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
l
m and pore sizes of 0.2–0.4
l
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-
X
films, where
X
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-
X
TFCmembranes, where
X
denotes to the plasma power (in watt) uti-lized for EDA polymerization in preparation of PTFE–PEDA-
X
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
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
2
. 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 (
a
water/organic compound
) was calculatedfrom equation of
a
water
=
organic compound
¼ ð
Y
water
=
Y
organic compound
Þ
=
ð
X
water
=
X
organic compound
Þ
;
where
Y
and
X
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
2
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
2
. 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
2
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
A
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
Leave a Comment