Journal of Membrane Science 322 (2008) 6773

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Journal of Membrane Science

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Crosslinking of sulphonated poly (ether ether ketone) using aromatic bis(hydroxymethyl) compound
Varsha R. Hande, Swati Rao, S.K. Rath, Avinash Thakur, M. Patri
Naval Materials Research Laboratory, Shil-Badlapur Road, P.O. Anandnagar, Ambernath 421506, India

a r t i c l e

i n f o

a b s t r a c t
2,6-Bis(hydroxymethyl)-4-methyl phenol and 1,4-bis(hydroxymethyl) benzene have been used as crosslinkers in sulphonated poly (ether ether ketone) (SPEEK DS 65%, IEC 1.84 mequiv./g) for the preparation of proton exchange membranes (PEMs). Crosslinking of SPEEK has been achieved by thermally activated bridging of the polymer chain with the hydroxymethyl group of crosslinker through condensation reaction with sulphonic acid group. The physico-chemical properties of uncrosslinked and crosslinked membrane were evaluated in terms of ion exchange capacity (IEC), water uptake, ionic conductivity and mechanical properties. The crosslinked membrane showed controlled swelling, ionic conductivity of 2550 mS/cm at 80 C and good mechanical properties. The chemical stability of the crosslinked membranes was studied by Fentons test. The % loss in weight and changes in physico-chemical properties of the treated membranes were determined. 2008 Elsevier B.V. All rights reserved.

Article history: Received 7 September 2007 Received in revised form 4 May 2008 Accepted 12 May 2008 Available online 28 May 2008 Keywords: Proton exchange membrane Sulphonated poly (ether ether ketone) (SPEEK) Crosslinker Physico-chemical properties

1. Introduction Poly (ether ether ketone) (PEEK) is a thermally stable and mechanically tough polymer. On sulphonation, the polymer becomes hydrophilic and ionically conductive [1]. Because of these properties, SPEEK membranes nd application as polymer electrolyte membrane in electrochemical devices such as proton exchange membrane fuel cell (PEMFC), super capacitor, etc. [27]. SPEEK membrane can be prepared using wide variety of solvents since it is easily soluble in polar solvents. The solubility of SPEEK depends on the degree of sulphonation. As the degree of sulphonation increases, the solubility in water increases. But this leads to deterioration of mechanical properties [8]. Further, in aqueous environment at relatively high temperature (fuel cell operating temperature) SPEEK membrane swells extensively and as a result the mechanical property is not adequate enough to be useful for long-term application in fuel cells. Many research efforts have been undertaken to prepare more stable and mechanically strong membranes through crosslinking [916]. Crosslinking of sulphonated aromatic hydrocarbons can be achieved through bridging the reactive sulphonic acid group available in the polymer. The bridging can be brought about either by inter-chain self-condensation or through crosslinker involving sulphonic acid groups. Kerres et al.

Corresponding author. Tel.: +91 251 2620401; fax: +91 251 2620604. E-mail address: mrpatri@rediffmail.com (M. Patri). 0376-7388/$ see front matter 2008 Elsevier B.V. All rights reserved. doi:10.1016/j.memsci.2008.05.040

carried out extensive studies on the development of covalently and ionically crosslinked sulphonated polyarylene [911]. The covalent crosslinking was achieved through alkylation of sulnate group with - dihalogenoalkanes [9] which enhanced the thermal stability but the nal product was brittle. Ionically crosslinked membranes were prepared by blending the acidic ionomers with basic (aminated) polymer in binary and ternary compounds [10,11]. Crosslinking of SPEEK has also been obtained by aliphatic/aromatic amines [12] and imide containing amines [13]. Advantages and disadvantages of such efforts have recently been elaborated [14,15]. Kaliaguine and co-workers carried out detailed study on crosslinking of SPEEK using glycol, glycerol and erythritol in different solvent/solvent pair [14]. The authors measured proton conductivity at room temperature, but water uptake has been measured both at room temperature as well as high temperature [15]. While water uptake at room temperature is around 30%, these membranes suffer from extensive swelling at high temperature. No results on fuel cell performance for these membranes are currently available in literature. The choice of casting solvent also plays a very important role in preparation of membrane. It has been recently brought out by Robertson et al. that use of dimethyl formamide (DMF) and dimethyl acetamide (DMAC) leads to formation of dimethyl amine (DMA) which reacts with sulphonic acid group and forms dimethylaminium hydrogensulphate [17]. This in turn forms stable DMA-sulphonic acid adduct. The solvent (DMF and DMAC) interaction with SPEEK reduces proton conductivity or the number of proton available for proton transport.

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The present communication deals with two issues such as selection of solvent for preparation of membrane and crosslinking of SPEEK. Two types of aromatic bis(hydroxymethyl) compounds, namely 2,6-bis(hydroxymethyl)-4-methyl phenol (BHMMP) and 1,4-bis(hydroxymethyl) benzene (BHMB) have been used as crosslinkers. The membrane preparation and its physico-chemical properties have been discussed. 2. Experimental 2.1. Materials PEEK (450 PF) obtained from Victrex, USA was used as received. 1,4-Bis(hydroxymethyl) benzene from Fluka, concentrated sulphuric acid (98 wt%) from E. Merck, India, p-cresol, formaldehyde (37% aqueous solution), potassium carbonate, ethyl alcohol and H2 O2 (30% solution) all from S.D. Fine Chemicals, India were used as received. 2.2. Synthesis of 2,6-bis(hydroxymethyl)-4-methyl phenol Synthesis of BHMMP has been carried out as per procedure reported elsewhere [18]. 2.3. Sulphonation of PEEK Sulphonation of PEEK was carried in concentrated sulphuric acid according to method reported earlier [19]. Concentration of PEEK in sulphuric acid was varied from 4% to 16%. The solution was stirred at 30 C for 1 h and then at 55 C for desired time with vigorous stirring. The sulphonated polymer in sulphuric acid was poured into crushed ice with vigorous agitation where SPEEK separated out as ber-like material. The precipitate was repeatedly washed with ice-cold distilled water till the pH of the ltrate was >5. The sulphonated polymer was dried at room temperature for 48 h and then at 100 C under reduced pressure till constant weight. The degree of sulphonation (DS) was calculated using the method given in literature [19]. 2.4. Membrane preparation SPEEK having DS 65% and ion exchange capacity (IEC) 1.84 mequiv./g has been used for membrane preparation. SPEEK was dissolved in waterethanol mixture (1:1) containing either BHMMP or BHMB as crosslinker under hot condition. The crosslinker content was varied from 0.5 mol/mol to 1 mol/mol repeat unit of SPEEK. To get a clear solution the procedure adopted is as follows. 10 g dry SPEEK was initially swollen in 50 ml distilled water at 70 C. To the swollen mass 50 ml ethanol was added under stirring and heated for 510 min at 70 C to get the solution. The crosslinker was added to the solution and stirred well till complete dissolution. The solution was degassed under vacuum for 15 min and cast onto a glass plate. The lm was dried under ambient condition for 2 days and then cured under vacuum for 8 h at different temperatures. The sequence of heating was; 50 C for 2 h, 100 C for 2 h, 120 C for 2 h and 135 C for 2 h. Thus, the membranes prepared using BHMMP and BHMB have been referred as membrane A and membrane B, respectively. To compare the properties of uncrosslinked and crosslinked SPEEK membrane, the uncrosslinked SPEEK membrane was cast using DMAc as solvent, since uncrosslinked SPEEK when dissolved in water:ethanol mixture results in membrane which is brittle.

2.5. Characterization of SPEEK membranes IR spectra of SPEEK membrane and crosslinked SPEEK membrane were recorded in PerkinElmer (1650) FTIR spectrophotometer. 2.6. Ion exchange capacity IEC of the membranes was determined by suspending about 0.5 g SPEEK in 0.5 M NaCl solution, equilibrating for 24 h with slow stirring and titrating the liberated acid with 0.05 M NaOH solution. 2.7. Water uptake Water uptake at different temperatures was determined by the weight difference between the fully hydrated membrane and dried membrane. Each dried lm was cut to a size of about 5 cm 5 cm and equilibrated in distilled water at different temperatures viz. 30 C, 40 C, 50 C, 60 C, 70 C and 80 C for about 8 h, then removed from water, extra water on the membrane was wiped out using the tissue paper. The water uptake was calculated as follows: water uptake = Wwet Wdry Wdry 100

Wwet is the weight of membrane after keeping in water, and Wdry is the weight of dry membrane. 2.8. Mechanical properties Tensile properties of crosslinked SPEEK membrane as well as H2 O2 treated membrane equilibrated in water for 24 h at 30 C as strip (100 mm 10 mm 0.1 mm) were measured using an Hounseld UTM (model no. 50K-S). The crosshead speed of 10 mm/min was maintained for all the samples. 2.9. Proton conductivity measurement Transverse proton conductivity of the membranes were carried out by AC impedance spectroscopy using Auto lab with Frequency Response Detector over a frequency range of 100 mHz to 1 MHz. Prior to measurement of conductivity SPEEK membrane was pretreated with 1 M H2 SO4 followed by equilibration by immersing in water for 24 h at 30 C. Circular membrane sample having 15 mm diameter was cut from the acid-free membrane and was sandwiched between two stainless electrodes. The conductivity was measured at 30 C and 80 C under 95% RH. The electrode containing sample was kept in a cell to which steam was continuously passed to maintain 95% humidity. The proton conductivity was calculated from the impedance data, using the relationship = d/RS, where d and S are the thickness (cm) and area (cm2 ) of the sample. R (resistance) was derived from the Nyquist plot. 2.10. Chemical stability: Fentons test Fentons reagent was prepared by dissolving ammonium ferrous sulphate (4 ppm) in 3% H2 O2 aqueous solution. Prior to experiment membranes were dried in vacuum oven at 60 C for 12 h. Predried and pre-weighed SPEEK membranes were stirred in Fentons reagent at 70 C for different time interval. The membranes were then taken out of the solution and immersed in deionized water to prevent further degradation. Treated membranes were dried at 60 C for 12 h. The % loss in weight and changes in physico-chemical properties of the treated membranes were determined.

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Fig. 1. Degree of sulphonation with respect to time at different concentration of PEEK/H2 SO4 .

3. Results and discussion PEEK was sulphonated at 55 C using concentrated sulphuric acid. The reaction was studied by varying the concentration of PEEK and time. The dpendance of degree of sulphonation on time at different PEEK concentrations is presented in Fig. 1. From the results, it is seen that DS increases with increase in reaction time and decrease in concentration of PEEK in sulphuric acid. Detailed kinetics of sulphonation of PEEK has been studied by Huang et al. [19]. The results presented in Fig. 1 follow similar trend. For the present study SPEEK was synthesized using 13% PEEK in H2 SO4 . The DS was 65 2% and the resultant polymer was soluble in water:ethanol mixture, DMF and DMAC. Kaliaguine et al. [15] observed that SPEEK with DS >75% can be dissolved in ethanol:water and acetone:water mixtures. However, in the present case we have been able to dissolve SPEEK with DS 65 2% in water:ethanol mixture by adopting the procedure explained in experimental. On casting and drying the resultant lm was devoid of any entrapped solvent. Further, there is little likelihood of hydroxyl interaction with acid group due to very low boiling point

of ethanol, which is about 4 C under vacuum. This process is advantageous since removal of solvent involves only heating as compared to other solvents which require elaborate procedures. Deb et al. [16] reported the removal of entrapped solvent in crosslinked SPEEK with phenol formaldehyde resin as crosslinker. In the present study the entrapped DMAC for uncrosslinked membrane was removed by adopting the same procedure. SPEEK was crosslinked by using two types of aromatic bis hydroxymetyl compounds, BHMMP and BHMB. The possible chemical reaction occurring on crosslinking is shown in Scheme 1. Hydroxymethyl group of aromatic compound reacts with sulphonic acid resulting in the formation of C SO2 O C linkage. The schematic is only an idealistic representation of the possible reactions, as intramolecular condensation and self-condensation of the crosslinker cannot be ruled out. In case of BHMMP, phenolic OH group is presumed to be inactive in the crosslinking. Deb et al. reported that the phenolic OH does not participate in the crosslinking process for SPEEK membranes crosslinked with phenol formaldehyde resin [16]. From Scheme 1, it is evident that both crosslinker and SPEEK being aromatic have structural similarity and aromatic ring attached to hydroxymethyl group will facilitate the reaction with SO3 H group. As mentioned in the experimental section, the crosslinking reaction has been carried out by progressively heating the membrane. It was observed that heating the membrane around 100 C the crosslinking was incomplete as the membrane dissolves in hot water. Conversely, the membrane heated at 135 C was found to have pin holes. In all our experiments it was observed that the membrane changed colour while heating from brownish yellow to dark brown. This change is visible when concentration of crosslinker is more than 0.5 mol. Similar observation was made for SPEEK crosslinked with aliphatic alcohol [14]. Attempt was made to extract the unreacted crosslinker from the membrane. Both the crosslinker were heated up to 135 C as the same sequence of heating opted for the membrane. It was found that the BHMMP did not dissolve in water:ethanol mixture while the solution of BHMB became viscous. To extract unreacted BHMMP and BHMB, the crosslinked membrane was heated in

Scheme 1. Possible crosslinking reaction of SPEEK with crosslinker.

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Fig. 4. Conductivity of crosslinked membrane with respect to different concentration of crosslinker. Uncrosslinked SPEEK conductivity 65 mS/cm. Fig. 2. IR spectra of (A) SPEEK membrane, (B) crosslinked SPEEK BHMMP and (C) crosslinked SPEEK BHMB membrane.

to presence of sulphonic acid group and sulphonate ester group in crosslinked SPEEK. 3.1.2. Water uptake Water uptake plays a very important role in polymer electrolyte membrane, since proton transport involves coordination of water molecules with proton to move through the membrane. Results of water uptake at different temperature for crosslinked and uncrossliked membrane are presented in Fig. 3. In uncrosslinked membrane swelling increases with increasing temperature, but the temperature effect is more as the ion exchange capacity is increased. In case of SPEEK (IEC 1.84 mequiv./g) excessive swelling occurred after 60 C. In crosslinked membrane it is seen that with increase in temperature (3080 C) the water uptake of the membrane increases. The increase up to 60 C is marginal while beyond that the water uptake increases signicantly. This is probably due to the fact that at lower temperature the increase in water uptake depends on the number of ionic groups present, as the temperature increases the water lls into the sub-microspores of the polymer thereby swelling the membrane [20,21]. Despite this the water uptake values for crosslinked SPEEK membranes are less than the uncrosslinked ones. As the concentration of crosslinker increased, the water uptake of the membrane decreased. This is attributed to the fact that increase in amount of crosslinker results in involvement of more number of sulphonic acid groups in crosslinking. Thus, at 0.5 mol BHMMP and BHMB the variation in water uptake with respect to temperature is large due to less crosslinking. However, beyond 0.75 mol the variation in water uptake is not signicant and at 1.0 mol concentration the change in water uptake is marginal with respect to temperature. The water uptake of crosslinked SPEEK using BHMMP and BHMB (1.0 mol) is only 35% which is close to the water uptake value of Naon. It may be mentioned here that Kaliaguine and co-workers have measured the water uptake of SPEEK croslinked with ethylene glycol at room temperature as well as at 80 C [15]. Although the water uptake at room temperature is 32%, at 80 C the water uptake was 2100%. Similarly membranes crosslinked with glycerol had water 47% and 2900% at 25 C and

Fig. 3. Water uptake with respect to temperature at different crosslinker concentration. (A) Crosslinked SPEEK BHMMP membrane; (B) crosslinked SPEEK BHMB membrane.

alcohol. However, no trace of BHMMP and BHMB was found, this is possibly because BHMMP and BHMB might have undergone selfcondensation during crosslinking. 3.1. Characterization of crosslinked SPEEK membrane 3.1.1. FTIR spectra Infrared spectra of SPEEK and crosslinked SPEEKBHMMP and SPEEKBHMB are shown in Fig. 2. Absorption bands associated with sulphonic acid group in all the three types of membranes were observed at 34503365 cm1 , 12251218 cm1 , 1077 cm1 and 1020 cm1 . In crosslinked SPEEK, additional peaks at 3075 cm1 , 2924 cm1 and 2854 cm1 appeared due to aliphatic CH stretching of methylene group of crosslinker. The peak due to sulphonic acid group at 1225 cm1 in uncrosslinked SPEEK is sharp where as in case of crosslinked SPEEK this peak is found to be broad. The broadness of the absorption peak around 1225 cm1 is possibly due

Table 1 Ion exchange capacity of SPEEK membrane crosslinked with BHMMP and BHMB before and after Fentons test Ion exchange capacity (mequiv./g) BHMMP crosslinked membrane 0.5 mol After crosslinking After H2 O2 treatment % of difference after treatment 1.40 (23.9)a 1.31 6.4 0.75 mol 1.31 (28.8) 1.18 10 1 mol 1.2 (34.2) 1.01 15.8 BHMB crosslinked membrane 0.5 mol 1.3 (29.5) 1.15 11.4 0.75 mol 1.22 (33.6) 1.08 11.4 1 mol 1.18 (35.8) 1.12 5

SPEEK IEC before crosslinking: 1.84 mequiv./g. a Figures in parentheses are yield of crosslinking (%).

V.R. Hande et al. / Journal of Membrane Science 322 (2008) 6773 Table 2 Weight loss, mechanical properties of SPEEK membrane crosslinked with BHMMP and BHMB before and after Fentons test Properties Uncrosslinked SPEEK Crosslinked SPEEK membrane BHMMP 0.5 mol Weight loss (%) 1h 2h 3h 4h Tensile strength (MPa) Before Fentons test 1 h after Fentons test Elongation (%) Before Fentons test 1 h after Fentons test
a

71

BHMB 0.75 mol 11

a a a

1 mol 8 70
a a

0.5 mol 12 15
a a

0.75 mol 7 11 16 75 35 23 17 9

1 mol 6 9 13 30 42 35 13 7

85
a a a

13
a a a

34
a

35 19 23 8

37 20 20 7

45 37 12 5

29 14 20 10

150
a

Membrane disintegrated.

80 C, respectively. We also had similar observations for membranes crosslinked with ethylene glycol and glycerol. 3.1.3. Ion exchange capacity The ion exchange capacity for various crosslinked membranes is shown in Table 1. From the results it is observed that with increase in the amount of crosslinker there is a gradual decrease in IEC due to participation of sulphonic acid group in crosslinking for both the crosslinkers. In order to determine the effective participation of crosslinkers in the crosslinking process, we evaluated the yield of crosslinking in the membranes. It is observed that the % yield of crosslinking, a measure of the amount of sulphonic acid group consumed by the active hydroxyl group of the crosslinker, increases monotonically with increase in crosslinker for both the crosslinkers, as expected. The yield of crosslinking for BHMMP crosslinked SPEEK membranes increases from 23% to 34% while the values varies from 29% to 35.8% for BHMB. This implies that BHMB is able to consume a higher fraction of SO3 H group compared to BHMMP. This could be attributed to structural difference of the two crosslinkers, where steric hindrance of the substituent groups in case of BHMMP probably retards the reactivity of the hydroxyl group. Irrespective of the crosslinker type, the yield of crosslinking is relatively low even when the crosslinker concentration is 1 mol/repeat unit of SPEEK. It implies that the reaction is far from being efcient since the crosslinking is performed in the dry state which favors the crosslinking within the ionic domains and probably the interpolymer chain crosslinking.

3.1.4. Proton conductivity The proton conductivity of membrane depends on the degree of sulphonation (the number of available acidic group), pretreatment of the membrane and sulphonic acid group dissociation capability in water and relative humidity [22]. The proton conductivity of crosslinked, uncrosslinked SPEEK membrane at 30 C and under fully humidied condition is reported in Fig. 4. From the results it is seen that uncrosslinked SPEEK has higher conductivity compared to crosslinked SPEEK. Further it is also seen that the conductivity increases with increase in temperature and humidity and decreases with increase in crosslinker concentration. In case of uncrosslinked membrane and crosslinked membrane using 0.5 mol of crosslinker, more sulphonic acid groups may aggregate into hydrophilic clusters that provide pathway for proton transport than the membrane crosslinked with 1 mol of crosslinker. However, conductivity of SPEEK crosslinked with 0.51 mol BHMMP and BHMB varies from 50 mS/cm to 25 mS/cm which is close to the reported value of uncrosslinked SPEEK [3,23]. 3.1.5. Mechanical properties The tensile strength and elongation at break of crosslinked SPEEK membranes equilibrated with water at 30 C for 24 h are presented in Table 2. From the result it is seen that crosslinked SPEEK membranes have reasonably good mechanical properties when compared to uncrosslinked SPEEK. With increase in crosslinker concentration the tensile strength increases marginally. Elongation at break is decreased due to increase in degree of crosslinking. Similar trend was observed in both the crosslinked membrane.

Fig. 5. FTIR spectra of crosslinked BHMB membrane before () and after (- - -) Fentons test.

Fig. 6. FTIR spectra of crosslinked BHMMP membrane before () and after (- - -) Fentons test.

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Table 3 FTIR characteristic spectral bands of SO group of crosslinked BHMMP and BHMB membrane after Fentons test Mole of crosslinker Crosslinked BHMMP membrane ratio of S O/C O (1077/1644 cm1 /1020/1644 cm1 ) Before treatment 0.5 0.75 1 2.54 2.34 2.39 2.36 2.34 2.20 After treatment 2.20 2.08 2.24 2.12 2.20 2.01 %Decrease of intensity 13.38 11.1 6.27 10.16 5.98 8.6 Crosslinked BHMB membrane ratio of S O/C O (1077/1644 cm1 /1020/1644 cm1 ) Before treatment 2.63 2.53 2.35 2.37 2.29 2.26 After treatment 2.35 2.30 2.20 2.17 2.16 2.08 %Decrease of intensity 10.64 9.0 6.38 8.4 5.67 7.9

3.1.6. Chemical stability Ageing of membranes in fuel cell is a known phenomenon. The degradation is known to occur due to the formation of HO and HOO radicals. The conditions under which these radicals are formed in a fuel cell and concentration of these radicals is unknown. Researchers have reported two different hypotheses to explain the degradation. According to Buchi et al. degradation may occur at the anode due to formation of HO and HOO radicals formed by the reaction of H2 and O2 [24]. According to Gao et al. degradation may occur at the cathode due to the oxygen reduction process [25]. In order to simulate the fuel cell environment, membranes were immersed in Fenton reagent. Changes in mechanical properties and physico-chemical properties of treated membranes were noted. The changes in IEC values after Fenton test is presented in Table 1. For BHMB crosslinked SPEEK, we observe the drop in IEC is about 11% for 0.5 M and 0.75 M concentration of crosslinker. At 1 M crosslinker concentration the decrease in IEC drops to 5%, implying increased stability with increased crosslinking density. However, an unusual trend of increasing drop in IEC values with increased concentration of crosslinker for BHMMP crosslinked SPEEK is observed. This discrepancy has been investigated in IR study which is discussed later. Table 2 shows the weight loss and mechanical properties of the treated and untreated crosslinked, uncrosslinked membranes. From the results it is seen that, in uncrosslinked SPEEK membrane the degradation is very high within 1 h. Weight loss and the tensile properties of crosslinked membrane deteriorate with the treatment as expected. As of the trend with respect to increasing crosslinker percentage, the drop in tensile strength as well as weight loss decreases, for both the crosslinkers. From the weight loss results it is seen that BHMMP crosslinked membranes stability is poorer compared to BHMB crosslinked membranes. At 1 M concentration of BHMB the weight loss is 30% even after 4 h treatment with H2 O2. This implies that BHMB imparts better structural stability to the membranes. In order to ascertain the structural changes inicted to the membrane upon treatment of Fentons reagent, we carried out FTIR analysis of the membranes. The spectra for the treated membranes are presented in Figs. 5 and 6. From the results (Fig. 5) we observe that the cumulative area for the OH absorption decreases upon treatment for BHMB crosslinked polymer, as a result of degradation of SO3 H linkage. However, the extent of deterioration decreases with increase in crosslinker. At 0.75 M and 1 M crosslinker concentration, the decrease in intensity is negligible. But, band area for OH groups is found to increase with increase in crosslinker concentration upon treatment for BHMMP crosslinked membranes (Fig. 6). This could be attributed to the oxidation of the free phenolic group present in the crosslnker. Varagnet et al. reported such oxidation of phenols by hydrogen peroxide and ammonium ferrous sulphate leading to the formation of mixtures of dihyroxy benzenes [26]. Because of the oxidation of phenolic moiety to dihydroxy ben-

zene, the overall molecular weight of the crosslinker would increase which in turn would increase the equivalent weight thereby reducing the IEC of the crosslinked SPEEK membrane. Thus, the unusual trend of increased % difference in IEC with increase in BHMMP concentration is not only due to degradation of sulphonic acid group but also due to the above oxidative process. Attempts to deconvolute the spectra in order to ascertain the individual contributions were made, but unfortunately because of the enormity of the peaks present, this was not possible. Similar difculty has been expressed by other groups in quantication of the results [27]. However, the qualitative trend is quite discernible. Further to evaluate the effect of treatment on the region corresponding to sulphonic group we concentrated on the band range of 13001000 cm1 . We attempted the quantication of the chemical stability of the membranes by taking into account the relative decrease in the intensity of S O peaks. The peak at 1644 cm1 corresponding to the C O of PEEK, is chosen as the relative standard and we found a decrease in intensity of absorption band at 1077 cm1 and 1020 cm1 . The ratios S O/C O (1077/1644 cm1 and 1020/1644 cm1 ) were taken as the measure of the extent of degradation of sulphonic groups upon H2 O2 treatment. From the results (Table 3), it is observed that the ratio decreases upon treatment, as expected. Further we observe that the % decrease in the ratio decreases with increasing crosslinker concentration for the treated membrane, implying improved stability. The % decrease in the ratio was found to be higher for the BHMMP crosslinked membranes compared to the BHMB. Thus, the IEC and FTIR results show increased structural stability with increase in crosslinker concentration for BHMB and BHMMP crosslinked membranes. The BHMB crosslinked membrane shows superior chemical stability than the BHMMP crosslinked membrane. The structure of BHMMP has two alcoholic groups in addition to one phenolic ring and a methyl group. This leads to steric hindrance since the molecule is crowded and hence BHMMP is prone to oxidative degradation. In our experimental studies it was observed that SPEEK without crosslinker undergoes heavy swelling and looses its mechanical properties within 1 h. The crosslinked membranes lose their mechanical integrity after treatment in Fentons reagent for 2 h in case of BHMMP and 4 h in case of BHMB. Zhang and Mukerjee [28] have also found that uncrosslinked SPEEK broke down completely into dark powder like pieces after 1 h on exposure to Fentons reagent. Similar observation have been made by Roziere and Jones in the H2 O2 treatment of SPEEK membrane [29]. 4. Conclusion Synthesis condition for sulphonation of PEEK with respect to PEEK concentration has been optimized. Sulphonation of 13% PEEK in H2 SO4 for 35 h at 55 C has been found to provide SPEEK having DS 65 2% which can be recovered easily. By following sequential heating procedure, it was possible to get crosslinked SPEEK

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membrane using waterethanol mixture as solvent. Crosslinking of SPEEK has been achieved involving SO3 H group by using BHMMP and BHMB, respectively as crosslinkers. A comparative study of the physicochemical and chemical stability of the membranes crosslinked with the two different crosslinkers was carried out. The membranes showed controlled swelling behaviour as well as good mechanical properties. Though the physico-chemical properties of both the crosslinked membrane were found to be similar, the chemical stability of BHMP crosslinked membrane was found to be better than the BHMMP crosslinked membrane. References
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