new polymeric materials - challenges and perspectives · jubilee scientific conference “practical...

JUBILEE SCIENTIFIC CONFERENCE “PRACTICAL APPLICATIONS OF INNOVATIVE SOLUTIONS RESULTING FROM SCIENTIFIC RESEARCH”

New Polymeric Materials -

Challenges and Perspectives

Krzysztof Pielichowski Cracow University of Technology

Department of Chemistry and Technology of Polymers

“PRACTICAL APPLICATIONS OF INNOVATIVE SOLUTIONS RESULTING FROM SCIENTIFIC RESEARCH”

INTRODUCTION

MATERIALS:

CERAMICS

METALS

POLYMERS: 1950 – 1,5 mln t → 2014 – 260 mln t

High growth potential, e.g. BRIC countries

Novel polymeric materials: copolymers, blends,

(nano)composites, hybrids, …


INTRODUCTION

• POLYMER – a compound of high molecular weight

consisting of repeating units called „mers”

(„macromolecule” – Hermann Staudinger, (1920). "Über

Polymerisation". Ber. Deut. Chem. Ges. 53 (6): 1073.)

• PLASTICS – polymer + additives (eg. fillers, stabilizers)

=> composites, blends

e.g. poly(vinyl chloride)


POLYMERS CLASSIFICATION

POLYMERS

Natural Synthetic

Elastomers

• proteins, eg. fibroin

(silk), colagen

• polysaccharides, eg.

cellulose, starch

• natural resins (Gutta-

percha, amber)

• natural rubber,

• polyurethanes

----------------------------

• amorphous

• (semi)crystalline

• thermoplastics– PE, PS

• thermosets:

thermoset (e.g. phenol-

formaldehyde resins),

chemically cured resins

(e.g. epoxies)


THERMOPLASTICS THERMOSETS

CAN be reshaped – weak interactions bonds

between linear chains

CAN’T be reshaped -

crosslinked

processable (e.g. extrusion, injection

molding)

curing (heat, pressure,

catalyst)

e.g. food containers, lighting panels, pipes,

garden hoses, plastic bags, …

e.g. glues, varnishes, in

electronic components such

as circuit boards, …

easy to recycle hard to recycle


HISTORICAL BACKGROUND • 1868 – nitrocellulose, Alfred Nobel

• 1850-1875 – first plastic on industrial scale – celluloid (USA)

• 1909 – phenol-formaldehyde resin, Baekeland, USA

• 1915 – synthetic rubber, Germany

• 1920-30: H. Staudinger, macromolecule definition (1953 Noble prize, discoveries in the field of

macromolecular chemistry)

• 1927 – poly(vinyl chloride)

• 1933-35: PE (Imperiacl Chemical Industries), PS (UK)

• 1936 – Nylon® (PA) W.T. Carothers,

• 1936 – poly(methyl methacrylate)

• 1939-50: patents for other polymers (1950 – Badische Anilin & Soda-Fabrik PS; 1950-56: Ziegler-Natta

catalysts 1st class.; 1963 – O. Wichterle, patent for hydrogel HEMA, contact lenses;

• 1991 – first polymer nanocomposite in industrial scale (PA6/MMT, Toyota)

• 1995 – ATRP (K. Matyjaszewski, M. Sawamoto)

• 1998 – RAFT (CSIRO, Australia)

• 2000 – H. Heeger, A. McDiarmid, H. Shirakawa, Nobel prize for the discovery and development of

conductive polymers

• … (bio, nano, …)

[http://www.polymerexpert.fr/en/presentation/histoire-des-polymeres/]


BIOCOMPOSITES / BIOPOLYMERS

Fig. Trends in the development of biocomposites/biopolymers [Product overview and

market projection of emerging bio-based plastics PRO-BIP 2009, Final report]


OUR RESEARCH DIRECTIONS

• Phase change materials

• Hydrogels

• Organic-inorganic hybrid materials


Phase change materials (PCM)

http://www.textileworld.com/Issues/2004/March/Features/Phase_Change_Materials, http://www.rgees.com/technology.php

http://www.textileworld.com/Issues/2004/March/Features/Phase_Change_Materials


Phase change materials (PCM)

Progress in Materials Science 65 (2014) 67–123

Fig. The number of articles dedicated to PCMs for thermal energy storage for the period of 1994–2013. Source: Science Direct, ‘‘phase change materials’’ and ‘‘thermal energy storage’’.


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PEO Degree of

crystallinity [%]

PEO 400 59,4

PEO 1000 77,4

PEO 3400 84,7

PEO 10000 90,3

PEO 20000 81,4

PEO 35000 84,8

Table. Degree of crystallinity vs average molar mass of PEO

Fig. DSC curves for melting and crystallization process of PEO

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PEG-based PCMs disadvantages - solid-liquid phase transition and in consequence leakage, poor thermal conductivity

Shape stabilization with cellulose and polysaccharides

Incorporation of carbon nanomaterials (fullerenes, carbon nanotubes, graphene)


12

12

Tab . Temperatures and heat of phase transition for melting and crystallization

process for PEO/cellulose and PEO/cellulose derivatives

PEO/cellulose and its derivative systems


PEO/starch PCMs

Hydrogen interactions in PEO/starch blends: (a) EO/amylopectine, (b) PEO/amylose.


HYDROGELS - OVERVIEW


HYDROGELS – TISSUE ENGINEERING

“PRACTICAL APPLICATIONS OF INNOVATIVE SOLUTIONS RESULTING FROM SCIENTIFIC RESEARCH” 16

• PEG hydrogels – appl. in biotechnology, tissue engineering, drug delivery

systems – hydrophilic character, porous structure, biocompatibility, however

low mechanical stability

• nanoparticles – reinforcement of hydrogel matrix (silicates, e.g. Laponite)

• hydrogels PEG/Laponite – gel when low concentration of Laponite, high

concentration of Laponite – crosslinked materials

Fig. Nanoparticles addition lead to decrease of

pores size; hydrogels are characterized by highly

porous structure.

Fig. Nanoparticles are physically and covalently bonded

to PEG – formation of mechanically strong and flexible

material

HYDROGEL PEG/LAPONITE

[K. Shikinaka, K. Aizawa, Y. Murakami, Y. Osada, M. Tokita, J. Watanabe, K. Shigehara, J. Coll. Interf. Sci. 369 (2012) 470–476.]


HYDROGELS – DYNAMIC HYBRIDS

Fig. Schematics and optical

microscope images of pH-

responsive actuation using

electrochemically-generated

pH gradients [L.D. Zarzar, PhD

dissertation, Dynamic Hybrid

Materials: Hydrogel Actuators and

Catalytic Microsystems, HARVARD

Univ. 2013].


Fig. SEM microphotographs of swollen acrylic matrix

Przemysł Chemiczny, 2011, 90/7, 1000-1003


Fig. The dependence of swelling ratio upon the concentration of fertilizers in dried hydrogels

Fig. The dependence of ammonium ions release ratio upon the time

Fig. Synthesis of PAA hydrogel and synthesis of PAA/fertilizer hydrogels.

Polish J. of Environ. Stud. 2009, 18, 475-479


HYBRID MATERIALS

• goal : create

materials with

specific

combinations of

properties by

combining different

molecular building

blocks in various

ratios and by

controlling their

mutual arrangement

Fig. Inorganic-Organic Hybrid Materials


HYBRID MATERIALS

Inorganic Building Blocks

Mechanical, optical,

electrical,

magnetical properties

Connecting Blocks Reduction of the crosslinking density,

coupling sites between inorganic /

organic components

Organic Building Blocks

Functional groups,

crosslinking,

A polymerizability

Flexibility, elasticity, processability

polyhedral cages

[S.-T. Zheng, T. Wu, C. Chou, A. Fuhr, P. Feng, X. Bu, J. Am. Chem. Soc., 134, 4517-4520, 2012].


A few examples of today’s applications of hybrid materials, arising from the game of invention . Starting with the ancient

creative imaginings of a hybrid being (part unicorn, part fish; inspired by art on the ceiling of the Church of St. Martin of Zillis) and

ending with speculation about the future. Intermediate examples of hybrid materials include: (1) a fresco containing Maya blue,

(2) hearing aids, (3) solar modules, (4) tennis balls, (5) flexible waveguide, (6) portable O2 sensor, (7) super gas barrier nylon,

(8) dental fillings, (9) antistatic coating, (10) rubbery monoliths, (11) tires, (12) herbicides, (13) colored glass coatings,

(14) electro-optical multichip module, (15) biocatalyst lipase on silica, (16) persistent luminescent nanoparticles for small animal

imaging [G.L. Drisko, C. Sanchez, Eur. J. Inorg. Chem. 2012, 5097–5105].


POLYMERIC NANOHYBRIDS

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.

Fig. Schematic representation of different materials dimensions


HYBRID MATERIALS - POSS

Network Modifiers (non-reactive organic groups)

Precursors with Functional Organic Groups

3-dimensional structure

One or more reactive

groups (grafting,

polymerization)

Thermally and chemically

robust hybrid (organic-

inorganic) framework

Nanoscale

Si-Si distance = 0.5 nm

R-R distance = 1.5 nm

Unreactive organic ( R )

groups (solubilization and

compatibilization)

[G. Kickelbick, Prog. Polym. Sci., 28,

83-114, 2003]


NANOHYBRIDS POLYMER-POSS

Organic-inorganic nanohybrids materials – incorporation of inorganic groups

into polymer macrochains, eg. polyhedral oligomeric silsesquioxanePOSS

PROPERTIES:

increase the temperature range,

increase of oxygen stability,

increase of UV stability,

improvement of surface ,

improved mechanical properties,

reduced flammability,

reduced heat released during combustion,

higher density

Fig. POSS-polymer system

Adv. Polym. Sci. 2006, 201, 225-296


POSS can be incorporated into a polymer chain as (i) a side branching of the

main macrochain, (ii) a network node or (iii) as a part of the polymer backbone

chain. POSS-polymer hybrids are an interesting class of materials, but

microphase separation effects may decrease possible advantages of nanoscale

incorporation.

Chemical ways of POSS incorporation into the polymer structure:

a. side branching,

b. network node,

c. part of backbone chain.

A physical way of POSS incorporation into the polymer matrix:

Through melt processing of polymers, e.g. by extrusion

POSS as a nanofiller


Synthesis of PU/POSS

POSS as a side branching I STEP: Synthesis of PU prepolymer:

• diphenylmethane-4,4’-diisocyanate

(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


Morphology PU/POSS

POSS as a side branching

Lateral force AFM images for PU/POSS

V.N. Bliznyuk et al. Polymer, 49, 2008, 2298

For the sample with the smaller filler content, the POSS molecules

aggregate to nanometer size longitudinal crystallites (about 60–70 nm

in length), which form spherulites of several microns average sizes. At

higher filler content (PU10), POSS forms more regular crystallites of

about 120 nm sizes. These observations indicate that PHIPOSS

shows strong tendency to form crystallites in PU matrix, however of

different types, i.e. extended structures for PU04 and more regular,

smaller structures for the higher POSS content (PU10).

Polymer, 2010, 51 (3), 709-718


POSS impact on the thermal properties of polymers:

increased melting temperature,

shift the Tonset towards higher temperatures,

reduced heat emission increased thermal stability of hybrids.

Thermal stability


Py-GC/MS studies

Py-GC/MS thermograms for the non-oxidative thermal degradation of the 0-10% DSIPOSS/PU hybrid

elastomers. Note that in the unmodified elastomer a primary de-polymerization event (a) with an onset of

~250°C that is followed by a second high temperature process (b) e attributed to the degradation of the

monomer units. It is evident from these data that the inclusion of DSIPOSS both shifts (a) & (b) to higher

temperatures and decreases the overall yield of volatile degradation products.

Polymer Degradation and Stability, 2010, 95, 1099-1105


Research team/collaboration: - Dr. Bartłomiej Janowski (CUT) - Małgorzata Jancia (CUT) - Prof. Polycarpos Pissis (NTU Athens) - Dr. Konstantinos Raftopoulos (NTU Athens, CUT, TU

Muenchen) - Dr. Bożena Tyliszczak (CUT) - Dr. Katarzyna Bialik-Wąs (CUT) - Dr. Kinga Pielichowska (AGH-UST) - Dr. James Lewicki (LLNL, Livermore) - Dr. Joanna Pagacz (CUT) - Dr. Edyta Hebda (CUT) - Jan Ozimek (CUT)


THANK YOU FOR YOUR ATTENTION

JUBILEE SCIENTIFIC CONFERENCE “PRACTICAL APPLICATIONS OF INNOVATIVE SOLUTIONS RESULTING FROM SCIENTIFIC RESEARCH”

New Polymeric Materials -

Challenges and Perspectives

Krzysztof Pielichowski Cracow University of Technology

Department of Chemistry and Technology of Polymers

new polymeric materials - challenges and perspectives · jubilee scientific conference “practical...

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