DEPARTMENT OF CHEMISTRY DEPARTMENT OF CHEMISTRY AND TECHNOLOGY OF POLYMERSAND TECHNOLOGY OF POLYMERSCRACOW UNIVERSITY OF TECHNOLOGY CRACOW UNIVERSITY OF TECHNOLOGY
Profile :Profile :
Department of Chemistry and Technology of Polymers Department of Chemistry and Technology of Polymers (hereafter called “Department”) is a part of Faculty of (hereafter called “Department”) is a part of Faculty of Chemical Engineering and Technology at the Cracow Chemical Engineering and Technology at the Cracow University of Technology. In the Department there are 3 full University of Technology. In the Department there are 3 full professors, 1 associate professor, 9 adjuncts and 4 professors, 1 associate professor, 9 adjuncts and 4 members of staff. members of staff.
Faculty members of the Department are involved in Faculty members of the Department are involved in teaching and research in the area of polymer chemistry and teaching and research in the area of polymer chemistry and technology, including materials science issues. At the post-technology, including materials science issues. At the post-graduate level 45 students are trained within the graduate level 45 students are trained within the specialisation “technology of polymers”, performing at the specialisation “technology of polymers”, performing at the final semester M.Sc. works under supervision of faculty final semester M.Sc. works under supervision of faculty members at the Department. members at the Department.
Most of the research works is performed together with 12 Most of the research works is performed together with 12 Ph.D. students who are working towards their doctorates at Ph.D. students who are working towards their doctorates at the Department, being funded by Ministry of National the Department, being funded by Ministry of National Education and Science in Poland.Education and Science in Poland.
DEPARTMENT OF CHEMISTRY AND TECHNOLOGY OF POLYMERSDEPARTMENT OF CHEMISTRY AND TECHNOLOGY OF POLYMERSCRACOW UNIVERSITY OF TECHNOLOGY CRACOW UNIVERSITY OF TECHNOLOGY
Activities :Activities :
Education: the main teaching profile is technology and Education: the main teaching profile is technology and engineering engineering
of polymeric materials (polymers, copolymers, blends, of polymeric materials (polymers, copolymers, blends, (nano)composites, plastics, hybrid materials, etc.) and their (nano)composites, plastics, hybrid materials, etc.) and their application as innovative products in modern materials application as innovative products in modern materials engineering. engineering.
Research: synthesis, processing, characterisation and Research: synthesis, processing, characterisation and optimization optimization
of properties of polymeric materials for advanced applications. of properties of polymeric materials for advanced applications. Design Design
of structure / properties relationships in polymer of structure / properties relationships in polymer nanocomposites to fabricate value-added products and nanocomposites to fabricate value-added products and technologies.technologies.
Cooperation: established links with Polish polymer industry to Cooperation: established links with Polish polymer industry to develop jointly new products and technologies as well as to offer develop jointly new products and technologies as well as to offer training possibilities and research expertize. training possibilities and research expertize.
DEPARTMENT OF CHEMISTRY AND TECHNOLOGY OF POLYMERSDEPARTMENT OF CHEMISTRY AND TECHNOLOGY OF POLYMERSCRACOW UNIVERSITY OF TECHNOLOGY CRACOW UNIVERSITY OF TECHNOLOGY
Expertise on following materials:Expertise on following materials:
• polymerspolymers• copolymerscopolymers• blendsblends• (nano)composites(nano)composites• hybrid materialshybrid materials
DEPARTMENT OF CHEMISTRY AND TECHNOLOGY OF POLYMERSDEPARTMENT OF CHEMISTRY AND TECHNOLOGY OF POLYMERSCRACOW UNIVERSITY OF TECHNOLOGY CRACOW UNIVERSITY OF TECHNOLOGY
Actual research domains concerning materials Actual research domains concerning materials technology /Competences :technology /Competences :
Activities :Activities :
Research works performed at the Department focus on the Research works performed at the Department focus on the following areas:following areas:
• Synthesis of novel polymers for special applications (e.g. Synthesis of novel polymers for special applications (e.g. biodegradable polymers,biodegradable polymers, polymers from renewable polymers from renewable resources, polymer nanohydrogels),resources, polymer nanohydrogels),
• Preparation of polymer blends and nanomaterials for Preparation of polymer blends and nanomaterials for thermal energy storage materials,thermal energy storage materials,
• Polymer nanocomposites with enhanced thermal Polymer nanocomposites with enhanced thermal properties,properties,
• Recycling of polymers and plastics, particularly PVC Recycling of polymers and plastics, particularly PVC wastes,wastes,
• Flame retardancy of polymeric (nano)materials,Flame retardancy of polymeric (nano)materials,• Application of novel techniques in polymer synthesis and Application of novel techniques in polymer synthesis and
characterisation, e.g. MT-DSC, microwaves, thermovision.characterisation, e.g. MT-DSC, microwaves, thermovision.DEPARTMENT OF CHEMISTRY AND TECHNOLOGY OF POLYMERSDEPARTMENT OF CHEMISTRY AND TECHNOLOGY OF POLYMERS
CRACOW UNIVERSITY OF TECHNOLOGY CRACOW UNIVERSITY OF TECHNOLOGY
POM/MMTPOM/MMT
DEPARTMENT OF CHEMISTRY AND TECHNOLOGY OF POLYMERSDEPARTMENT OF CHEMISTRY AND TECHNOLOGY OF POLYMERSCRACOW UNIVERSITY OF TECHNOLOGY CRACOW UNIVERSITY OF TECHNOLOGY
Polyoxymethylene (POM) - engineering Polyoxymethylene (POM) - engineering thermoplastic polymerthermoplastic polymer
Properties:Properties:high mechanical strength, high mechanical strength, chemical resistance,chemical resistance,thermal resistance,thermal resistance,good electrical properties.good electrical properties.
Applications:Applications:gears, conveyors, gears, conveyors, elements of pumps, belt elements of pumps, belt fasteners, etc.fasteners, etc.
POM share in the worldwide POM share in the worldwide production of engineering production of engineering thermoplasticsthermoplastics
PC
POM
Other
PA
DEPARTMENT OF CHEMISTRY AND TECHNOLOGY OF POLYMERSDEPARTMENT OF CHEMISTRY AND TECHNOLOGY OF POLYMERSCRACOW UNIVERSITY OF TECHNOLOGY CRACOW UNIVERSITY OF TECHNOLOGY
Polymer/layered silicate nanocompositesPolymer/layered silicate nanocomposites
Advantages over classic compositesAdvantages over classic composites
Improved material performance at low filler loading Improved material performance at low filler loading (below 10 wt%, usually 3 -5 wt%)(below 10 wt%, usually 3 -5 wt%) d due to small ue to small interparticle distances and the conversion of a large interparticle distances and the conversion of a large fraction of the polymer matrix near their surfaces into an fraction of the polymer matrix near their surfaces into an interphase of different properties as well as to the interphase of different properties as well as to the consequent change in morphology.consequent change in morphology. Enhancement Enhancement ofof a variety of properties a variety of properties,, e e.g..g. mmechanical echanical strength, thermal stability, chemical resistance, barrier strength, thermal stability, chemical resistance, barrier propertiesproperties..Elimination or reduction of processing problems, such as Elimination or reduction of processing problems, such as substantialsubstantial changes in rheological properties, changes in rheological properties, deterioration of surface appearance.deterioration of surface appearance.
DEPARTMENT OF CHEMISTRY AND TECHNOLOGY OF POLYMERSDEPARTMENT OF CHEMISTRY AND TECHNOLOGY OF POLYMERSCRACOW UNIVERSITY OF TECHNOLOGY CRACOW UNIVERSITY OF TECHNOLOGY
Structures of ammonium compounds used Structures of ammonium compounds used for MMT modificationfor MMT modification
N
CH3
CH3
CH3
ClR N
CH3
R2
CH3
ClR1
N
H2C
CH3
H2C
ClR
CH2OH
CH2OH
OH CH2 N
CH2
R
CH2
CH2
CH2
OH
OH
Cl
N
CH3
CH3
CH3
ClR
1R3M 2R2M
RM2Et RB2Et
RA3M, where R contains amide group
DEPARTMENT OF CHEMISTRY AND TECHNOLOGY OF POLYMERSDEPARTMENT OF CHEMISTRY AND TECHNOLOGY OF POLYMERSCRACOW UNIVERSITY OF TECHNOLOGY CRACOW UNIVERSITY OF TECHNOLOGY
Structure of organo-modified MMTStructure of organo-modified MMT (o- (o-MMT)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).
6,55
5,85,0
2 7 12 172 theta, degree
Inte
nsi
ty
Na+MMT
MMT-RA3M, 50% CEC
MMT-RA3M, 100% CEC
(i) changing the hydrophilic 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.
More effective in dispersing the polymer matrix were o-MMT More effective in dispersing the polymer matrix were o-MMT with higher interlayer distances since organic compound with higher interlayer distances since organic compound facilitates exfoliation byfacilitates exfoliation by
DEPARTMENT OF CHEMISTRY AND TECHNOLOGY OF POLYMERSDEPARTMENT OF CHEMISTRY AND TECHNOLOGY OF POLYMERSCRACOW UNIVERSITY OF TECHNOLOGY CRACOW UNIVERSITY OF TECHNOLOGY
Melt blending of MMT into POM matrixMelt blending of MMT into POM matrix
Previous research on thermoplastic polymers indicated Previous research on thermoplastic polymers indicated that the degree of exfoliation/intercalation of MMT is that the degree of exfoliation/intercalation of MMT is favoured byfavoured by
Longer time of mixing Longer time of mixing Higher speed of rotorsHigher speed of rotors Higher melt viscosity (higher molecular weight of Higher melt viscosity (higher molecular weight of
polymer)polymer)
Since POM is susceptible to thermomechanical Since POM is susceptible to thermomechanical degradation the optimization of processing degradation the optimization of processing parameters is required.parameters is required.
DEPARTMENT OF CHEMISTRY AND TECHNOLOGY OF POLYMERSDEPARTMENT OF CHEMISTRY AND TECHNOLOGY OF POLYMERSCRACOW UNIVERSITY OF TECHNOLOGY CRACOW UNIVERSITY OF TECHNOLOGY
Nanocomposite structure characterization
WAXD diffractograms ofWAXD diffractograms of: :
a- pristine MMT, a- pristine MMT,
b - organo-modified MMT (MMT-2M2R),b - organo-modified MMT (MMT-2M2R),
c - POM/MMT-2M2Rc - POM/MMT-2M2R nanocomposite nanocomposite..
5.5
6.355.2
2 4 6 8 10 12 142θ, degrees
inte
nsity
, a.
u.
c
b
a
2θ peak at ca. 5.5º 2θ peak at ca. 5.5º indicatindicateses the presence of the presence of unintercalated stacks of unintercalated stacks of organomodified MMT organomodified MMT layers. However, taking layers. However, taking into account the weak into account the weak intensity of these peaks, intensity of these peaks, partial exfoliation of partial exfoliation of montmorillonite can be montmorillonite can be considered. considered.
DEPARTMENT OF CHEMISTRY AND TECHNOLOGY OF POLYMERSDEPARTMENT OF CHEMISTRY AND TECHNOLOGY OF POLYMERSCRACOW UNIVERSITY OF TECHNOLOGY CRACOW UNIVERSITY OF TECHNOLOGY
Model of structure of POM/MMT Model of structure of POM/MMT nanocompositenanocomposite
DEPARTMENT OF CHEMISTRY AND TECHNOLOGY OF POLYMERSDEPARTMENT OF CHEMISTRY AND TECHNOLOGY OF POLYMERSCRACOW UNIVERSITY OF TECHNOLOGY CRACOW UNIVERSITY OF TECHNOLOGY
Structure of nanocmposites Structure of nanocmposites
SEM microphotographs – homogenic distribution of MMT SEM microphotographs – homogenic distribution of MMT stacks and layersstacks and layers
POM/MMT-2R2M.POM POM/Na+MMT
DEPARTMENT OF CHEMISTRY AND TECHNOLOGY OF POLYMERSDEPARTMENT OF CHEMISTRY AND TECHNOLOGY OF POLYMERSCRACOW UNIVERSITY OF TECHNOLOGY CRACOW UNIVERSITY OF TECHNOLOGY
Core-shell structure of nanocomposite Core-shell structure of nanocomposite injection mouldinginjection moulding
SEM microphotographsSEM microphotographs of criofractured injection of criofractured injection moulding samplemoulding sample
247 μm
DEPARTMENT OF CHEMISTRY AND TECHNOLOGY OF POLYMERSDEPARTMENT OF CHEMISTRY AND TECHNOLOGY OF POLYMERSCRACOW UNIVERSITY OF TECHNOLOGY CRACOW UNIVERSITY OF TECHNOLOGY
Influence of MMT on crystallization Influence of MMT on crystallization process of POMprocess of POM
SampleSample
Enthalpy of meltingEnthalpy of meltingHHmm
[J/g][J/g]
Crystallinity Crystallinity degreedegree
CC%%
[%][%]
Core Core regionregion
Shell Shell regionregion
Core Core regionregion
Shell Shell regionregion
POMPOM 135.1135.1 133.7133.7 41.441.4 41.041.0
POM/NaPOM/Na++MMTMMT(microcomposit(microcomposit
e)e)145.4145.4 136.8136.8 44.644.6 41.941.9
POM/MMT-2R2M POM/MMT-2R2M (nanocomposite(nanocomposite
))168.0168.0 137.6137.6 51.551.5 42.242.2
DEPARTMENT OF CHEMISTRY AND TECHNOLOGY OF POLYMERSDEPARTMENT OF CHEMISTRY AND TECHNOLOGY OF POLYMERSCRACOW UNIVERSITY OF TECHNOLOGY CRACOW UNIVERSITY OF TECHNOLOGY
POSS – polyhedral oligomeric POSS – polyhedral oligomeric silsesquioxanessilsesquioxanes
DEPARTMENT OF CHEMISTRY AND TECHNOLOGY OF POLYMERSDEPARTMENT OF CHEMISTRY AND TECHNOLOGY OF POLYMERSCRACOW UNIVERSITY OF TECHNOLOGY CRACOW UNIVERSITY OF TECHNOLOGY
POSS – polyhedral POSS – polyhedral oligomeric silsesquioxanessilsesquioxanes
Structures of POSS occurring most often: a – T6, b – T8, c – T10, d i e
– T12.
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
Cubane cage of POSS (RSiO1,5)8
DEPARTMENT OF CHEMISTRY AND TECHNOLOGY OF POLYMERSDEPARTMENT OF CHEMISTRY AND TECHNOLOGY OF POLYMERSCRACOW UNIVERSITY OF TECHNOLOGY CRACOW UNIVERSITY OF TECHNOLOGY
Polyhedral oligomeric silsesquioxanesPolyhedral oligomeric silsesquioxanesCharacteristic and properties of POSS
Si O Si
O
Si O Si
O
O
O
SiOSi
O
SiOSi
O
O
O
XR
R R
R
R
R
R
Unreactive organic (R) groups for solubilization and compatibilization
One or more reactive groups for grafting or polymerization
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: 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 POLYMERSDEPARTMENT OF CHEMISTRY AND TECHNOLOGY OF POLYMERSCRACOW UNIVERSITY OF TECHNOLOGY CRACOW UNIVERSITY OF TECHNOLOGY
Polymeric nanohybrid materialsPolymeric nanohybrid materialsDefinitionsDefinitions
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 compositeHybrid composite Hybrid polymerHybrid 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 POLYMERSDEPARTMENT OF CHEMISTRY AND TECHNOLOGY OF POLYMERSCRACOW UNIVERSITY OF TECHNOLOGY CRACOW UNIVERSITY OF TECHNOLOGY
Nanohybrid materialsNanohybrid materials POSS/PolymerPOSS/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 POLYMERSDEPARTMENT OF CHEMISTRY AND TECHNOLOGY OF POLYMERSCRACOW UNIVERSITY OF TECHNOLOGY CRACOW UNIVERSITY OF TECHNOLOGY
Synthesis of PU - POSSSynthesis of PU - POSS
I STEP: Synthesis of PU prepolymer:
• 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 POLYMERSDEPARTMENT OF CHEMISTRY AND TECHNOLOGY OF POLYMERSCRACOW UNIVERSITY OF TECHNOLOGY CRACOW UNIVERSITY OF TECHNOLOGY
MorphologyMorphologyPU-POSS
Lateral force AFM images for PU/POSS
WAXD diffractograms of PU/POSS polymers
DEPARTMENT OF CHEMISTRY AND TECHNOLOGY OF POLYMERSDEPARTMENT OF CHEMISTRY AND TECHNOLOGY OF POLYMERSCRACOW UNIVERSITY OF TECHNOLOGY CRACOW UNIVERSITY OF TECHNOLOGY
Thermal analysisThermal analysisPU-POSS
Normalized DSC thermograms recorded with polyurethane matrix and the hybrids
Normalized TSDC thermograms for PU and hybrid PU/POSS
Composite TGA mass loss plots for PU/POSS hybrid systems
DEPARTMENT OF CHEMISTRY AND TECHNOLOGY OF POLYMERSDEPARTMENT OF CHEMISTRY AND TECHNOLOGY OF POLYMERSCRACOW UNIVERSITY OF TECHNOLOGY CRACOW UNIVERSITY OF TECHNOLOGY
Thermal analysisThermal analysisPU-POSS
DEPARTMENT OF CHEMISTRY AND TECHNOLOGY OF POLYMERSDEPARTMENT OF CHEMISTRY AND TECHNOLOGY OF POLYMERSCRACOW UNIVERSITY OF TECHNOLOGY CRACOW UNIVERSITY OF TECHNOLOGY
ACRYLATE HYDROGELSACRYLATE HYDROGELS
DEPARTMENT OF CHEMISTRY AND TECHNOLOGY OF POLYMERSDEPARTMENT OF CHEMISTRY AND TECHNOLOGY OF POLYMERSCRACOW UNIVERSITY OF TECHNOLOGY CRACOW UNIVERSITY OF TECHNOLOGY
AcrylateAcrylate hydrogelshydrogels – – polymerpolymer matrix matrix
Hydrogels matrix have some different properties Hydrogels matrix have some different properties such as their capacity to allow controlled release, such as their capacity to allow controlled release, changing their swellability by ionic strength, pH , changing their swellability by ionic strength, pH , temperature, chemical activity to interact with temperature, chemical activity to interact with adsorbates and selectivity to some species (i.e., adsorbates and selectivity to some species (i.e., metal ions, proteins and enzymes)metal ions, proteins and enzymes)
Applications:Applications:medical applications, medical applications, including drug delivery including drug delivery systems, scaffold materials systems, scaffold materials to organize cells into to organize cells into a a three-dimensional three-dimensional architecture, tissue architecture, tissue replacements, wounds replacements, wounds dressings and immobilization dressings and immobilization of proteins, cells, of proteins, cells, agriculturalagricultural applicationsapplications
DEPARTMENT OF CHEMISTRY AND TECHNOLOGY OF POLYMERSDEPARTMENT OF CHEMISTRY AND TECHNOLOGY OF POLYMERSCRACOW UNIVERSITY OF TECHNOLOGY CRACOW UNIVERSITY OF TECHNOLOGY
Crosslinking reaction of acrylic acid Crosslinking reaction of acrylic acid with N,N`-methylenobisacryloamide with N,N`-methylenobisacryloamide
Swelling of hydrogels
DEPARTMENT OF CHEMISTRY AND TECHNOLOGY OF POLYMERSDEPARTMENT OF CHEMISTRY AND TECHNOLOGY OF POLYMERSCRACOW UNIVERSITY OF TECHNOLOGY CRACOW UNIVERSITY OF TECHNOLOGY
SEM microphotographs of swollen SEM microphotographs of swollen acrylic matrix acrylic matrix
DEPARTMENT OF CHEMISTRY AND TECHNOLOGY OF POLYMERSDEPARTMENT OF CHEMISTRY AND TECHNOLOGY OF POLYMERSCRACOW UNIVERSITY OF TECHNOLOGY CRACOW UNIVERSITY OF TECHNOLOGY
Available research infrastructure :Available research infrastructure :
• fully-equipped polymer processing laboratory (extrusion, fully-equipped polymer processing laboratory (extrusion, Brabender mixing, injection moulding, compression Brabender mixing, injection moulding, compression moulding, pressing, pelleting, grinding, etc),moulding, pressing, pelleting, grinding, etc),
• thermal analysis laboratory (TG, DSC, MT-DSC, DMA, thermal analysis laboratory (TG, DSC, MT-DSC, DMA, TG/DSC),TG/DSC),
• FTIR, FTIR microscopy, UV-Vis, NMR, AFM, GC/MS, GPC, FTIR, FTIR microscopy, UV-Vis, NMR, AFM, GC/MS, GPC, HPLC, HPLC,
• mechanical properties testing machines,mechanical properties testing machines,• LOI, thermovision camera, UL-94.LOI, thermovision camera, UL-94.
DEPARTMENT OF CHEMISTRY AND TECHNOLOGY OF POLYMERSDEPARTMENT OF CHEMISTRY AND TECHNOLOGY OF POLYMERSCRACOW UNIVERSITY OF TECHNOLOGY CRACOW UNIVERSITY OF TECHNOLOGY
Thank Thank yyou ou
ffor or your ayour attentionttention