PTFE/polyamide thin-film composite membranes using PTFE films modifiedwith ethylene diamine polymer and interfacial polymerization: Preparationand pervaporation application

Chung-Hao Yu, Irdham Kusumawardhana, Juin-Yih Lai, Ying-Ling Liu

R&D Center for Membrane Technology and Department of Chemical Engineering, Chung Yuan University, #200, Chung-Pei Road, Chungli, Taoyuan 32023, Taiwan

a r t i c l e i n f o

Article history:

Received 11 February 2009Accepted 21 March 2009Available online 5 April 2009

Keywords:

Plasma polymerizationInterfacial polymerizationComposite membranePoly(tetraﬂuoroethylene)

a b s t r a c t

Plasma polymerization of ethylene diamine (EDA) on PTFE film surfaces is applied to modify PTFE sur-faces to become hydrophilic and to incorporate amino groups onto PTFE surfaces. The surface-modifiedPTFE films are utilized as substrates for interfacial polymerization of EDA and trimesoyl chloride to pre-pare PTFE/polyamide thin-film composite (TFC) membranes. The effect of plasma power for plasma poly-merization on the morphology and performances of the PTFE/PA TFC membranes are examined anddiscussed. The presence of amino groups on the PTFE substrates provides chemical linkages betweenPTFE and PA layers in interfacial polymerization to make the PTFE/PA TFC membranes are stable for per-vaporation separations. A high permeation flux of 1910 g/h m

and a separation factor of 290 areobserved with the PTFE/PA TFC membranes for pervaporation dehydration on a 70 wt% isopropanol aque-ous solution at 70

C. This approach explores a new method to prepare PTFE-based TFC membranes viainterfacial polymerizations. The prepared TFC membranes could be potentially utilized in pervaporationand nanoﬁltration separations.

1. Introduction

Thin-film composite (TFC) membranes are attractive in mem-brane separations. One major approach to prepare TFC membranesis introduction of the selective layer to the top surfaces of poroussubstrates through interfacial polymerization[1–9]. In additionto reverse osmosis and nanofiltration, TFC membranes made frominterfacial polymerization have also been applied to pervaporationin liquid–liquidseparations.One exampleis polysulfone/polyimideTFC membranes and their application in pervaporation dehydra-tion on ethanol aqueous solutions[9].Another example is poly(acrylonitril)/polyamide TFC membranes, which were utilizedin the pervaporation dehydration on isopropanol (IPA)/water mix-tures[10,11]. However, the separation performances of the re-ported TFC membranes are not impressive enough due to thepoor stability of the membranes. Improvements on the stabilityof TFC membranes could be done with uses of high performancepolymersas thesubstratesofTFCmembranes. Forexamples,poly(-ether ether ketone)[12]and polyetherimide[13]were utilized as the substrates in preparation of TFC membranes basing on theirgood thermal stability and high chemical resistance. Another poly-mer being used as the porous support of TFC membranes waspoly(propylene)[14,15], which exhibits high durability, chemicalresistance, and sustainability in pH variation.Poly(tetrafluoroethylene), which possesses excellent chemicalresistance, good thermal stability, and environment sustainability,is attractive in the applications of membrane separations. How-ever, surface modifications on PTFE are requested for the applica-tions due to its surface inertness and hydrophobicity. To extendthe application scopes of PTFE in pervaporation separations, someof our previous efforts have been reported[16,18,17]. In 2006 wereported the first PTFE TFC membrane using porous PTFE films assubstrates and chitosan as the separation layers[18]. In 2008, wefurther applied the interfacial polymerization technique to preparePTFE/polyamide TFC membranes[17]. It was demonstrated thatincorporation of amine groups to PTFE surfaces is necessary forpolyamide interfacial polymerization to provide chemical linkagesbetweenthe PA selective layer and the PTFE substrate. In that workwe performed surface-initiated polymerization and post chemicalmodification to incorporate the amine groups to PTFE surfaces.However, the synthetic routes and steps were complicated andthe modification efficiency was not high.Plasma polymerization has been widely used in surface modifi-cations due to its simplicity and eases of operations[19–21].Therefore, in this work we try to employ plasma polymerizationinto the preparation route of the PTFE/PA TFC membranes to re-place the complicated surface-initiated polymerizations. Sinceamine groups are desired to be incorporated onto PTFE surfaceafter plasma polymerization, ethylene diamine (EDA) is utilizedas the monomer in plasma polymerization. The effect of plasmapower for plasma polymerization on the morphology and

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performances of the resulting PTFE/PA TFC membranes are exam-ined and discussed. The EDA plasma-polymerized PTFE ﬁlms aresuccessful for the preparation of PTFE/PA TFC membranes andthe membranes exhibits high performances in the pervaporationdehydration on an IPA aqueous solution.

2. Experimental

2.1. Materials

PTFE ﬁlms with a thickness of 500

m and pore sizes of 0.2–0.4

m were received from Yu-Min-Tai Co., Ltd., Taiwan. Ethylenediamine (EDA) was purchased from Acros Chemical Co. Trimesoylchloride (TMC) from Aldrich Chemical Co. was used as received.

2.2. Surface modiﬁcation on PTFE with EDA by plasma polymerization

PTFE surfaces were pre-treated with hydrogen plasma using acapacity coupling electrodes (Dressler HF-Technik GmbH, Ger-many; model CESAR-1310) under the conditions of a hydrogenmass ﬂow rate of 10 standard cubic centimeter per minute (sccm),a radio frequency of 13.56 MHz, a power of 50 W, a pressure of 0.3 torr, and a reaction time of 180 s[22]. Afterwards, the systemwasevacuatedtoapressureof 0.03 torr.EDA vaporwasintroducedto the system at 80

C under vacuum. Plasma polymerization of EDA on PTFE film surfaces was conducted with various plasmapowers for a polymerization time of 120 min. The flow rate of EDA was 13 sccm. The modified PTFE films were washed with dis-tilled water to remove out the physically absorbed EDA monomersand polymeric segments, and then dried under vacuum to result inthe PTFE–PEDA-

ﬁlms, where

denotes to the plasma power (inwatt) utilized for EDA polymerization.

2.3. Preparation of PTFE/PA TFC membranes via interfacial polymerization[17]

PTFE–PEDA films were immersed in a 5 wt% EDA aqueoussolution for 30 min. The films were taken out. After sweepingoff the EDA solution on the film surfaces, the films were put intoa TMC solution (1 wt% in toluene) for 3 min. The films were takenout, dried under ambient environment, and heat-treated at 70

Cfor 1 h. Finally the samples were washed with methanol anddried under ambient environment to give the PTFE/PA-

TFCmembranes, where

denotes to the plasma power (in watt) uti-lized for EDA polymerization in preparation of PTFE–PEDA-

ﬁlms.

2.4. Instrumental analysis

ATR–FTIR analysis on film and membrane surfaces were per-formed with a Perkin Elmer Spectrum One FTIR equipped witha multiple internal reflectance apparatus and a ZnSe prism asan internal reflection element. Scanning electron micrographs(SEM) were recorded with a Hitachi S-3000N SEM. Water contactangles were measured with an angle-meter (Automatic ContactAngle Meter, Model CA-VP, Kyowa Interface Science Co., Ltd., Ja-pan) at room temperature. Distilled water (5

L) was droppedon the sample surface at ten different sites. The average of tenmeasured values for a sample was taken as its water contactangle.

2.5. Pervaporation dehydration operation

Pervaporation dehydration operation was conducted with aconventional process[16]. The effective area of the used mem-brane is 6.7 cm

. The temperature of the feeding solution is 70

Cand the downstream (permeate side) pressure is 667–1067 Pa.Whilethesystemwasin steady-state(usuallyafterapre-operationin 2 h), the data was taken in 1 h period of continuing operation.The compositions of feeding solutions and permeates were deter-mined with a gas chromatography (China Chromatography GC-8700T). The separation factor (

water/organic compound

) was calculatedfrom equation of

water

organic compound

¼ ð

water

organic compound

water

organic compound

;

where

and

are the concentrations of permeate and feeding solu-tions, respectively, and the subscription (water and organic com-pound) indicates the species. Permeation ﬂux was determined bymeasuring the weight of permeate liquid through the membraneat given time. Data was obtained from the average of measuring re-sults from four pieces of separate membranes.

3. Results and discussion

3.1. EDA plasma polymerization on PTFE surfaces

Amino-functionalized PTFE surfaces were successfully utilizedin preparation of PTFE/PA TFC membranes via interfacial polymer-izationin the previous work[17]. To simplify the process of amino-functionalization on PTFE surfaces, plasma polymerization usingEDA as a monomer is utilized in this work (Fig. 1). After plasmapolymerization of EDA, some EDA polymer is deposited on PTFEfilm surfaces. The prepared PTFE–PEDAfilms possess amino groupson their surfaces and are reactive toward compounds with acylchloride groups (like TMC).Fig. 2shows the SEM micrographs of pristine PTFE and PTFE–PEDA films prepared at various plasmapowers. PEDA polymer covering on PTFE surfaces was observed.The EDA deposition yields are 0.077, 0.186, 0.216, and 0.211 mg/cm

for PTFE–PEDA ﬁlms prepared at a plasma power of 50, 100,150, and 200 W, respectively. Increase in the plasma powers from50 to 150 W increases the amounts of EDA polymers deposited onPTFE surfaces from 0.077 to 0.216 mg/cm

. However, etching effectbecomes more signiﬁcant for the sample prepared at high plasmapower of 200 W, as a relatively low EDA deposition yield of 0.211 mg/cm

and a very uneven surface are observed withPTFE–PEDA-200 (Fig. 2e). FTIR characterization on the PTFE/PEDAﬁlms provides supports to the presence of PEDA on the modiﬁedPTFE surfaces with the absorptions of N

H vibrations at 3353,

Fig. 1.

Preparation route and chemical structure of PTFE/PA TFC membranes.

C.-H. Yu et al./Journal of Colloid and Interface Science 336 (2009) 260–267

261

3262, 3175, and 1585 cm

(Fig. 3). The intensities of absorptionsrelating to N

H groups also increase with increasing the plasmapower in EDA polymerization, indicating high plasma power inEDA polymerization is effective to increase the PEDA amountsdeposited on PTFE surfaces. This result is coincident to the dataof the EDA deposition yields. The absorption at about 3300 cm

is attributed to the presence of

OH groups, which formed fromthe reaction between the radicals generated on the PTFE ﬁlm sur-face in plasma treatment and the oxygen in air. The presence of amine and hydroxyl groups results in the reductions of water con-tact angles of PTFE–PEDA ﬁlm surfaces from 120

to 45

. The sur-face densities of amine groups on PTFE–PEDA ﬁlms are alsomeasured using 4-nitrobenzaldehyde as a testing agent accordingto the reported method[23,24]. The surface densities of aminegroups of the PTFE/PDEA ﬁlms slightly increase with increases inthe plasma powers for EDA plasma polymerization, as values of about 5000 and 5800 groups/nm

are measured with PTFE–PEDA-50 and PTFE–PEDA-200, respectively. On the other hand,

Fig. 2.

Effect of plasma powers of EDA polymerization on the surface morphology (

1K) of PTFE–PEDA ﬁlms: (a) pristine PTFE (b) PTFE–PEDA-50, (c) PTFE–PEDA-100, (d)PTFE–PEDA-150, and (e) PTFE–PEDA-200. Plasma polymerization time: 120 min.262

C.-H. Yu et al./Journal of Colloid and Interface Science 336 (2009) 260–267