Journal of Membrane Science 347 (2010) 159164

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Journal of Membrane Science

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Assessing the oxidative degradation of polyamide reverse osmosis membraneAccelerated ageing with hypochlorite exposure
Alice Antony , Rudy Fudianto, Shane Cox, Greg Leslie
UNESCO Centre for Membrane Science and Technology, University of New South Wales, Kensington, Sydney, NSW 2052, Australia

a r t i c l e

i n f o

a b s t r a c t
The present work addresses the mechanistic aspect of hypochlorite attack on a commercial polyamide membrane and the oxidative degradation taking place under active (applied pressure with constant stirring) and passive (unpressurised and unstirred) conditions. The degree of membrane degradation was enumerated in terms of the decline in membrane performance, calculated from permeability and salt rejection for reverse osmosis (RO) feed water. For active exposures both permeability and salt rejection changed signicantly whilst only permeability varied for passive exposure. The structural changes in the polymeric backbone of the active surface layer were studied with attenuated total reectanceFourier transform infrared spectroscopy (ATRFTIR). For the chlorine damaged membranes, distinct peak suppression has been observed around 3330 cm1 . Minor but signicant shift in amide I and II bands and peak suppression in the ring stretching vibration at 1609 cm1 was also noticed. The suppression or shift in the characteristic peaks was observed for both active and passive contact, however the extent differed. The progress of membrane damage has been conrmed to advance up to ring chlorination, however the N-chlorinated substituent may not be considered as a short-lived intermediate in view of the fact that the chlorine substitution on nitrogen has been indicated through a change in the amide II band in the nal product. Perhaps the reaction products are both N-chlorinated products and ring chlorinated compounds, most likely their existence being inuenced by operating parameters. Especially pressure seems to have effect on the chlorine attack of polyamide surface, seeing that the rearrangement of Nchlorinated substituent to ring chlorination is favored by pressurized environment. Formation of ring chlorinated products appears to be the destroying phenomenon for the polyamide surface resulting in salt passage. Chlorine damaged membranes were tested for Fujiwara test, which is an indicative test generally performed in membrane autopsies to check the degradation of polyamide membranes with halogens. Whilst the membrane degradation was evident from the salt rejection values and the FT-IR patterns, Fujiwara analysis failed to diagnose the chlorine exposure at low concentrations, especially under passive conditions. 2009 Elsevier B.V. All rights reserved.

Article history: Received 13 May 2009 Received in revised form 3 October 2009 Accepted 12 October 2009 Available online 21 October 2009 Keywords: Reverse osmosis Polyamide ATRFTIR Fujiwara analysis Salt rejection

1. Introduction The application of membrane ltration in water and wastewater treatment sector is becoming common over the decades with increasing research and technology development. Increasing water scarcity and stringent regulations give an impetus for the development of membranes with high efciency, ruggedness and reliability. Polyamide thin-lm composite (TFC) membranes have become the most widely used reverse osmosis (RO) membrane for the water recycling and desalination applications due to their ability to withstand wide range of pH values and high recoveries. Regardless of the advantages, a major limitation with

Corresponding author. Tel.: +61 2 9385 5373; fax: +61 2 9385 5966. E-mail address: alicea@unsw.edu.au (A. Antony). 0376-7388/$ see front matter 2009 Elsevier B.V. All rights reserved. doi:10.1016/j.memsci.2009.10.018

the polyamide TFC membranes is its poor tolerance to chlorine [1]. RO membranes may become exposed to chlorine and the oxidizing environment it create in one of the two ways, chemical cleaning agents adopted for the ux recovery and disinfection agents added to the RO upstream to mitigate biofouling. The inuence of chlorine affects the structural integrity of the polyamide active layer leading to impaired performance [14]. Different pathways for the oxidative degradation of the polyamide membrane have been reported by several researchers. The degradation of polyamide is expected to take place through the N-chlorination mechanism followed by a rearrangement reaction. This mechanism is known as the Orton rearrangement, wherein the hydrogen on the amide nitrogen is substituted by chlorine followed by ring chlorination by intramolecular rearrangement [1]. The N-chlorination reaction has been claimed to be also reversible, with the possibility of N-chlorinated intermediate reverting to the

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A. Antony et al. / Journal of Membrane Science 347 (2010) 159164 Table 1 Mean water quality parameter for the RO feed. Parameter Conductivity, mho/cm pH Alkalinity, mg/L as CaCO3 Calcium, mg/L Magnesium, mg/L Sodium, mg/L Potassium, mg/L Chloride, mg/L Sulfate, mg/L Dissolved organic carbon, mg/L Value 2400 7.0 130 60 60 400 45 600 140 8.0

initial amide structure with alkali treatment. The chlorine attack of the polyamide membranes driving to a transition in morphology of the polymer, crystalline to amorphous state was proposed by Avlonitis et al. [5]. The signicant inuence of the chlorine attack was claimed to be due to the impact experienced by the amorphous regions enhancing the salt passage. Oxidation of polyamide membrane using monochloramine solution mediated through the presence of iron compounds was studied by Gabelich et al. [6] demonstrating the catalytic effect of iron. Soice et al. [7] suggested that the chlorine degradation of polyamide does not guide to any chain scission but separation of the barrier layer from the support, however this mechanism does not satisfy all pH conditions. Eventhough the operating performance of polymeric composite membranes depends on the active surface layer, the porous support is also found to have minor effect. In this line, the change in the transport parameters and chemical modications for polyamide/polysulfone membranes with aging and chemical agents were studied by Benavente et al. [8,9]. In these studies, both active and porous support layers were shown to be affected on exposing to those chemicals. Increase in permeability was observed upon treating with acids, whereas upon treatment with NaOH permeability decreased. The change in the membrane performance was attributed to the modication of the active surface layer. In the present study, the impact of pressure on the surface modication of polyamide reverse osmosis membrane was assessed. Performance decline of the membranes after accelerated ageing with hypochlorite solution, under pressurized and unpressurized conditions was studied through salt rejection and permeate ux parameters. The modication of functional groups occurred on the membrane active layer was studied through attenuated total reectanceFourier transform infrared spectroscopy (ATRFTIR). The effect of hypochlorite on the support layer was not discussed in this study. Fujiwara test has been performed as a cross-verication to check the exposure of membrane to chlorine damage and to check the validity of the test. 2. Methods and materials 2.1. Membranes and chemicals Commercially available polyamide RO membrane BW-30 FR supplied by Dow Filmtec was used in the study. The manufacturer reports an operating pH range between 2 and 11 and a maximum temperature and free chlorine tolerance of 45 C and <0.1 mg/L respectively. Accelerated membrane damage experiments were performed with commercial hypochlorite solution, with effective 10% free chlorine content. Appropriate concentrations were reached diluting with milliQ water, the pH of the hypochlorite solutions were 6.0. The chlorine concentrations selected in this study are 25, 62.5, 250 and 625 ppm and the exposure time was 16 h for all the experiments. In terms of ppm h, the chlorine exposure concentrations are 400, 1000, 4000 and 10,000 equivalent to an exposure of 0.1 mg/L concentration for 0.46, 1.14, 4.57 and 11.41 years. The salt rejection performance of the chlorine attacked membranes was studied using a RO feed water sourced from a pilot plant. Mean water quality data obtained for the RO feed is summarized in Table 1. 2.2. Experimental methodology The accelerated membrane damage tests were performed by bringing the membrane in contact to the hypochlorite solution

at both active (stirred and pressurized) and passive (static exposure) conditions. For the passive exposure, the membrane panels were immersed in sealed glass containers for the required time. For the active exposure, the membrane panels were placed in a stirred dead end ltration cell (Sterilitech Corporation) lled with hypochlorite solution and pressurized to 58 psig (4 bar) for designated period. The clean water permeability was measured for the virgin and hypochlorite exposed membranes, both before and after exposure. The ltration experiments were performed for the virgin and hypochlorite attacked membranes, by placing them in the direct mode ltration stirred cell lled with the RO feed water and pressuring at 174 psig (12 bar). The permeate ux and salt rejection were calculated at the 40%. 2.3. ATRFTIR study The ATRFTIR characterisation of the membrane samples was performed using Nicolet-5700 spectrophotometer (Thermo Electro Corporation, USA) equipped with diamond crystal ATR unit. All spectra were collected with 32 scans at 1 cm1 resolution and analysed with Omnic 7.3 software. 2.4. Fujiwara analysis The membrane panels of the required size were cut and positioned in sealed test tubes. 10 mL of 10 M sodium hydroxide and equal amount of pyridine solution was added to the test tube and placed in a boiling water bath for 2 min after sealing the test tubes. The test tubes were cooled and observed for any color change. 3. Results and discussion 3.1. Water ux and salt rejection performance The virgin and aged membrane performances were determined from their permeability and salt rejection. The permeability and salt rejection were calculated at 40% permeate recovery for membranes operating under specied conditions and the values were normalized to the reference conditions (25 C and 1 bar). As can be seen in Fig. 1(a), the membrane permeability increases with increasing chlorine concentration, the increasing trend is more pronounced under active conditions. For the chlorine exposure concentration of 10,000 ppm h, the observed increase in permeability was 42% and 21% for active and passive conditions respectively. The extent of membrane damage calculated in terms of salt rejection is shown in Fig. 1(b). A linear decrease in the salt rejection values was observed for the active conditions, whilst no substantial change was seen for the passive conditions. The average decrease in salt rejection is 1.3% for 1000 ppm h of exposure to hypochlorite under active conditions.

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Fig. 1. (a) Permeability and (b) salt rejection for the degraded membrane at active and passive conditions.

The permeability is observed to increase reasonably for the passively damaged membranes. However, the salt rejection parameter rebounds in the same fashion as that for virgin membrane. But for the actively damaged membranes there is signicant increase in both permeability and salt passage. Obviously there is some factor underpinning the disparity in the way the membrane surface modied under the pressurized and unpressurized conditions. Referring to the research performed by Avlonitis et al. [5] the chlorination could lead to the change in the polymer morphology transforming them from crystalline to amorphous state, which changes the membrane performance. The high permeability and salt passage under pressurized conditions could be owing to the increase in the chain exibility and the transformation of crystalline to more amorphous state. At the same time, exposure at passive conditions seems to affect the polymer surface, but not well up to the level of salt passing through it. 3.2. FTIR analysis FT-IR spectroscopy is an effective tool to identify the modications/changes occurred on the polyamide active layer surface of the membrane. Typical FTIR spectrum obtained for the fresh BW30 FR membrane is shown in Fig. 2. The observed peak/band at characteristic wavenumbers are (A) Broad band around 3330 cm1 and multiple peaks in 33303060 cm1 region represents the hydrogen bonded NH stretching vibration [10]/NH stretching contributed by a coating over the BW-30 membrane/overlapping of OH stretching and NH vibration mode [11,12]. (B) Peak at 1664 is attributed to amide I band, contributed by the C O stretching in majority, but also by CN stretching and CCN deformation vibration.

(C) Peak at 1609 cm1 is representative of the C C ring stretching vibration. (D) Peak at 1542 cm1 is attributed to the amide II band stand for the NH in plane bending. The modication in the hydrogen bonding behavior and ring chlorination during the hypochlorite exposure has been studied with FTIR patterns. During the chlorine exposure the aromatic ring chlorination has been investigated to be the major change. Change in the hydrogen bonding mode, shift from intermolecular to intramolecular type of bonding has been observed to be the reason for membrane failure, both in linear [13] and cross-linked aromatic polyamide membrane [14,15]. In a virgin polyamide membrane hydrogen bonding is formed between a proton donor group (amide group) and a proton acceptor group (carbonyl group), which is then destroyed during the course of exposure to hypochlorite solution. The disturbance in the hydrogen bonding alters the force constant of both the groups and affects both stretching and bending vibrations of the groups. Hence the existence of hydrogen bonding in a virgin membrane will result in NH bending shifted to higher frequency, whereas the C O stretching and NH stretching frequency shifted to lower frequency. Therefore the breaking of the hydrogen bonds as a result of chlorination is expected to free the carbonyl group and the C O stretching peak to have a positive shift in frequency. Similarly the NH stretching vibrations will be shifted to higher frequency. The peak corresponding to NH bending will be shifted to lower frequency with hydrogen bond breaking. However the peak shift will be of lesser degree for the C O group compared to that of the NH group [16]. The FTIR spectra obtained for the virgin and chlorine damaged membranes at various concentrations of active conditions are shown on a common scale Fig. 3(a) and (b), the regions 38002500 and 18001500 cm1 , respectively. After chlorination, signicant reduction in the absorbance was observed in the hydrogen bonded NH stretching (3330 cm1 ). Also the increase in chlorine concentration was found to reduce the stretching concurrently, indicating the fall in extent of hydrogen bonding. The reduction in the absorbance could also be attributed to the loss of the coating over the polyamide layer upon chlorine exposure, referring to research performed by Tang et al. [12]. During chlorination, amide I band is shifted from its original position of 1664 cm1 to a higher frequency due to the replacement of hydrogen (on the amide nitrogen which is susceptible to chlorination) with chlorine. The increase in chlorine concentration weakens the bond strength and hence this brings a change in carbonyl group bonding fashion, from hydrogen bound to free carbonyl. For the 10,000 ppm h, a shift to higher frequency in the peak position of amide I band to 8 cm1 was observed.

Fig. 2. FTIR absorption spectrum obtained for the BW-30 FR virgin membrane.

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Fig. 4. FTIR spectra for the virgin membrane and membranes exposed to varying hypochlorite concentrations, 400, 1000, 4000 and 10,000 ppm h under passive conditions: (a) wavenumber 30002500 cm1 and (b) wavenumber 18001500 cm1 . Fig. 3. FTIR spectra for the virgin membrane and membranes exposed to varying hypochlorite concentrations, 400, 1000, 4000 and 10,000 ppm h under active conditions: (a) wavenumber 30002500 cm1 and (b) wavenumber 18001500 cm1 .

Before chlorination, the NH in plane bending (amide II band) at 1542 cm1 is restricted due to its hydrogen bonding with the neighboring groups. But, after chlorination, conversion of NH to NCl destroys or weakens the hydrogen bonds thereby resulting in the suppression and shifting of the characteristic peak to lower frequency. A shift of 3 cm1 has been observed for the 10,000 ppm h active exposure. The decline in peak intensities, at 1609 cm1 is a representation of the ring chlorination and suppression in the C C ring stretching vibration. Similarly the spectra obtained at the passive conditions are shown in Fig. 4(a) and (b). The change in peak absorbance at 3330 cm1 is signicant. However, the change is less pronounced for passive conditions compared to that of active conditions. The shift or suppression in the amide I and II bands were almost to the same extent as that of active conditions. The key difference between the two exposures is the ring stretching vibration peak at 1609 cm 1 , whose change is less signicant for the passive exposures. The suppression in the peak intensities for the active exposure was increasing with rise in chlorine concentrations, and the result is reproducible for the chlorine damaged membranes of different batches. But for the passively damaged membranes, the peak suppression was not changing as a function of chlorine concentration. To emphasize the modications in the characteristic peak positions, superimposed spectra for the highest chlorine concentration at active and passive exposure is presented in Fig. 5. The C C ring stretching vibrations at 1610 cm1 are suppressed strongly during active conditions than during passive ones. The extent of shift in the amide I and II bands are similar for the two exposure modes which implies that the change in hydrogen bonding behaviour is same for both the conditions. But change in the ring

stretching vibrations gets intensied under dynamic conditions. Chlorine damage of the polyamide surface is driven to the formation of N-chlorinated products at all conditions, but the further rearrangement seems to be encouraged by the external forces. To be precise, mechanical forces like stirring and pressurizing have effect on the progress of the reaction step, N-chlorinated amide structure to ring chlorinated structure (Orton rearrangement). Recalling the fact that salt passage was observed only with the actively damaged membranes, applied pressure supports the ring stretching, bringing decline in the membrane performance. Based on the results obtained, the proposed mechanism [1,10] for the chlorine degradation of the polyamide membrane can be modied as follows, where the N-chlorinated substituent was not considered as a reaction intermediate.

Fig. 5. Overlaid spectra of the (1) virgin (2) 10,000 ppm h passive and (3) 10,000 ppm h active hypochlorite exposed membranes, wavenumber 18001500 cm1 .

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The N-chlorinated substituent may not be completely considered as a short-lived intermediate, since the chlorine substitution on the amide nitrogen has been indicated through a change in the amide II band. Given that the nal product has no chlorine substitution at the nitrogen, there should be restricted NH in-plane bending. Instead, the results obtained show clear and permanent shift in the amide II position, for both active and passive exposures. Therefore the oxidative degradation of membrane is proposed to proceed to the formation of mixture of compounds, both Nchlorinated substitute and the rearranged structure of chlorinated ring. Given that the membrane chlorine damage is taking place by ring chlorination, the membrane modication can be targeted by the chemical modication of the polyamide active surface layer. The NH group being an ortho, para directing group, the chlorine substitution in the aromatic ring is expected to take place at the ortho or para position. Attaching pendant groups at these positions can prevent or minimize further attachment of chlorine to the aromatic ring. 3.3. Fujiwara analysis Originally, Fujiwara analysis is a test performed to quantify the presence of halogenated organics by spectrophotometric analysis, absorbance at 530 nm. These tests are capable of detecting concentrations as low as 1 g of the halogenated organics [1719]. However, in the area of membrane autopsy, Fujiwara test is being used as an indicative test to check if the membrane is affected by chlorine exposure. In the present study, Fujiwara tests were conducted qualitatively to test the applicability under different chlorine concentrations and two different exposure modes. These tests were also attempted as a quantitative assessment but were

not successful, which could be due to the low levels of the halogenated organics. The results of the Fujiwara tests obtained in the present study are shown in Table 2. The formation of the pink to red coloration in the organicaqueous phase is the positive result, conrming the oxidative degradation of the polyamide membrane. Negative results were obtained for the concentration of 4004000 ppm h for passive exposure and 400 ppm h for active exposure. Though the membrane damage was evident from the permeate ux, salt rejection values and the FIIR pattern, Fujiwara analysis is not accommodative enough to detect the membrane degradation of lesser degree. Even as qualitative test, Fujiwara tests may fail under certain conditions and therefore it would be worthwhile to adopt some accurate analytical methods in membrane autopsies to effectively address the oxidative degradation. 4. Conclusions The salt rejection and membrane permeability results indicate that the extent of membrane damage was dissimilar for the two different modes of exposure. Actively damaged membranes showed increase in permeability and salt passage. However, passively damaged membranes showed reasonable increase in permeability, but not the salt passage. The impaired membrane performance is brought in only at active exposures. Based on the results of the FTIR study, the chlorine attack has been found to affect the hydrogen bonding behavior and the ring stretching vibrations. Also the FTIR patterns due to the chlorine exposure are different for the passive and active conditions. The changes in the amide bands are almost same for both the exposures. On the other hand, the ring stretching vibrations are more prominent for the active conditions. Based on the shift in amide II bands for all exposure conditions and the difference in the extent of ring stretching, it is suggested that the reaction products could be mixture of both N-chlorinated and ring chlorinated products; and applied pressure seems to favor the rearrangement of Nchlorination to ring chlorination. Under active conditions of oxidative degradation, the reaction seems to progress right up to the formation of ring chlorination, bringing maximum damage to the membrane. The ring stretching and the formation of the chlorinated products, under vigorous operating conditions, appear to be the prime cause for the impaired

Table 2 Results of the Fujiwara analysis for the chlorine attacked membrane panels. Hypochlorite concentration, ppm h 400 1,000 4,000 10,000 Passive Negative Negative Negative Positive Active Negative Positive Positive Positive

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A. Antony et al. / Journal of Membrane Science 347 (2010) 159164 [7] N.P. Soice, A.R. Greenberg, W.B. Krantz, A.D. Norman, Studies of oxidative degradation in polyamide RO membrane barrier layers using pendant drop mechanical analysis, J. Membr. Sci. 243 (2004) 345355. [8] J. Benavente, M.I. Vzquez, Effect of age and chemical treatments on characteristic parameters for active and porous sublayers of polymeric composite membranes, J. Colloid Interface Sci. 273 (2004) 547555. [9] J. Benavente, M.I. Vzquez, R. de Lara, Modication of active and porous sublayers of aged polyamide/polysulfone composite membranes due to HNO3 treatment: effect of treatment time, J. Colloid Interface Sci. 297 (2006) 226234. [10] G.-D. Kang, C.-J. Gao, W.-D. Chen, X.-M. Jie, Y.-M. Cao, Q. Yuan, Study on hypochlorite degradation of aromatic polyamide reverse osmosis membrane, J. Membr. Sci. 300 (2007) 165171. [11] O. Coronell, B.J. Marias, X. Zhang, D.G. Cahill, Quantication of functional groups and modeling of their ionization behavior in the active layer of FT30 reverse osmosis membrane, Environ. Sci. Technol. 42 (2008) 52605266. [12] C.Y. Tang, Y.-N. Kwon, J.O. Leckie, Probing the nano- and micro-scales of reverse osmosis membranesa comprehensive characterization of physiochemical properties of uncoated and coated membranes by XPS, TEM, ATRFTIR, and streaming potential measurements, J. Membr. Sci. 287 (2007) 146156. [13] J. Glater, M.R. Zachariah, Mechanistic Study of Halogen Interaction with Polyamide Reverse-Osmosis Membranes, in: ACS Symposium Series, Philadelphia, PA, USA: ACS, 1985. [14] Y.-N. Kwon, J.O. Leckie, Hypochlorite degradation of crosslinked polyamide membranes. II. Changes in hydrogen bonding behavior and performance, J. Membr. Sci. 282 (2006) 456464. [15] K. Young-Nam, Y.T. Chuyang, O.L. James, Change of chemical composition and hydrogen bonding behavior due to chlorination of crosslinked polyamide membranes, J. Appl. Polym. Sci. 108 (2008) 20612066. [16] R.M. Silverstein, G.C. Bassler, T.C. Morrill, Spectrometric Identication of Organic Compounds, fth ed., John Wiley & Sons, Inc., 1991. [17] F.P. Milanovich, S.B. Brown, B.W. Colston Jr., P.F. Daley, K.C. Langry, A ber-optic sensor system for monitoring chlorinated hydrocarbon pollutants, Talanta 41 (1994) 21892194. [18] T. Uno, K. Okumura, Y. Kuroda, Mechanism of the Fujiwara reaction: structural investigation of reaction products from benzotrichloride, J. Org. Chem. 46 (1981) 31753178. [19] W.H. Cole, The pyridine test as a quantiative method for the estimation of minute amounts of chloroform, J. Biol. Chem. (1926) 173.

performance of membrane. Therefore minimizing the environment dynamism during chlorine contacts can reduce the membrane damage in industrial situation. Fujiwara analysis cannot be taken as an exclusive appraisal to evaluate the membrane damage by halogen exposure during the membrane autopsy, but necessarily be combined with other accurate analytical techniques. FTIR provides the structural modications on the membrane surface that occurs even with very low concentration and therefore can be deemed as an interactive tool in evaluating the membrane integrity loss. Acknowledgements We would like to thank Dow Filmtec for providing membranes for this study. We also thank Dr. Wolfgang Gernjak and Dr. Michael Lawrence from AWMC, University of Queensland, for their help in this study. References
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