REPORT ON

Summer Internship 2011-12

AT

UNIVERSITY OF HOUSTON, HOUSTON, TEXAS, USA

Submitted by PALLAV SURABATHUNI (0801ME33)

Department Of Mechanical Engineering INDIAN INSTITUTE OF TECHNOLOGY PATNA August 2011

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Acknowledgements
Before I thank anybody I would like to express my deepest regards and thanks to Prof.Haleh Ardebili who was a hugely appreciative and tolerant mentor during the entire period of my research. It was her faith that motivated me more than anything else. This work was not a solitary work of literature but is a result of a lot of hard-work and support from the dedicated research group of Dr.Ardebili. I would specially like to thank Eric Wood, Carolina Andrade and Chaitanya Patel, undergraduate researchers in Dr.Ardebilis lab, Stephen Pair and Veronica Richter, visiting students from Texas A&M and Trinity College respectively and Qin, who would be continuing my work at U of H. Last but not the least I would like to thank Prof.Anil Kumar Bhowmick and Prof.Ramanan Krishnamoorti for giving me the opportunity to work with such a great team.

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CONTENTS
1. PEM Fuels Cells---------------------------------------------6 a. Introduction-------------------------------------------6 b. Working------------------------------------------------7 c. Properties of an Ideal PEM---------------------------8 2. Literature Review of Possible Materials which can be employed as Membrane in a PEM Fuel Cell----------------10 a. Nafion-------------------------------------------------10 i. Properties---------------------------------------10 ii. Applications-------------------------------------11 iii. Functional Aspects------------------------------12 iv. Morphology--------------------------------------14 3. Other materials researched as alternatives to Nafion17 a. PVDF g styrene------------------------------------18 b. Aromatic Polymers-----------------------------------19 c. Complexes of Basic Polymers------------------------20 d. Other Polymers--------------------------------------20 4. Main Research Focus Fillers to improve performance on Nafion membranes-----------------------------------------20 a. Silica--------------------------------------------------24 b. Titanium Dioxide-------------------------------------24 c. Metal Oxides-----------------------------------------24 d. Layered Phosphates----------------------------------25 e. Zeolites-----------------------------------------------26 5. Experimental Focus----------------------------------------26
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6. Experimental Methods------------------------------------27 a. Materials---------------------------------------------27 b. Fabrication of Membranes--------------------------27 c. SEM characterization-------------------------------27 d. Water Uptake Measurements-----------------------33 e. Results------------------------------------------------33 7. References-------------------------------------------------34

List of Figures
FIGURE 1 SCHEMATIC DIAGRAM OF A PEM FUEL CELL .................................... - 7 FIGURE 2 NAFION STRUCTURE ........................................................................ - 12 FIGURE 3 NAFION - A MORE GENERAL FORMULA ............................................ - 12 FIGURE 4 CLUSTER NETWORK MODEL OF NAFION......................................... - 14 FIGURE 5 WATER CHANNEL MODEL OF NAFION ............................................ - 15 FIGURE 6 YEAGER 3 PHASE MODEL OF NAFION .............................................. - 16 FIGURE 7 STRUCTURE OF PVDF ....................................................................... - 18 FIGURE 8 DIAS ANALYTICS POLYMER............................................................. - 18 FIGURE 9 SULPHONATION OF PEEK ................................................................ - 19 FIGURE 10 SULFONATION OF PPBP ................................................................. - 19 FIGURE 11 TYPES OF PBI .................................................................................. - 19 FIGURE 12 SEM IMAGES OF UNMODIFIED NAFION ..................................... - 22 FIGURE 13 SEM IMAGES OF SILICON RECAST NAFION ............................... - 22 FIGURE 14 CURRENT CHARACTERISTICS AT HIGH TEMPERATURES OF 130 DEGREE
CELSIUS CLEARLY SHOW THE ADVANTAGE OF USING SILICA FILLERS .... - 22

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FIGURE 15 THE GRAPHS SHOW CONSISTENT IMPROVEMENT OF COMPOSITE

CHARACTERISTICS OVER THAT OF PURE

NAFION ..................................... - 23 -

FIGURE 16 CURRENT CHARACTERISTICS OF ALUMINA RECAST MEMBRANES - 24 FIGURE 17 SEM MICROGRAPH OF CROSS SECTION OF NAFION ZEOLITE
COMPOSITE ................................................................................................. - 25

FIGURE 18 SEM IMAGE OF HYDROXYAPATITE SHOWING THE POROUS

STRUCTURE.................................................................................................. - 27

FIGURE 19 SEM IMAGE OF MNO2 NANORODS (NANOAMOR) .................... - 27 FIGURE 20 PURE NAFION - THE FOLDS ARE DUE TO ACCELERATED HEATING OF
SOLUTION ................................................................................................... - 29

FIGURE 21 NAFION + HAP THE SAME FOLDS ARE OBSERVED AT A MUCH LARGER
SCALE .......................................................................................................... - 29

FIGURE 22 NAFION + HAP SHOWING AGGREGATE DISPERSION OF HAP AS A

LARGE QUANTITY OF

HAP WAS USED IN PREPARING SOLUTION\.......... - 30 -

FIGURE 23 A MORE CLOSER LOOK AT THE ABOVE IMAGE ............................... - 30 FIGURE 24 A BETTER NAFION MEMBRANE PREPARED THE SECOND TIME WITH
SLOWER HEATING NOW SHOWS LESS PRONOUNCED FOLDS ..................... - 31

FIGURE 25 SIDE VIEW OF THE PURE NAFION SHOWS UNIFORM DISTRIBUTION

OF

SOLUTION PARTICLES ........................................................................... - 31 -

FIGURE 26 A BETTER DISPERSION OF HAP PARTICLES DUE TO LESS (5%)

AMOUNT USED THE SECOND TIME ............................................................. - 32

FIGURE 27 SIDE VIEW OF NAFION + HAP SHOWS A STRUCTURE WITH A LOT OF

CHANNELS AS COMPARED TO PURE

NAFION ............................................. - 32 -

FIGURE 28 WATER UPTAKE FOR PURE NAFION ............................................. - 33 FIGURE 29 WATER UPTAKE FOR NAFION HAP COMPOSITE ......................... - 33 -

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PEM Fuel Cells

The polymer exchange membrane fuel cell (PEMFC) is one of the most promising fuel cell technologies. It is probable that you find these guys providing power to the largest of things like plants and cars to the smallest such as watches and mobile phones. The PEMFC uses one of the simplest reactions of any fuel cell. There are four basic elements of a PEMFC are:

The anode, the negative post of the fuel cell, has several jobs. It conducts the electrons that are freed from the hydrogen molecules so that they can be used in an external circuit. It has channels etched into it that disperse the hydrogen gas equally over the surface of the catalyst. The cathode, the positive post of the fuel cell, has channels etched into it that distribute the oxygen to the surface of the catalyst. It also conducts the electrons back from the external circuit to the catalyst, where they can recombine with the hydrogen ions and oxygen to form water. The electrolyte is the proton exchange membrane. This specially treated material, which looks something like ordinary kitchen plastic wrap, only conducts positively charged ions. The membrane blocks electrons. For a PEMFC, the membrane must be hydrated in order to function and remain stable. The catalyst is a special material that facilitates the reaction of oxygen and hydrogen. It is usually made of platinum nanoparticles very thinly coated onto carbon paper or cloth. The catalyst is rough and porous so that the maximum surface area of the platinum can be exposed to the hydrogen or oxygen. The platinum-coated side of the catalyst faces the PEM.

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Figure 1 Schematic Diagram of a PEM Fuel Cell

Working:
The pressurized hydrogen gas (H2) enters the fuel cell on the anode side. This gas is forced through the catalyst by the pressure. When an H2 molecule comes in contact with the platinum on the catalyst, it splits into two H+ ions and two electrons (e-). The electrons are conducted through the anode, where they make their way through the external circuit (doing useful work such as turning a motor) and return to the cathode side of the fuel cell.
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Meanwhile, on the cathode side of the fuel cell, oxygen gas (O2) is being forced through the catalyst, where it forms two oxygen atoms. Each of these atoms has a strong negative charge. This negative charge attracts the two H+ ions through the membrane, where they combine with an oxygen atom and two of the electrons from the external circuit to form a water molecule (H2O). This reaction in a single fuel cell produces only about 0.7 volts. To get this voltage up to a reasonable level, many separate fuel cells must be combined to form a fuel-cell stack. Bipolar plates are used to connect one fuel cell to another and are subjected to both oxidizing and reducing conditions and potentials. A big issue with bipolar plates is stability. Metallic bipolar plates can corrode, and the byproducts of corrosion (iron and chromium ions) can decrease the effectiveness of fuel cell membranes and electrodes. Low-temperature fuel cells use lightweight metals, graphite and carbon/thermoset composites (thermoset is a kind of plastic that remains rigid even when subjected to high temperatures) as bipolar plate material.

PROPERTIES OF AN IDEAL PEM

As seen from the above discussion we can see the importance of the Proton Exchange Membrane in the whole operation of the fuel cell. In many cases this is the limiting element and the major determinant of the efficiency of the fuel cell as a whole. Due to this the selection of a suitable Proton Exchange Membrane assumes greater importance. Some of the many points to be kept in mind for fabricating novel polymer membranes are as listed below: Good ion conductivity, but should be an insulator This is of paramount importance as good ionic conductivity increases the output and indirectly the efficiency of the cell but it should also at the same time not allow electrons to cross over to the other side as this may cause a catastrophic short circuiting of the cell.
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 Low permeability to fuel and oxidant The membrane of a fuel cell should also be impervious to the flow of fuel and oxidant through it as this may cause a reaction midway which will again lead to an effective short circuiting of the cell. Low water transport through diffusion and electro-osmosis Though good water transfer is essential for the proper functioning of a fuel cell there should be minimum back transfer of moisture due to diffusion and osmosis as it would induce an electro-osmotic drag on the flow of the conductive protons. Chemical, thermal and hydrolytic stability The membrane should be chemically stable against the attack by the fuel and oxidant; it should withstand the high operating temperature prevalent during the normal operation of the fuel cell. Ability to form thin films and ease of fabrication into MEAs (Membrane Electrode Assemblies) The films should be sufficiently stable mechanically so as to be able to form thin films which can be fabricated into Membrane Electrode Assemblies to form fuel cell stacks. Good mechanical properties in both dry and hydrated states The real life operating conditions may vary from sub - zero temperatures during winters to hot conditions during summers, hence the membrane should have good moisture uptake and retention properties to sustain operations over the whole range of temperatures. Low Cost In addition to the above mentioned capabilities the membranes should be economical to fabricate and incorporate into cells to be practically viable.

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Literature Review of Possible Materials which can be employed as Membrane in a PEM Fuel Cell
There has been a lot of contemporary research which focuses on finding and fabricating novel materials which have the requisite properties for operation under practical conditions in a fuel cell. Following sections explore the materials which have been considered as candidates for membranes in a PEM fuel cell.

Nafion
One material which has been in commercial use for a considerable time is a trademarked material from Du Pont Corporation Nafion. Nafion was developed by Dr. Walther Grot at DuPont in the late 1960s by modifying Teflon. Nafion was the first synthetic polymer ever developed with ionic properties, and it started an entirely new class of polymers called ionomers. These ionic properties of Nafion were created by adding sulfonic acid groups, a chemical with very strong ionic properties, into the bulk polymer matrix.

Properties
Nafion combines the physical and chemical properties of its Teflon base material with ionic characteristics that give the final material the following properties: 1. Nafion is extremely resistant to chemical attack. According to DuPont, only metallic alkali metals (sodium in particular) can attack Nafion directly under normal conditions of temperature and pressure. This means Nafion does not release fragments or degradation products into the surrounding medium.

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2. Nafion has relatively high working temperatures compared to many polymers. Nafion is used in some applications at temperatures up to 190 C. 3. Nafion is highly ion-conductive. It functions as a cation exchange polymer. 4. Nafion is a super-acid catalyst. The sulfonic acid groups attached to the Teflon backbone within Nafion function as an extremely strong proton donor due to the stabilizing effect of the large polymer matrix attached to the sulfonic acid. 5. Nafion is very selectively and highly permeable to water. The sulfonic acid groups in Nafion have a very high water-ofhydration, so they very efficiently absorb water. Interconnections between the sulfonic acid groups lead to very rapid transfer of water through the Nafion.

Applications
These unusual properties are exploited in the four main applications of Nafion today. 1. Nafion is used to fabricate ion-exchange membranes used to produce chlorine gas and lye (sodium hydroxide) by the electrolysis of salt water. 2. Nafion is used to selectively dry or to humidify gases. The largest segment of this application involves drying or humidifying breath for anesthesia, respiratory care, or plethysmography, but many applications exist in the laboratory and in industrial use. 3. Nafion is used as the proton exchange membranes in polymer electrode fuel cells. 4. Nafion is used as a super-acid catalyst in the production of fine chemicals.

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Figure 2 Nafion Structure

Figure 3 Nafion - A more general formula

Functional Aspects
Nafion is initially produced in a salt form with its sulfonic acid groups neutralized. In this form, Nafion is thermoplastic (extrudable and formable using heat and pressure), but not chemically active. Once extruded into its final form (typically sheet or tubing), Nafion is chemically activated by conversion of the salt form to the acid form. At this stage, Nafion is a translucent plastic that is similar in appearance to Teflon, but clearer and less opalescent. Once activated, Nafion immediately begins to react with its surrounding environment. Moisture is absorbed and exchanged with the surroundings. Reactive organic gas components within the surrounding air may undergo chemical changes when exposed to the super-acid catalytic activity of Nafion. These organic gases may combine to form larger compounds that are liquid or solid in nature. Over time, these organic residues build up a deposit on the Nafion. The original color of the Nafion changes gradually from translucent to yellow, then brown, then even black.
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The chemical nature of the Nafion itself is not changed by this process. The Nafion is not directly attacked, and the Nafion is not degraded. Its properties of water permeability, ion-exchange, and acid catalysis are not directly affected. For Nafion to transport water (dry or humidify gases), the water must be able to reach the active sites on the surface of the Nafion. In extreme cases, deposits of organic residues can build up on the Nafion to the point where the surface of the Nafion is sufficiently occluded to reduce its functionality. When this occurs, the discoloration of the Nafion is severe, black rather than merely yellow or brown. Even in these extreme cases, Nafion is still functional, it merely loses efficiency. Loss of a few percent of its total functionality due to partial occlusion means that a gradual decline in performance will be observed, not a catastrophic failure. Under typical storage or operating conditions, Nafion will turn somewhat yellow within a year and brown within three to five years. Even after turning brown, the Nafion is still fully functional, and no loss of performance efficiency is likely to be observed. These unwanted chemical reactions in the air surrounding Nafion are stimulated by exposure to light and to elevated temperatures. Storage in sealed bags in the dark will extend the pristine original appearance of Nafion. The original clear appearance of Nafion can be restored by cleaning. Various cleaning solvents may be used if desired, usually non-polar solvents such as hexane. The most effective cleaning method (used by Perma Pure in its dryer service procedures) is to boil it in strong acid. Nafion is not damaged by these procedures, but the discolored surface residues are eliminated.

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Morphology
The morphology of Nafion membranes is a matter of continuing study to allow for greater control on its properties. Other properties must be related to the Nafion structure such as water management, hydration stability at high temperatures, electro-osmotic drag, as well as the mechanical, thermal, and oxidative stability. The first model for Nafion, called the Cluster-Channel or ClusterNetwork Model, consisted of an equal distribution of sulfonate ion clusters (also described as 'inverted micelles') with a 40 (4 nm) diameter held within a continuous fluorocarbon lattice. Narrow channels about 10 (1 nm) in diameter interconnect the clusters, which explains the transport properties.

Figure 4 Cluster Network Model of Nafion

The difficulty in determining the exact structure of Nafion stems from inconsistent solubility and crystalline structure among its various derivatives. Advanced morphological models have included a core-shell model where the ion-rich core is surrounded by an ion poor shell, a rod model where the sulfonic groups arrange into crystal-like rods, and a sandwich model where the polymer forms two layers whose sulfonic groups attract across an aqueous layer where transport occurs. Consistency between the models include a network of ionic clusters;
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the models differ in the cluster geometry and distribution. Although no model has yet been determined fully correct, some scientists have demonstrated that as the membrane hydrates, Nafion's morphology transforms from the Cluster-Channel model to a rod-like model. A more recent water channel model was proposed based the simulations on small-angle X-ray scattering data and solid state nuclear magnetic resonance study. In this model, the sulfonic acid functional groups self-organize into hydrophilic water channels of ~ 2.5 nm diameter through which small ions can be easily transported; while hydrophobic polymer backbone with crystallites provides good mechanical stability.

Figure 5 Water Channel Model of Nafion

Another model thats gaining increased attention is the Yeager 3 phase model The Yeager Three Phase Model is a phenomenological based model and is based on a three-phase clustered system with interconnecting channels within the polymer.
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The three regions consist of (A) a fluorocarbon backbone, some of which is microcrystalline, (B) an interfacial region of relatively large fractional void volume containing some pendant side chains, some water, and those sulfate or carboxylic groups and counter ions which are not in clusters (C) the clustered regions where the majority of the ionic exchange sites, counter ions, and sorbed water exists. From experimental means, such as, small-angle x-ray scattering (SAXS) it has been determined that the phase-separated morphology is on the order of 30-50 Bragg spacing. However, upon hydration, Nafion with its unique ability to sorb relatively large amounts of water, can increase its dry weight by as much as 50 percent or more depending upon equivalent weight, counter ion, and temperature. Upon hydration, however, cluster diameter and the number of exchange sites are thought to increase, leading to fewer, larger clusters.

Figure 6 Yeager 3 phase model of Nafion

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Another alternative description for the above concept is that the Nafionpolymer contains three different phases: The sulphonic acid groups are clustered in hydrophilic inclusions (A) where most of the counter ions and water are located. These clusters are approximately 30 in diameter and are interconnected by aqueous channels with a diameter of approximately 10 . The Teflon-like polymer backbone (B) is essentially hydrophobic . The interfacial domain (C) is intermediate in hydrophilicity.

Other materials researched as alternatives to Nafion

PVDF g Polystyrene : As extensively reported in the literature, styrenic monomers are widely available and easy to modify, and their polymers are easily synthesized via conventional free radical and other polymerization techniques. An advantage of the PVDFg-polystyrene membranes is the relatively mild sulfonation conditions required (compared to conc. Of H SO with chlorosulfonic acid in 1,1,2,2-tetrachloroethane) . Future work will involve making improvements to the MEA (i.e. electrolyte / electrode double layer) and also investigating the effects of changing the synthetic procedure (i.e. varying the radiation dose,grafting reaction conditions and thickness of the base polymer). Analogous are phenol sulfonic acid resin & poly(trifluoro styrene sulfonic acid). Commercial PEMs based on styrene are BAM (Ballard) & Sulfonated styrene-ethylene-butylene-styrene (SEBS) (Dias Analytics)
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Figure 7 Structure of PVDF

Figure 8 Dias Analytics Polymer

Aromatic

Polymers

such

as

poly(oxy-1,4-phenyleneoxy-1,4poly(1,4-phenylene), poly(phenylene sulfuric acid,

phenylenecarbonyl-1,4-phenylene)(PEEK), poly(4-phenoxybenzoyl-1,4-phenylene)(PPBP), are easily Sulfonated using

sulfide) are also employed as backbones. These aromatic polymers concentrated chlorosulfonic acid, pure or complexed sulfur trioxide and acetyl sulfate. Poly(ether ether ketone) (PEEK) is an aromatic, high performance, thermal semicrystalline polymer chemical with extremely electrical good and stability, resistance,and

mechanical properties.Easily sulfonated because of electron

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pulling

nature

of

carbonyl

group.

Figure 9 Sulphonation of PEEK

Figure 10 Sulfonation of PPBP

Figure 11 Types of PBI

Complexes of Basic Polymers like poly(ethylene oxide)(PEO), poly(acrylamide)(PAAM), polybenzimidazole (PBI) and poly(vinyl alcohol)(PVA) with strong acids such as phosphoric or sulfuric acid possess high proton conductivities in both dehydrated and
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hydrated states. Because of their unique proton conduction mechanism by self-ionization and self-dehydration, H3PO4 and H2-SO4 exhibit effective proton conductivity even in an anhydrous (100%) form. When a basic polymer is present, the interaction between these acids and the polymer through hydrogen bonding or protonation would increase the acid dissociation, compared to that of anhydrous acids. Based on Polyimides,Polyphosphazenes and high performance polymeric backbones like Poly(phenylquinoxaline), Poly(2,6ether dimethyl-1,4-phenylene oxide)(PPO), Poly(phthalazinone

ketone)(PPEK) are also been researched

Main Research Focus Fillers to improve performance on Nafion membranes

The main obstacles to greater commercialization of polymer electrolyte fuel cells are mostly related to the low-proton conductivity at low-relative humidity of the known ionomeric membranes, to their high permeability and poor mechanical properties above 130 degree Celsius. A possible solution for these problems has been found in the development of composite membranes, where particles of suitable llers are dispersed in the ionomer matrix. These fillers have physical and chemical properties which impart desirable changes in the physical structure and properties of the host polymers thereby making them more suitable for day to day usage. The research on fillers was maily concentrated on Nafion as Nafion is already a commercially viable product and has been in use in a variety of fuell cell in different applications. The main restraining of the true
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potential of Nafion as a polymer electrolyte membrane is caused by its low retentivity of water at high operating temperatures which drastically reduce its proton conductivity as the protons require and aqueous medium for transportation through Nafion as described in the earlier sections. A variety of materails have already been researched for use as fillers to fabricate composite Nafion membranes. Among them the ones that have shown some promise are : Silica - The silicon oxide Naon membranes exhibit lower resistances and higher current densities at 130 and 140C than the unmodied Naon membranes. The silicon oxide essentially lowers the vapor pressure of the water in the membrane, i.e., the hydrated silicon oxide provides better water retention than unmodied Naon at reduced relative humidity. Also, the impregnation of the silicon oxide into the nanopores of Naon cause the silicon oxide Naon membranes to be less susceptible to high-temperature damage. Dehydration of the unmodied Naon at elevated temperatures leads to the destruction of the pore structure as detected by a decrease in proton conductivity. The presence of the silicon oxide within the membranes apparently prevents these temperature-related structural changes, and conductivity is maintained even after thermal cycling above the observed dehydration temperature of 130C of the unmodied Naon membrane.

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Figure 12 SEM images of Unmodified Nafion

Figure 13 SEM images of Silicon Recast Nafion

Figure 14 Current Characteristics at high temperatures of 130 degree celsius clearly show the advantage of using silica fillers

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 Titanium Oxide - The introduction of TiO2 inorganic ller supplies the composite membrane with a good mechanical and thermal resistance and improves the water uptake and IEC values if compared to the commercial Naon membrane.

Figure 15 The graphs show consistent improvement of composite characteristics over that of pure Nafion

Metal Oxides Utilising metal oxides (Al2O3 and ZrO2)as fillers have shown to reduce the resistivities of Nafion Composite Membranes

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Figure 16 Current Characteristics of Alumina Recast Membranes

Layered

Phosphates

Layered

Phosphates

especially

of

Zirconium have been researched on. With zirconium phosphate there is no or only minor formation of a multi-layered structure inside Naon but rather of monolayers of zirconium phosphate existing inside the Naon structure. Since the channel diameter and cluster size of Naon 1100 is about 1 and 4 nm, re-spectively and the interlayer distance of zirconium phosphate is 0.75 nm, spatial restraints could prevent the growth of several layers. Hence, the zirconium phosphate should be incorporated in the channels and clusters of the Naon-structure. Further evidence of this is given by the strong decrease of crystalline areas of the matrix with increasing concentration of zirconium phosphate. The ionic interaction between the ller and the hydrophilic clusters could be very strong and reduce the ability of the backbone regions of Naon to align into crystallites.

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 Zeolites The zeolites are of much interest due to their 3-D network of channels that have the unique property of molecular sieving which are also theoritically expected to increase water retentivity and increase structural stability. Though zeolite nafion composites are yet to show any significant improvement over pure nafion membranes researchers are optimistic on its prospects.

Figure 17 SEM micrograph of cross section of Nafion Zeolite composite

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Experimental Focus
After a thorough literature review of all the materials considered as pure membranes and also of the various fillers used with Nafion. A consensus was reached that fabricating completely novel membranes was not a feasible task considering the time frame available. Thus, all the effort was then focussed on finding novel fillers which could be used to fabricate composite membranes with Nafion. This was a reasonable choice as Nafion is already an established commercial product of choice for use as membranes in Fuel Cells and has been found to perform better than other alternatives. But the full scale utilisation of the fuel cells in practical situations like cars demand more ruggedness on the part of the membranes with respect to both water retentivity, conductivity and mechanical stability. Following the abovementioned chain of thoughts and keeping in mind the expertise available in the lab, two materials were chosen to be used as fillers for fabrication of composite membranes: Hydroxyapatite - Hydroxylapatite, also called hydroxyapatite (HA), is a naturally occurring mineral form of calcium apatite with the formula Ca5(PO4)3(OH), but is usually written Ca10(PO4)6(OH)2 to denote that the crystal unit cell comprises two entities. Hydroxylapatite is the hydroxyll endmember of the complex apatite group. Hydroxylapatite can be found in teeth and bones within the human body. Thus, it is commonly used as a filler to replace amputated bone or as a coating to promote bone ingrowth into prostheticc implants. Hydroxyapatite was chosen as a candidate due to its high mechanical strength and inherent
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porosity which would lead towards both increased water retention and also better stability at high temperatures.

Figure 18 SEM image of Hydroxyapatite showing the porous structure

MnO2 Nano rods SEM images of MnO2 Nano rods were quite promising as they could fortify the Nafion structure as well as increase water transport through their channels.

Figure 19 SEM image of MNO2 nanorods (NanoAmor)

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Experimental Methods
Materials
Nafion (5 wt. % mixture in alcohols and water - Sigma Aldrich catalogue - 510211), Nafion (10 wt. % dispersion in water - Sigma Aldrich catalogue - 527106), DMF (Anhydrous 99.8% - Sigma Aldrich catalogue - 227056), Ethanol (Sigma Aldrich catalogue - 459844) and Hydroxyapatite (nanopowder Sigma Aldrich catalogue - 677418) were obtained from Sigma Aldrich while the Manganese Dioxide nano-rods were obtained from Nanostructured and Amorphous Materials Inc., Houston.

Fabrication of Membranes
The Nafion solution obtained from Aldrich was used as it was received and a solution of it was prepared using ethanol and DMF as specified in [12]. The resulting solution was stirred for 2 hrs and then sonicated for 30 minutes and was then poured into a teflon dish for preparing pure Nafion membranes. The solution was then kept at 80C under vacuum overnight to form the membranes. For preparing the Nafion Hydroxyapatite membranes the nanopowder was dispersed in the above mentioned Nafion solution and the same procedure was followed for preparing the membranes.

SEM characterization
SEM characterization was carried out by a Gemini SEM for both pure Nafion and Nafion Hydroxyapatite composite.
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Figure 20 Pure Nafion - The folds are due to accelerated heating of solution

Figure 21 Nafion + HAP The same folds are observed at a much larger scale

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Figure 22 Nafion + HAP showing aggregate dispersion of HAP as a large quantity of HAP was used in preparing solution\

Figure 23 A more closer look at the above image

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Figure 24 A better Nafion membrane prepared the second time with slower heating now shows less pronounced folds

Figure 25 Side view of the pure Nafion shows uniform distribution of Solution particles

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Figure 26 A better dispersion of HAP particles due to less (5%) amount used the second time

Figure 27 Side view of Nafion + HAP shows a structure with a lot of channels as compared to pure Nafion

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Water Uptake Measurements

Water uptake measurements were taken at regular intervals of 1000 seconds through 15,000 seconds of the weights of membranes which were submerged under water at room temperature to study the diffusion characteristics of water in the membranes. Membranes were also soaked overnight and the weights of the wet membranes were measured to calculate the water uptake as a percentage of their weights using the following formula:
WaterUptake% Mwet Mdry X 100 Mdry

Results
The water uptake characteristics of Nafion was observed to show near Fickian diffusion of water into the membrane while for the composite water uptake was found to be occurring in steps, which possibly points towards differential diffusion of water in hydroxyapatite particles due to the heterogeneous nature of the membrane . Below are the time plots of the weight of the membranes at regular time intervals.

Figure 28 Water Uptake for Pure Nafion

Figure 29 Water Uptake for Nafion HAP composite

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References
1. Goward NMR Group McMaster University 2. Alternative Polymer Systems for Proton Exchange Membranes (PEMs) - Michael A. Hickner, Hossein Ghassemi, Yu Seung Kim, Brian R. Einsla and James E. McGrath 3. Sara D Flint and Robert C.T Slade, Department of Chemistry, University of Exeter, Exeter EX4 4QD, UK 4. Dias Polymer Electrolyte - Sheng-Li Chena, L. Krishnana, S. Srinivasana, J. Benziger, A.B. Bocarslya - Department of Chemistry, Princeton University 5. Proton conducting composite membranes from polyether ether keton and heteropolyacids for fuel cell applications - S.M.J. Zaidi, S.D. Mikhailenkoa, G.P. Robertsonb, M.D. Guiver, S. Kaliaguine 6. Properties of selected sulfonated polymers as proton-conducting electrolytes for polymer electrolyte fuel cells - J.-M. Bae, I. Honma, M. Murata, T. Yamamoto, M. Rikukawa, N. Ogata 7. Approaches and Recent Development of Polymer Electrolyte Membranes for Fuel Cells Operating above 100 C - Qingfeng Li, Ronghuan He, Jens Oluf Jensen and Niels J. Bjerrum 8. Silicon Oxide Naon Composite Membranes for Proton-Exchange Membrane Fuel Cell Operation at 80-140C - K. T. Adjemian, S. J. Lee, S. Srinivasan, J. Benziger and A. B. Bocarslya 9. NaonTiO2 hybrid membranes for medium temperature polymer electrolyte fuel cells (PEFCs) - A. Sacc, A.Carbone , E.
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Passalacqua, A. DEpifanio, S. Licoccia, E. Traversa, E. Sala, F. Traini, R. Ornelas 10. Function and Characterization of Metal Oxide Nafion

Composite Membranes for Elevated-Temperature H2/O2 PEM Fuel Cells - Kevork T. Adjemian,Raymond Dominey, Lakshmi Krishnan, Hitoshi Ota, Paul Majsztrik, Tao Zhang, Jonathan Mann, Brent Kirby, Louis Gatto,Melanie Velo-Simpson, Jacklyn Leahy, Supramanian Srinivasan, Jay B. Benziger andAndrew B. Bocarsly 11. COMPOSITE MEMBRANES FOR MEDIUM-TEMPERATURE PEM FUEL CELLS - G. Alberti and M. Casciola 12. Zeolite/Naon composites as ion conducting membrane

materials, Vincenzo Tricoli, Francesco Nannetti 13. Water sorption, desorption and transport in Naon

membranes - Paul W. Majsztrik , M. Barclay Sattereld, Andrew B. Bocarsly , Jay B. Benziger 14. Synthesis and characterization of novel acidbase polymer

blends for application in membrane fuel cells - Jochen Kerres , Andreas Ullrich, Frank Meier, Thomas Haring - Universitat Stuttgart, Institut f ur Chemische Verfahrenstechnik, Boblinger Str. 72, D-70199 Stuttgart, Germany 15. 16. www.wikipedia.com www.howstuffworks.com

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