DEPARTMENT OF CHEMISTRY
AND TECHNOLOGY OF POLYMERS
CRACOW UNIVERSITY OF TECHNOLOGY
ul. Warszawska 24
31-155 Krakow Poland
www.pk.edu.pl
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 post-graduate 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:
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•
•
•
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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:
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•
•
•
•
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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
Other
 Applications:
gears, conveyors,
elements of pumps, belt
fasteners, etc.
PA
POM
PC
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
N
CH3
Cl
R1
N
Cl
R2
2R2M
1R3M
CH3
H2C
CH3
CH2OH
CH2 CH2 OH
R
N
H2C
CH3
Cl
OH
CH2 N
CH2 CH2 OH
RM2Et
CH2OH
R
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 (o-MMT)
XRD diffractograms of sodium MMT and o-MMT modified with
different amounts of ammonium modifier (50 and 100% of cation
exchange capacity of MMT).

Intensity
More effective in dispersing the polymer matrix were o-MMT with higher
interlayer distances since organic compound facilitates exfoliation by
(i)
changing
the
hydrophilic
5,0 5,8
character of montmorillonite into
Na+MMT
6,55
organophilic one thus allowing
MMT-RA3M, 50% CEC
macromolecules to intercalate into
MMT-RA3M, 100% CEC
MMT
galleries,
and,
(ii) increasing the distance between
montmorillonite
layers
and
simultaneously
weakening
electrostatic forces responsible for
2
7
12
17
2 theta, degree
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
5.2
b
intensity, a.u.
6.35
a
5.5
c
2
4
6
8
10
2θ, degrees
12
14
2θ peak at ca. 5.5º 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
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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
μm
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
(microcomposite)
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 silica-type 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
Polyhedral oligomeric silsesquioxanes
Characteristic and properties of POSS
R
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)
Si
O
R Si O
O
O
Si
O
Si R O
O
X
Si
O
Si R O
O
O
R
Si
R
Si
O R
One or more reactive groups
for grafting or polymerization
Unreactive organic (R)
groups for solubilization and
compatibilization
POSS Properties:
 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 highperformance 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:
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4,4 -methylenebis(phenylisocyanate)
(MDI)
poly(tetramethylene glycol)
(Terathane 1400) (PTMG)
1,2-propanediol-heptaisobutyl-POSS
(PHIPOSS)
Temperature: 80°C
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, agricultural
applications
DEPARTMENT OF CHEMISTRY AND TECHNOLOGY OF POLYMERS
CRACOW UNIVERSITY OF TECHNOLOGY
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
Contact person:
Prof. Krzysztof Pielichowski
Head of Department
Tel. : +48-12-6282727
Fax : 6282947
e-mail : kpielich@usk.pk.edu.pl
DEPARTMENT OF CHEMISTRY AND TECHNOLOGY OF POLYMERS
CRACOW UNIVERSITY OF TECHNOLOGY
Thank you
for your attention