European Polymer Journal 41 (2005) 23432353

EUROPEAN POLYMER JOURNAL

www.elsevier.com/locate/europolj

Expanded poly(tetrauoroethylene) membrane surface modication using acetylene/nitrogen plasma treatment

Chen-Yuan Tu a, Yi-Chieh Wang b, Chi-Lan Li b, Kueir-Rarn Lee J. Huang c, Juin-Yih Lai a
a

b,*

R&D Center for Membrane Technology, Department of Chemical Engineering, Chung Yuan University, Chung Li 32023, Taiwan b Department of Chemical Engineering, Nanya Institute of Technology, Chung Li 32034, Taiwan c Yeu Ming Tai Chemical Industrial Co., Ltd., Taichung Industrial Park, Taichung 407, Taiwan Received 18 January 2005; received in revised form 16 April 2005; accepted 17 April 2005 Available online 28 June 2005

Abstract In this article, expanded poly(tetrauoroethylene) (e-PTFE) membrane surface modication was carried out using acetylene/nitrogen plasma treatment (p-e-PTFE). The variation in surface morphology of the p-e-PTFE membranes was conrmed by FTIR-ATR, scanning electron microscopy (SEM), and contact angle measurements. It was found that the surface hydrophilicity increased with increasing nitrogen content in the feed gas mixture, RF power, and plasma treatment time. The surface pore size decreased with increasing RF power and plasma treatment time. The water contact angles of the modied e-PTFE membrane decreased from 125.8 to 34.1 through the acetylene/nitrogen plasma treatment. 2005 Elsevier Ltd. All rights reserved.
Keywords: Expanded poly(tetrauoroethylene); Plasma treatment; Hydrophilicity; Contact angle

1. Introduction Polytetrauoroethene (PTFE) displays many highly desirable bulk and surface properties, e.g., high thermal stability, chemical inertness, low dielectric constants, and extreme frictional resistance and low surface energy [1,2], based on the low polarizability of the CAF bond. These properties are desired in many applications like multilayer electronic packages, low friction lms, sealing or biomedical applications. The hydrophobic surface of

* Corresponding author. Tel.: +886 3453 5521; fax: +886 3436 1747. E-mail address: krlee@nanya.edu.tw (K.-R. Lee).

PTFE is a distinguishing property but a dicult problem in adhesion with other materials. Therefore, pretreatment is usually required to achieve satisfactory hydrophilicity and adhesion. There have been many studies on improving the surface properties of PTFE using various surface modication methods, such as chemical etching with sodium naphthalene [3], UVlasers, electron and ion beams irradiation [4,5], and plasma modication [1,68]. All of these lead to large increases in surface energy and surface hydrophilicity. Among these methods, plasma modication is the most notable technique. Plasma surface modied polymer surfaces can achieve the necessary properties, such as surface hydrophilicity, adhesion, material selectivity, and biocompatibility [9].

0014-3057/$ - see front matter 2005 Elsevier Ltd. All rights reserved. doi:10.1016/j.eurpolymj.2005.04.022

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Matching Network MFC MFC

Many kinds of gases can be used as a plasma medium including noble and reactive gases or organic volatile compounds. The former refers to polymer surface activation by plasma, while the latter refers to surface polymerization by plasma. Both methods can incorporate hydrophilic functional groups, such as carbonyl, carboxyl, hydroxyl, hydroperoxide, and amino groups to improve the polymer surface properties, such as surface wettability and biocompatibility. Surface polymerization by plasma enhances chemical vapor deposition (PECVD) and can also reduce the surface pore size of porous polymer membranes for reverse osmosis [10 13], pervaporation [14] and gas separation [15]. C2H2/N2 plasma systems were used in this work to systematically investigate the role of plasma treatment in e-PTFE membrane surface modication. C2H2/N2 plasma easily polymerizes the thin hydrophilic lm on the e-PTFE membrane surface. The addition of nitrogen to the hydrocarbon plasma reduces the degree of crosslinking in the polymeric material and forms polar or hydrophilic functional groups such as amines on the substrate polymer surface [16]. The plasma condition eects such as the power, monomer ow rate, and plasma treatment time on the surface hydrophilicity and morphology of the e-PTFE membranes are discussed in details.

Mixing Box
Pressure Gauge View port

13.56 MHz

C2H2 N2

membrane Heater

Exhaust

Thermocouple

Fig. 1. The schematic diagram of the plasma reactor system.

power were xed at 300 mTorr and 50300 W, respectively. The acetylene/nitrogen gas ow rate ratios were varied. The total gas mass ow rates were xed at 15 sccm (standard cm3/min). 2.3. Surface analysis 2.3.1. FTIR-ATR spectrum The spectrum of the pristine e-PTFE and the p-e-PTFE membranes were detected using a Fourier transform infrared spectrum analyzer with a attenuated total reection element (ATR), collected at 4 cm1 resolutions, and analyzed with a built-in standard software package (PerkinElmer Spectrum One, PerkinElmer Co., Norwalk, CT, USA). 2.4. Surface and cross-section morphology studies The morphologies of pristine e-PTFE and the p-ePTFE membranes were analyzed with scanning electron microscopy (SEM, Hitachi Model S4700). The membranes were immersed in liquid nitrogen to fracture and then sputtered wit Pt before analysis. 2.5. Surface hydrophilicity characterization The surface hydrophilicity of the pristine e-PTFE and the p-e-PTFE membranes was characterized using the surface contact angle of water. The contact angles of water on the membranes were measured in air at room temperature using the sessile drop method using an anglemeter (Automatic Contact Angle Meter, Model CA-VP; Kyowa Interface Science Co., Ltd., Japan). Increasing and decreasing the volume of the water drop until the three-phase boundary moves on the membrane surface measured the advancing and receding contact angles. The distilled water were dropped at least ten different sites on each sample, and the measured values of the contact angle were averaged. 2.6. Wateralcohol mixtures dehydration using vapor permeation measurement A traditional vapor permeation process was used [17]. The feed vapor is in direct contact with the membrane

2. Experimental 2.1. Materials The expanded PTFE membranes used were commercially available from YMT Co., Ltd., Taiwan, with a melting point of about 327 C. The mean pore size of the e-PTFE membranes was about 0.4 lm, with a thickness of 150 lm. The expanded PTFE membranes were cut to 5 cm 5 cm dimensions and provided as specimens for the surface modication experiments. The sample sheets were prepared by Soxhlet extraction. The nitrogen and acetylene used for the plasma treatments were pure grade (99.5% purity). 2.2. Plasma treatment by C2H2/N2 mixture gas Plasma treatment was carried out in a plasma enhanced chemical vapor deposition (PECVD) reactor system with two internal electrodes. This device was tted with a monomer inlet, pressure gauge, vacuum system, and matching network for 13.56 MHz radio frequency (RF) source capacity coupling. A schematic diagram of the plasma reactor system is shown in Fig. 1. The vacuum reactor system was evacuated to 20 mTorr with a rotary pump before plasma treatment. The monomers with controlled ow rates using a mass ow controller (MFC) system were then introduced into the reactor through a showerhead. The operating pressure and

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that eective area was 3.3 cm2. In this experimental, the permeation rate was measured the weight of permeate. The permeant compositions were measured using gas chromatography (G.C. China chromatography 8700T).

3. Results and discussion 3.1. Plasma condition eects on the surface hydrophilicity of the e-PTFE membranes The C2H2/N2 plasma treatment eect on the surface hydrophilicity of the e-PTFE membranes was investigated using water contact angle measurement, as shown in Table 1. It shows that the contact angle of the pristine e-PTFE membrane is 125.8, higher than that of the plasma treated p-e-PTFE membranes with dierent C2H2/N2 gas ow rate ratio. These phenomena might be due to the fact that the amine groups introduced onto the e-PTFE surface via plasma treatment resulted in the p-e-PTFE surface becoming more hydrophilic. Moreover, the surface hydrophilicity increased with increasing nitrogen content in the C2H2/N2 mixture gas. However, the hydrophilicity of the p-e-PTFE membranes did not increase using pure nitrogen plasma treatment. The chemical composition on the pristine ePTFE and C2H2/N2 plasma modied e-PTFE surfaces was analyzed with XPS. The XPS spectra for the above membrane surfaces are shown in Fig. 2. The C1s core level spectrum of pristine e-PTFE membrane (Fig. 2(a)) presented only a peak at 292.7 eV attributing to CF2 species. After C2H2/N2 plasma treatment, a new peak at 285 eV, which was contributed from CAH group. The other two peaks found for plasma treated PTFE membranes (Fig. 2(b)(d)) at 288.6 eV and 287.5 eV were due to the existence of CAN, C@O and CAO groups, respectively. The N1s core level spectrum of the C2H2/N2 plasma treated e-PTFE membranes (Fig. 2(e)(g)) exhibit N1s component at the bonding energy of 399.7 eV and 400.7 eV, which attributable to the amide and imide groups, respectively. These results conrmed that through the C2H2/N2 plasma treatment suc-

Table 1 Eect of C2H2/N2 gas ow rate ratio on the surface contact angle of the p-e-PTFE membrane C2H2/N2 gas ow rate ratio Surface contact angle of water () Pristine membrane 15/0a 10/5a 7.5/7.5a 5/10a 0/15a 125.8 2.0 90.6 2.9 58.7 1.6 56.3 1.9 53.6 1.4 115.0 5.5

a RF power: 100 W, 300 mTorr of system pressure, and 180 s plasma treatment time.

cessfully induce the hydrophilic functional groups onto the e-PTFE membrane surface, resulting in the p-ePTFE membranes with lower water contact angle than that of the pristine e-PTFE membrane. These results correspond well with the results from the surface water contact angle study, as indicated in Table 1. The p-e-PTFE membrane surface structure characterization using FTIR-ATR measurement can further explain the above phenomenon. Fig. 3 shows the FTIRATR spectrum of pristine e-PTFE and p-e-PTFE membranes using dierent C2H2/N2 mixture gas ow rate ratios. For the pristine e-PTFE (Fig. 3(a)), the two strong absorbance peaks appeared at 1200 cm1 and 1148 cm1 were due to the CAF asymmetric and symmetrical stretching vibrations in the e-PTFE. When treated with pure C2H2 gas plasma (Fig. 3(b)), a thin hydrocarbon lm was deposited onto the e-PTFE surface. The absorbance peaks appeared at 2920 cm1 and 1450 cm1 were due to the CAH stretching vibrations; 1740 cm1 and 3300 cm1 due to the carbonyl and hydroxyl groups, respectively. Those oxygen-containing functional groups were incorporated by the residual free radicals that reacted readily with oxygen and water in the air. However, the e-PTFE treated with C2H2/N2 mixture gas plasma, introduced dierent functional groups onto the e-PTFE surface. The new absorbance peaks appeared at 2820 cm1 due to the stretching vibration of the CAH bond of the NACAH group, and 1640 cm1 were due to the NAH bending of primary amine. When the C2H2/N2 mixture gas were excited to a plasma phase, the C2H2 and N2 gas molecules might be excited to form hydrocarbon and nitrogen atoms or free radicals from electrons. These reactive atoms and free radicals could be recombined to form another molecule. Amine groups were thus formed on the e-PTFE membrane surface. Increasing the nitrogen content in the mixture gas provided more nitrogen atoms to combine with the hydrocarbon radicals to increase the amine group concentration on the p-e-PTFE surface, as shown in Fig. 3. These amine groups introduced onto the ePTFE surface resulted in the membrane surface becoming more hydrophilic. This observation corresponds well with the results shown in Table 1. Tables 2 and 3 show the RF power and plasma treatment time inuence on the p-e-PTFE surface hydrophilicity, respectively. The p-e-PTFE surface hydrophilicity increased with increasing RF power and plasma treatment time. These results show that the active species from the acetylene and nitrogen gas mixture dissociation increases when the RF power increases. Thus, the amine group on the p-e-PTFE membrane surface increased, resulting from the recombination of active species. In addition, the higher RF power supplied to the C2H2/N2 mixture gas also increased the deposition rate in the plasma treatment system. For example, RF power increased to 300 W induced the hydrophobic pristine

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Fig. 2. C1s core-level XPS spectra of (a) pristine e-PTFE, (b) C2H2/N2 = 10/5, (c) C2H2/N2 = 7.5/7.5, (d) C2H2/N2 = 5/10 plasma treated e-PTFE membrane, and N1s core-level XPS spectra of (e) C2H2/N2 = 10/5, (f) C2H2/N2 = 7.5/7.5, (g) C2H2/N2 = 5/10 plasma treated e-PTFE membrane.

e-PTFE surface (contact angle with water = 125.8 2.0) to become a hydrophilic surface (contact angle with water = 34.1 0.9). Fig. 4 shows that the intensity of the 1640 cm1 (due to the NAH bending of primary amine) increases with increasing the RF power. This result conrms that the p-e-PTFE surface hydrophilicity increased with increasing the RF power. 3.2. Aging time inuence on the surface hydrophilicity of p-e-PTFE membrane To investigate the eect of storage time on the surface hydrophilicity of p-e-PTFE membrane, the plasma trea-

ted membrane was stored in the environment keep in 25 C and relative humidity of 70%, as shown in Fig. 5. After plasma treatment (C2H2/N2 = 5/10 sccm, 100 W, 300 mTorr, 180 s), the p-e-PTFE surface became a hydrophilic surface (water contact angle = 53.6 1.4). However, the surface hydrophilicity decreased rapidly and leveled o after 2 weeks storage in atmosphere. These phenomena might be due to polymers modied using plasma caused a reversible conformational transformation. The plasma modied layer might be submerged to change the surface free energy of a polymer stored in air [18]. Thus, the hydrophilicity of the p-e-PTFE membrane decreases in the initial aging

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(a) (b) (c) (d) (e)

transmittance

(f)

4000

3500

3000

2500

2000

1500

1000

wave number

(cm-1)

Fig. 3. FTIR-ATR spectrum of the plasma treated e-PTFE membranes by dierent C2H2/N2 gas ow rate ratio (100 W, 180 s). (a) Pristine, (b) 15/0, (c) 10/5, (d) 7.5/7.5, (e) 5/10, (f) 0/15 (sccm).

Table 2 Eect of RF power on the surface contact angle of p-e-PTFE membrane RF power Pristine membrane 50 Wa 100 Wa 150 Wa 200 Wa 250 Wa 300 Wa Surface contact angle of water () 125.8 2.0 69.0 2.1 53.6 1.4 48.4 1.0 44.4 2.9 39.3 1.3 34.1 0.9

Table 3 Eect of plasma treatment time on the surface contact angle of p-e-PTFE membrane Plasma treatment time Pristine membrane 30 sa 180 sa 300 sa 600 sa Surface contact angle of water () 125.8 2.0 79.1 1.3 34.1 0.9 33.7 2.1 33.6 2.4

a C2H2/N2 gas ow rate ratio of 5/10 sccm, RF power of 300 W, and 300 mTorr of system pressure.

a C2H2/N2 gas ow rate ratio of 5/10 sccm, 300 mTorr of system pressure, and 180 s plasma treatment time.

test period. The surface contact angle of water remained at about 63 until 2 weeks storage in air. The hydrophobic recovery phenomenon is due to the migration of hydrophilic groups that are form by the plasma treatment from the surface layer into the bulk layer because of the thermal motion of polymer chain. If we can restrain the migration of polymer chain, the hydrophobic recovery rate might be suppressed. With increasing the plasma treatment time, the amount of hydrophilic functional groups can be introduce onto the e-PTFE membrane surface (as shown in Fig. 6). Thus the long

hydrophilic polymer chain is dicult to migrate into the bulk layer, and the modied polymer surface will keep hydrophilic. 3.3. Post-treatment inuence on p-e-PTFE surface hydrophilicity The polymer treated with plasma could produce many free radicals on the polymer surface even in atmosphere. These highly reactive radicals might react rapidly with oxygen and water in air to form oxygen-containing species such as hydroperoxides, alcohols, acids, ketones, etc. When the plasma treated p-e-PTFE membrane was

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(a) (b) (c) (d) (e)

transmittance

(f) (g)

4000

3500

3000

2500

2000

1500

1000

wave number (cm-1)

Fig. 4. FTIR-ATR spectrum of the plasma treated e-PTFE membranes by dierent RF power (C2H2/N2 = 5/10 sccm, 180 s). (a) Pristine, (b) 50 W, (c) 100 W, (d) 150 W, (e) 200 W, (f) 250 W, (g) 300 W.
70

Contact angle with water (degree)

60

50

air. The water contact angle of the w-p-e-PTFE membrane was obviously smaller than that of the p-e-PTFE membrane. In addition, increasing the acetylene content in the C2H2/N2 mixture gas followed by post-treatment resulted in increased hydrophilicity in the p-e-PTFE membrane. The acetylene plasma excited a great amount of free radicals because of the unsaturated acetylene molecule bond. 3.4. Scanning electron microscopy studies Scanning electron micrographs of p-e-PTFE membranes treated under dierent plasma conditions are shown in Figs. 79. The C2H2/N2 mixture gas ow rate ratio eects on the surface morphology of p-e-PTFE membranes are shown in Fig. 7. Compared with the pristine e-PTFE membrane (Fig. 7(a)), the surface pore size of the p-e-PTFE membrane was reduced slightly with increased acetylene content in the gas mixture. When acetylene content in the mixture gas was increased, thus increasing the amount of polymerized species and deposition rate, resulting in reduced p-e-PTFE membrane surface pore size. In addition, the RF power and plasma treatment time eects on the p-e-PTFE membrane surface morphology are shown in Figs. 8 and 9, respectively. The surface pore size decreased with

40

30 0

10

20

30

40

50

60

Time (day)
Fig. 5. Eect of aging time on the surface hydrophilicity of the p-e-PTFE membrane (C2H2/N2 = 5/10 sccm, 100 W, 300 mTorr, 180 s).

immediately immersed into distilled water (w-p-ePTFE), the residual radicals could react directly with the water to form hydrophilic species. Table 4 shows the post-treatment eect on p-e-PTFE membrane surface contact angle with water after 2 days storage in

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(a) (b) (c) (d)

transmittance

(e)

4000

3500

3000

2500

2000

1500

1000

wave number (cm-1)

Fig. 6. FTIR-ATR spectrum of the plasma treated e-PTFE membranes by dierent treatment time (C2H2/N2 = 5/10 sccm, 300 W). (a) Pristine, (b) 30 s, (c) 180 s, (d) 300 s, (e) 600 s.

increasing RF power and plasma treatment time, forming a thin lm on the e-PTFE surface. Yasuda stated that, for the power-decient, the deposition rate is linearly dependent [19]. The higher supplied RF power increased the deposition rate to reduce the p-e-PTFE membrane surface pore size. Fig. 8(c) shows that many spherical particles were deposited onto the e-PTFE surface. As the higher RF power supplied to excite the monomer gas formed too many active species, the
Table 4 Eect of post-treatment on the surface contact angle of p-ePTFE membranes C2H2/N2 gas ow rate ratio Pristine membrane 15/0b 10/5b 7.5/7.5b 5/10b 0/15b
a

plasma polymerization of C2H2/N2 might be dominant in the gas phase reaction. The polymerization took place in the gas phase and deposited onto the e-PTFE surface. Fig. 10 shows a cross-sectional view of pristine e-PTFE and plasma treated p-e-PTFE membranes. It shows that the plasma polymerization is located on the surface also in the bulk e-PTFE membrane. This demonstrates that for a porous polymer membrane, plasma could pass through the pores and modify the inner membrane layers. 3.5. Water contact angle hysteresis of p-e-PTFE membranes The water contact angle of a material surface is a function of the surface topography, surface heterogeneity, swelling and supercial reorganization. Wenzel [20] developed the rst equation relating the surface water contact angle and surface roughness: cos hw r cos h where hw is the contact angle on a rough surface, h is the contact angle observed on a smooth surface, and r is the surface roughness or the average ratio of the actual to the apparent areas. The surface roughness can therefore increase or decrease the water contact angle depending

Surface contact angle of water () e-p-PTFE (2 day) w-p-e-PTFEa (2 day) 92.2 1.5 79.1 1.1 75.5 5.2 70.2 2.6 116.2 2.0 60.9 5.0 62.7 4.3 65.7 3.4 73.2 3.4 110.2 5.4

w-p-e-PTFE: immersed the plasma treated p-e-PTFE membrane into distill water immediately. b RF power: 300 W, 300 mTorr of system pressure, and 180 s plasma treatment time.

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Fig. 7. Surface scanning electron micrographs of the plasma modied e-PTFE membranes by C2H2/N2 gas ow rate ratio (100 W, 180 s). (a) Pristine, (b) 10/5, (c) 7.5/7.5, (d) 5/10, (e) 0/15 sccm.

on the equilibrium contact angle value on a smooth surface. Thus, the water contact angle hysteresis data of the pristine e-PTFE and p-e-PTFE membranes were shown in Table 5. It shows that the water contact angle hysteresis decreased with increasing the C2H2/N2 plasma treatment time. These phenomena might be due to the fact that the C2H2/N2 plasma treatment time increased results the surface pore size and/or surface roughness of the p-e-PTFE membrane decreased. 3.6. Waterethanol mixture dehydration using vapor permeation The plasma treatment eects on the vapor permeation performance of 90 wt% aqueous ethanol solution

through the e-PTFE and p-e-PTFE membranes are shown in Table 6. The permeation rate of the pristine e-PTFE membrane was higher than that for the C2H2/ N2 plasma treated p-e-PTFE membrane. An opposite trend for the water concentration in the permeate was also observed. These phenomena might be because the C2H2/N2 plasma deposited a thin lm onto the e-PTFE surface resulting in decreased pore size and porosity. The results discussed in the preceding paragraph were further conrmed by SEM analysis. The SEM study in Fig. 11 shows that the surface structure of the pristine e-PTFE membrane has high porosity. However, the surface of the C2H2/N2 plasma treated p-e-PTFE membrane was smooth, tight, and with fewer voids. Thus, the permeation rate of the p-e-PTFE membrane was

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Fig. 8. Surface scanning electron micrographs the plasma treated e-PTFE membranes by dierent RF power (C2H2/N2 = 5/10 sccm, 180 s). (a) Pristine, (b) 50 W, (c) 100 W, (d) 150 W, (e) 200 W, (f) 250 W, (g) 300 W.

Fig. 9. Surface scanning electron micrographs of the plasma treated e-PTFE membranes by dierent plasma treatment time (300 W, C2H2/N2 = 5/10 sccm). (a) 30 s, (b) 180 s, (c) 300 s, (d) 600 s.

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Fig. 10. Cross-section view of scanning electron micrographs of the plasma modied e-PTFE membranes (C2H2/N2 = 5/10 sccm, 300 s). (a) Pristine and (b) 300 W.

Table 5 Water contact angle hysteresis of e-PTFE and p-e-PTFE membranea Item/treatment time (s) Advancing angle () Receding angle () Contact angle hysteresis ()
a

0 152.3 101.8 50.5

30 93.5 44.9 48.6

180 65.8 27.1 38.7

300 57.1 23.9 33.2

600 37.8 14.2 23.6

lower and the water concentration in the permeate was higher than that from the e-PTFE membrane. These results correspond well with the results from the vapor permeation study, as indicated in Table 6.

4. Conclusions With the goal of improving the surface hydrophilicity of e-PTFE membranes, an investigation was performed to test the eects of C2H2/N2 mixture gas plasma on the surface morphology of e-PTFE membrane. It was found that the surface hydrophilicity increased with increasing nitrogen content in the mixture gas, RF power, and plasma polymerization time. The water contact angles of the pristine e-PTFE and acetylene/nitrogen plasma treated p-e-PTFE membrane were 125.8 and 34.1, respectively. However, the surface hydrophilicity decreased with increasing aging time in an atmosphere environment within 2 weeks. The surface pore size could be controlled using dierent plasma parameters. As the plasma treatment time was increased, a thin

C2H2/N2 plasma condition: C2H2/N2 gas ow rate ratio of 5/10 sccm, RF power of 300 W, and 300 mTorr of system pressure.

Table 6 Eect of C2H2/N2 plasma treatment on the vapor permeation of 90 wt% aqueous ethanol solutions through e-PTFE membrane Membrane Pristine e-PTFE p-e-PTFEa Permeation rate (g/m2 h) 31,078 666 H2O in permeate (wt%) 10 72

a C2H2/N2 mixture gas ow rate ratio: 5/10; power: 300 W; pressure: 300 mTorr; plasma deposition time: 30 min.

Fig. 11. Surface scanning electron micrographs of the plasma modied e-PTFE membranes (C2H2/N2 = 5/10 sccm, 30 min). (a) Pristine e-PTFE and (b) 300 W.

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hydrophilic layer was deposited onto the e-PTFE membrane surface. The vapor permeation results were obtained using a p-e-PTFE membrane with 30 min. C2H2/N2 plasma deposition, giving a permeation rate of 666 g/m2 h and water concentration in permeate of 72 wt% for a 90 wt% aqueous ethanol mixtures.

Acknowledgements The authors wish to sincerely thank the Ministry of Economic Aairs and National Science Council of Taiwan, ROC, for the nancial support of this work.

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