Annexure B

Ph.D. Research Proposal

Physico-Chemical Studies on Degradation and

Stabilization of Polymer Membranes and Their
Nanocomposites

By

Mr. Omkar Singh Kushwaha, JRF

Research Guide

Dr. R. P. Singh

Polymer Science and Engineering Division

National Chemical Laboratory, Pune-411008

1) Objective and Scope of the present Study

Degradation of polymers is a very important phenomenon which affects the

performance of all plastic materials in daily life. Effects of degradation are discernible in the
reaction kettle, where a polymer is synthesized, in the extruder, where it is fabricated, during
its service –life when it gives its useful performance, and after its failure when it is either
recycled or discharged into the environment.

Knowledge of the degradation chemistry of polymers had led to development of more

efficient stabilizers for improving the product performance on one hand and development of
sensitizers to produce degradable plastics, to preserve the environment. Thus degradation of
polymers is like a double-edged sword: it has harmful as well as beneficial aspects. If
unchecked it can lead to safety hazards of fire and toxicity but if properly harnessed, it can be
used for producing new and better materials.

The time factors causing degradation of polymers are UV light and the heating effects
of solar radiation as well as the working environment. Additional relevant factors include
ozone, atmospheric contaminants and induced radiation. It is the impurities present in
commercial polymers that initiate degradation by photochemical and thermal reactions. The
main light absorbing species are carbonyls, metallic impurities, di-enes, tri-enes, hydro-
peroxides and oxygen-polymer charge transfer complexes.

Effect of degradation on polymers may be assessed from the changers in chemical

structure, changes on surface, loss in mechanical properties, embrittlement, reduction in
molecular weight due to chain scission or increase due to cross-linking, generation of free
radicals and impairment of transparency.

To improve all aspects of the stability of polymers, a fundamental understanding of

the degradation involved is essential. The photo-oxidative degradation has attracted
considerable interest for practical as well as fundamental reasons. Many studies on polymeric
films and their nanocomposites by ultraviolet and visible light, γ-rays and heat have received
extensive attention during the past decade. At molecular level the effect of irradiation on
polymers is chain scission resulting in the formation of free radicals which migrate along the
chain but the probability of radical combination is dependent on polymer morphology,
especially for crystalline and semi-crystalline polymers.
 Although photo-oxidative degradation of many polymeric films has been studied but
little attention has been paid to the degradation study of Polyelectrolyte membranes used in
fuel cells i.e. Nafion, Polybenzimidazole etc. and their composites.

Nanoscience and nanotechnology have emerged as frontier areas of research in view of the
exciting new science as well as its novel and diverse applications, in particular as catalysts,
magnetic materials, nanocomposites, nanodevices, chemical sensors, degradation of toxic
chemicals, or even as possible carriers of isotopes for medical applications [1]. Because of
the quantum effect and large surface to volume ratio, nanosize exhibits changes in their
mechanical, optical, chemical, electrical and magnetic properties that are dramatically
different as shown by the bulk materials. A part from this, size and shape of nanomaterials
are also key points in nanotechnology. Sometimes, a single nanomaterial cannot fulfill all the
property requirements, hence, we have to go for combining two materials (nanocomposite) to
get properties of both the materials that combines separate elements in order to obtain the
best properties of each component. Nanocomposites can dramatically improve certain
properties like, mechanical properties including strength, modulus, dimensional stability,
electrical conductivity, thermal stability, chemical resistance and surface appearance.

Proton exchange membrane fuel cells (PEMFCs) as clean and efficient power sources
are receiving increasing attention both for stationary and transportation applications [2-5].
The currently well-developed PEMFC technology is based on Polybenzimidazole and Nafion
membranes [6]. Nafion membranes are dependent on the presence of water to solvate the
protons from the sulfonic acid groups. Consequently, the operational cell temperature is
limited to below 100 ◦C [7]. These kinds of PEMFCs face two main limitations. Firstly, the
use of PFSA polymer membranes requires proper humidification to keep the ionic conduction
high enough for PEMFC applications, which complicate the design of the fuel cell system;
secondly, CO impurities seriously poison the Pt/C catalysts below 100 ◦C [8]. The
H3PO4/PBI HT-PEMFC operates at temperatures around 150–200 ◦C without humidification
which not only resolves the above mentioned problems but also provides other advantages,
such as enhanced reaction kinetics at the elevated cell temperature for both electrodes [6,9],
elimination of cathode flooding and ease of heat management [10,11]. The life of a PEMFC
is a major concern for commercialization. The life tests of mid-low temperature PEMFCs
have been widely investigated [12-14]. However, the detailed reasons for the performance
degradation of H3PO4/PBI HT-PEMFC have not been reported. After the test, the catalysts,
the PBI membrane and the MEA structure were analyzed by TEM, SEM and EDS. On the
basis of the preliminary results, the deterioration of the MEA performance was determined.

One of the most significant challenge for PBI membranes and their fuel cells is to
improve lifetime. 40,000 h of operation for stationary uses and 5000 h of operation for
automobile uses are commonly required with limited performance decay, less than 10%.

The reasons for failure of a PEMFC are numerous and not fully understood. For PBI cells, the
most likely mechanisms include

1) Degradation of the polymer membranes due to the attack by *OH and *OOH.

2) Leaching of the doped acid from the membrane electrolyte

3) Loss of catalyst activities due to the catalyst sintering, catalyst dissolution and the carbon
support corrosion.
2) A survey of work done in the research area and the need for more
research

The thermal stability of several aromatic polymers and their sulfonated derivatives
were evaluated under inert and saturated vapor conditions. Most of the sulfonated derivatives
were much less stable than their unsulfonated analogues under inert conditions, but only
slightly less stable in saturated water vapor. Decomposition analysis done in one atmosphere
superheated steam was thermally driven and resulted in the loss of sulfonic acid groups and
in fragmentation of the polymer chain. Analysis of sulfonated polymer residues following
saturated vapor decomposition confirmed that aromatic desulfonation was occurring under
these conditions. Attempts are going for making high temperature PEMFC membrane to
outperform Nafion. The need to design novel PEMs is to obtain a molecular-level
understanding of chemistry, morphology, transport and degradation in existing membranes,
such as Nafion, under various operating conditions [15].

There were many composite membranes prepared and tested to improve the cell
performance but little work is done to understand the degradation mechanism of these
membranes. Many workers have studied decrease in the cell performance due to prolong use
but they are still not able to give any mechanism. Regardless of this degradation studies of
many other polymeric membranes have been done in detail and are applicable for the
degradation and stabilization of the polymers.

In addition to the proton conductivity, fuel cell operation constitutes

very demanding requirements for materials. The environment inside the membrane
is aqueous, strongly acidic and holds a relatively high temperature.
Furthermore, peroxides are formed as side products on the catalysts. This is
fatal for all kinds of aliphatic hydrocarbons, due to oxidative attack and
chain-cutting. For example, sulfonated polystyrene membrane fuel cells first
had very short lifetimes. Instead, fluorination makes aliphatic carbon chains
very stable to oxidative degradation [16], which is the reason for the
development of different fluorinated polymers for FCs. Nafion is
unquestionably the most famous example of polytetrafluroethylene backbone PEM
materials. Another class of sufficiently stable polymers is the aromatic
polymers with an aromatic backbone [16] for example, poly (arylene ether) and
Polybenzimidazole [17] more exotic are the silicates and phosphazenes.

Besides chemical stability, materials must also be mechanically strong. In

gels, the strength is dependent on the cross-linking, which can be either
chemical or physical. Prevalently, these polymers are physically cross-linked
by non-sulfonated regions in their chains, which are usually more hydrophobic
and cause the formation of hydrophobic clusters. Thus, fine tuning of the
molecular structures (number and distribution of sulfonic acid groups as well
as chemical cross-linkers) is needed to achieve the best combination of proton
transport, fuel impermeability and mechanical strength.
 Proposed Schemes

1. Study of Thermal degradation of polymers and their nanocomposites under oxidative

conditions in different mass ratios.

PBI-2 Comparative Study

&
PBI-4 Characterization by

PBI-5 Thermal exposure, O2 FT-IR

100 h, 200 h, 300 h, 350 h, 500 h XPS
PBI-6 XRD
SEM
PBI-7 UV
GPC
PBI-10
Mechanical Testing
DMPBI-ISO Comparative Study
&
TMPBI-I-I-25 Characterization by

DMPBI-BuI FT-IR
Thermal exposure, O2 XPS
TMPBI-BuI 100 h, 200 h, 300 h, 350 h, 500 h XRD
SEM
DBZABPBI UV
GPC
[Link].I
Mechanical Testing

Comparative Study
PBI- I &
Characterization by
PBI-B
Thermal exposure, O2 FT-IR
PBI-Py 100 h, 200 h, 300 h, 350 h, 500 h XPS
XRD
PBI-HFA SEM
UV
GPC

Mechanical Testing

Long hours of exposure to high temperatures under oxidative conditions followed by

the characterization at regular intervals of time by IR, XRD and GPC of the samples,
followed by mechanical testing
2. Study of Photo degradation of polymers and their nanocomposites under oxidative
environment using ultraviolet and gamma irradiations.

DMPBI-ISO Comparative Study

&
TMPBI.I.I-25 Characterization by

DMPBI-BuI Photo-irradiation, O2 FT-IR

100 h, 200 h, 300 h, 400 h, 500 h XPS
TMPBI-BuI XRD
SEM
DBZABPBI UV
GPC
[Link].I
Mechanical Testing

Comparative Study
PBI- I &
Characterization by
PBI-B
FT-IR
Photo-irradiation, O2
PBI-Py XPS
100 h, 200 h, 300 h, 400 h, 500 h
XRD
PBI-HFA SEM
UV
GPC

Mechanical Testing
 PBI-2 Comparative Study
&
PBI-4 Characterization by

PBI-5 FT-IR
Photo-irradiation, O2 XPS
PBI-6 100 h, 200 h, 300 h, 400 h, 500 h XRD
SEM
PBI-7 UV
GPC
PBI-10
Mechanical Testing

Exposure to UV light under oxidizing conditions and its characterization using IR,
XRD and GPC, followed by mechanical testing.
3. Study of Chemical degradation of polymers and their nanocomposites under
oxidative environment using acidic environment of a) HNO3 b) HCl c) H3PO3 d)
H2SO4

PBI-2 Comparative Study

&
PBI-4 Characterization by

PBI-5 FT-IR
ACIDIC ENVIRONMENT, O2 XPS
PBI-6 100 h, 200 h, 300 h, 350 h XRD
SEM
PBI-7 UV
GPC
PBI-10
Mechanical Testing

Comparative Study
PBI- I &
Characterization by
PBI-B
ACIDIC ENVIRONMENT, O2 FT-IR
PBI-Py 100 h, 200 h, 300 h, 350 h XPS
XRD
PBI-HFA SEM
UV
GPC

Mechanical Testing
DMPBI-ISO Comparative Study
&
TMPBI-I-I-25 Characterization by

DMPBI-BuI FT-IR
ACIDIC ENVIRONMENT, O2 XPS
TMPBI-BuI 100 h, 200 h, 300 h, 350 h XRD
SEM
DBZABPBI UV
GPC
[Link].I
Mechanical Testing

Exposure of samples to acid vapours for long hours followed by characterization at

regular interval by using IR, XRD and GPC and mechanical testing.
4. Effect of nanoparticles on polymer degradation and stabilization and on gas
permeability.

Characterization
by

Polymer FT-IR
Polymer Dispersion of Nanocomposites XPS
Nanomaterials XRD
SEM
UV
GPC
Thermal exposure, O2 Mechanical
100 h, 200 h, 300 h, 350 h, 500 h
Testing
Photo-irradiation, O2
100 h, 200 h, 300 h, 400 h, 500 h

ACIDIC ENVIRONMENT, O2
100 h, 200 h, 300 h, 350 h

Characterization

Preparation of polymer nanocomposite material and exposure to UV, gamma

radiations and thermal environments followed by characterization

5. To design, synthesize and property evaluation of specific polymeric stabilizers,

polymer bound stabilizers and pigments. It includes Stabilizers (additives ≤ 0.6%),
Metal Nanoparticles, Nano-modified additives and Modified CNT’s
Study of effect of stabilizers on polymer degradation using accelerated degradation
conditions will be followed by characterization.
6. Characterization of synthesized polymeric and degraded films and their
nanocomposites.
a) UV-VIS spectroscopy
b) Infra-red Spectroscopy
c) Nuclear Magnetic Resonance Spectroscopy
d) Mass Spectroscopy
e) X-ray Photoelectron Spectroscopy
f) Scanning Electron Spectroscopy
g) Transmission Electron Spectroscopy
h) Gel Permeation Chromatography
i) Rheometeric analysis
j) Gas Permeability Tester
k) Thermogravimetric Analyzer
l) Differential Scanning Calorimeter

7. External factors affecting polymeric films, leading to degradation

a) UV Light
b) Environmental temperature
c) Ozone in lower atmosphere
d) Contaminants of atmosphere
e) Free radicals

8. Internal factors affecting polymeric films stability

a) Functional groups i.e. carbonyls etc.

b) Metallic impurities
c) Di-enes and tri-enes
d) Hydroxy peroxides
e) Charge transfer complexes

9. Degradation of polymer leads to following changes in polymer

a) Chemical structure
b) Surface morphology
c) Mechanical properties i.e. tensile etc.
d) Embrittlement
e) Molecular weight (due to chain scission)
f) Free radical generation
g) Transparency
h) Crystallinity
References:

1) Kharisov, B. I; Nanotechnology. 2008, 2, 3.

2) H.A. Gasteiger, S.S. Kocha, B. Sompalli, F.T. Wagner, Appl. Catal. B: Environ. 56
(2005) 9.

3) S.D. Knights, K.M. Colbow, J. St-Pierre, [Link], J. Power Sources 127

(2004) 127.

4) C. Pan, R.H. He, Q.F. Li, J.O. Jensen, N.J. Bjerrum, H.A. Hjulmand, A.B. Jensen, J.
Power Sources 145 (2005) 392.

5) X. Cheng, L. Chen, C. Peng, Z.W. Chen, Y. Zhang, Q.B. Fan, J. Electrochem. Soc.
151 (2004) A48.

6) S. Gottesfeld, T.A. Zawodzinski, in: R.C. Alkire, H. Gerischer, D.M. Kolb, C.W.
Tobias (Eds.), Advances in Electrochemical Science and Engineering, vol. 5, Wiley–
VCH, Weinheim, 1997, p. 195.

7) Q.F. Li, H.A. Hjuler, N.J. Bjerrum, Electrochim. Acta 45 (2000) 4219.

8) R.F. Savinell, E. Yeager, D. Trysk, U. Landau, J. Wainright, D. Weng, K. Lux, M.

Litt, C. Rogers, J. Electrochem. Soc. 136 (1989) 41C.

9) S.K. Zecevic, J.S. Wainright, M.H. Litt, S.L. Gojkovic, R.F. Savinell, J. Electrochem.
Soc. 144 (1997) 2973.

10) Q.F. Li, R.H. He, J.O. Jensen, N.J. Bjerrum, Chem. Mater. 15 (2003) 4896.

11) Y.L. Ma, [Link], M.H. Litt, R.F. Savinell, J. Electrochem. Soc. 151 (2004) A8.

12) D.P. Wilkinson, J. St-Pierre, Durability, in: W. Vielstich, H. Gasteiger, A. Lamm

(Eds.), Handbook of Fuel Cells: Fundamentals, Technology and Applications, vol. 3,
Wiley, 2003, Chapter 47.

13) J.R. Yu, T. Matsuura, Y. Yoshikawa, M.N. Islam, M. Hori, Phys. Chem. Chem. Phys.
7 (2005) 373.
 14) L.H. jiang, G.Q. Sun, [Link], [Link], Q. Xin, Z.H. Zhou, B. Zhou
Electrochem. Commun. 7 (2005) 661.

15) Ram devanathan; Energy and environment 2008, 1, 101-119

16) B. Smitha, S. Sridher, A.A. Khan, J. Memb. Sci., 2005, 259, 10
17) J. A. Asensio, S. Borrós, P. Gómez-Romero, J. Polym. Sci. A., 2002, 40, 3703

Mr. Omkar Singh Kushwaha Dr. R. P. Singh

(Research Student) (Research Guide)