
reinforcement of the surface,
increased glass-transition temperature value,
reduced flammability,
enhanced mechanical strength,

System of POSS-polymer.
DEPARTMENT OF CHEMISTRY AND TECHNOLOGY OF POLYMERS
CRACOW UNIVERSITY OF TECHNOLOGY

Synthesis of PU - POSS
I STEP: Synthesis of PU
prepolymer:

4,4
-methylenebis(phenylisocyanate)
(MDI)
poly(tetramethylene glycol)
(Terathane 1400) (PTMG)
1,2-propanediol-heptaisobutylPOSS (PHIPOSS)
Temperature: 80C
Atmosphere: N2

II STEP: Synthesis of PU
elastomer:

1,4-butanediol

DEPARTMENT OF CHEMISTRY AND TECHNOLOGY OF POLYMERS


CRACOW UNIVERSITY OF TECHNOLOGY

Morphology
PU-POSS

Lateral force AFM images for PU/POSS

WAXD diffractograms of
PU/POSS polymers

DEPARTMENT OF CHEMISTRY AND TECHNOLOGY OF POLYMERS


CRACOW UNIVERSITY OF TECHNOLOGY

Thermal analysis
PU-POSS

Normalized TSDC thermograms for PU and hybrid


PU/POSS

Normalized DSC thermograms recorded with


polyurethane matrix and the hybrids

Composite TGA mass loss plots


for PU/POSS hybrid systems

DEPARTMENT OF CHEMISTRY AND TECHNOLOGY OF POLYMERS


CRACOW UNIVERSITY OF TECHNOLOGY

Thermal analysis
PU-POSS

DEPARTMENT OF CHEMISTRY AND TECHNOLOGY OF POLYMERS


CRACOW UNIVERSITY OF TECHNOLOGY

ACRYLATE HYDROGELS

DEPARTMENT OF CHEMISTRY AND TECHNOLOGY OF POLYMERS


CRACOW UNIVERSITY OF TECHNOLOGY

Acrylate hydrogels polymer matrix


Hydrogels matrix have some different properties
such as their capacity to allow controlled release,
changing their swellability by ionic strength, pH ,
temperature, chemical activity to interact with
adsorbates and selectivity to some species (i.e.,
metal ions, proteins and enzymes)
Applications:
medical applications,
including drug delivery
systems, scaffold materials
to organize cells into
a
three-dimensional
architecture, tissue
replacements, wounds
dressings and immobilization
of proteins,
cells,
DEPARTMENT OF CHEMISTRY AND TECHNOLOGY
OF POLYMERS
CRACOW UNIVERSITY OF TECHNOLOGY
agricultural applications

Crosslinking reaction of acrylic acid


with N,N`-methylenobisacryloamide

Swelling of hydrogels

DEPARTMENT OF CHEMISTRY AND TECHNOLOGY OF POLYMERS


CRACOW UNIVERSITY OF TECHNOLOGY

SEM microphotographs of swollen


acrylic matrix

DEPARTMENT OF CHEMISTRY AND TECHNOLOGY OF POLYMERS


CRACOW UNIVERSITY OF TECHNOLOGY

Available research infrastructure :

fully-equipped polymer processing laboratory (extrusion,


Brabender mixing, injection moulding, compression
moulding, pressing, pelleting, grinding, etc),
thermal analysis laboratory (TG, DSC, MT-DSC, DMA,
TG/DSC),
FTIR, FTIR microscopy, UV-Vis, NMR, AFM, GC/MS, GPC,
HPLC,
mechanical properties testing machines,
LOI, thermovision camera, UL-94.

DEPARTMENT OF CHEMISTRY AND TECHNOLOGY OF POLYMERS


CRACOW UNIVERSITY OF TECHNOLOGY

Thank you
for your attention

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