Construction of Renewable Superhydrophobic Surfaces via Thermally Induced Phase Separation and Mechanical Peeling

We report a simple preparation method of a renewable superhydrophobic surface by thermally induced phase separation （TIPS） and mechanical peeling. Porous polyvinylidene fluoride （PVDF） membranes with hierarchical structures were prepared by a TIPS process under different cooling conditions, which were confirmed by scanning electron microscopy and mercury intrusion porosimetry. After peeling off the top layer, rough structures with hundreds of nanometers to several microns were obtained. A digital microscopy determines that the surface roughness of peeled PVDF membranes is much higher than that of the original PVDF membrane, which is important to obtain the superhydrophobicity. Water contact angle and sliding angle measurements demonstrate that the peeled membrane surfaces display super- hydrophobicity with a high contact angle （152°） and a low sliding angle （7.2°）. Moreover, the superhydrophobicity can be easily recovered for many times by a simple mechanical peeling, identical to the original superhydrophobicity. This simple preparation method is low cost, and suitable for large-scale industrialization, which may offer more opportunities for practical applications.

PREPARATION OF MICROPOROUS ULTRA HIGH MOLECULAR WEIGHT POLYETHYLENE (UHMWPE) BY THERMALLY INDUCED PHASE SEPARATION OF A UHMWPE/LIQUID PARAFFIN MIXTURE

Ultra-high molecular weight polyethylene (UHMWPE) with a microporous structure was prepared via thermally induced phase separation (TIPS).Liquid paraffin (LP) was used as a diluent in the preparation of microporous UHMWPE. Small angle laser light scattering (SALLS) and differential scanning calorimetry (DSC) were used to determine the phase separation temperatures,i.e.the cloud points and the dynamic crystallization temperatures,respectively.It was found that the cloudI points were coincident with the cryst...

Effect of Diluent on the Morphology and Performance of IPP Hollow Fiber Microporous Membrane via Thermally Induced Phase Separation

Isotactic polypropylene （iPP） hollow fiber microporous membranes were prepared using thermally induced phase separation （TIPS） method. Di-n-butyl phthalate （DBP）, dioctyl phthalate （DOP）, and the mixed solvent were used as diluents. The effect of α （DOP mass fraction in diluent） on the morphology and performance of the hollow fiber was investigated. With increasing α, the morphology of the resulting hollow fiber changes from typical cellular structure to mixed structure, and then to typical particulate structure. As a result, the permeability of the hollow fiber increases sharply, and the mechanical properties of the hollow fiber decrease obviously. It is suggested that the morphology and performances of iPP hollow fiber microporous membrane can be controlled via adjusting the compatibility between iPP and diluent.

Effects of F127 on Properties of PVB/F127 Blend Hollow Fiber Membrane via Thermally Induced Phase Separation

Hydrophilic poly(vinyl butyral)(PVB) /Pluronic F127(F127) blend hollow fiber membranes were prepared via thermally induced phase separation(TIPS) ,and the effects of blend composition on the performance of hydrophilic PVB/F127 blend hollow fiber membrane were investigated.The addition of F127 to PVB/polyethylene glycol(PEG) system decreases the cloud point temperature,while the cloud point temperature increases slightly with the addition of F127 to 20%(by mass) PVB/F127/PEG200 system when the concentration of F127 is not higher than 5%(by mass) .Light scattering results show that the initial inter-phase periodic distance formed from the phase separation of 20%(by mass) PVB/F127/PEG200 system decreases with the addition of F127,so does the growth rate during cooling process.The blend hollow fiber membrane prepared at air-gap 5mm,of which the water permeability increases and the rejection changes little with the increase of F127 concentration.For the membrane prepared at zero air-gap,both water permeability and rejection of the PVB/F127 blend membrane are greater than those of PVB membrane,while the tensile strength changes little.Elementary analysis shows that most F127 in the polymer solution can firmly exist in the polymer matrix,increasing the hydrophilicity of the blend membrane prepared at air-gap of 5mm.

PREPARATION OF HIGH DENSITY POLYETHYLENE/POLYETHYLENE-BLOCK-POLY(ETHYLENE GLYCOL)COPOLYMER BLEND POROUS MEMBRANES VIA THERMALLY INDUCED PHASE SEPARATION PROCESS AND THEIR PROPERTIES

High density polyethylene （HDPE）/polyethylene-block-poly（ethylene glycol） （PE-b-PEG） blend porous membranes were prepared via thermally induced phase separation （TIPS） process using diphenyl ether （DPE） as diluent. The phase diagrams of HDPE/PE-b-PEG/DPE systems were determined by optical microscopy and differential scanning calorimetry （DSC）. By varying the content of PE-b-PEG, the effects of PE-b-PEG copolymer on morphology and crystalline structure of membranes were studied by scanning electron microscopy （SEM） and wide angle X-ray diffraction （WAXD）. The chemical compositions of whole membranes and surface layers were characterized by elementary analysis, Fourier transform infrared spectroscopy-attenuated total reflection （FTIR-ATR） and X-ray photoelectron spectroscopy （XPS）. Water contact angle, static protein adsorption and water flux experiments were used to evaluate the hydrophilicity, antifouling and water permeation properties of the membranes. It was found that the addition of PE-b-PEG increased the pore size of the obtained blend membranes. In the investigated range of PE-b-PEG content, the PEG blocks could not aggregate into obviously separated domains in membrane matrix. More importantly, PE-b-PEG could not only be retained stably in the membrane matrix during membrane formation, but also enrich at the membrane surface layer. Such stability and surface enrichment of PE-b-PEG endowed the blend membranes with improved hydrophilicity, protein absorption resistance and water permeation properties, which would be substantially beneficial to HDPE membranes for water treatment application.

Fabrication of poly(vinylidene fluoride) membrane via thermally induced phase separation using ionic liquid as green diluent

Ionic liquid(IL),1-butyl-3-methylimidazolium hexafluorophosphate([BMIM]PF6)as a new and environmentally friendly diluent was introduced to prepare poly(vinylidene fluoride)(PVDF)membranes via thermally induced phase separation(TIPS).Phase diagram of PVDF/[BMIM]PF6 was measured.The effects of polymer concentration and quenching temperature on the morphologies,properties,and performances of the PVDF membranes were investigated.When the polymer concentration was 15 wt%,the pure water flux of the fabricated membrane was up to nearly 2000 L·m-2·h-1,along with adequate mechanical strength.With the increasing of PVDF concentration and quenching temperature,mean pore size and water permeability of the membrane decreased.SEM results showed that PVDF membranes manufactured by ionic liquid(BMIm PF6)presented spherulite structure.And the PVDF membranes were represented asβphase by XRD and FTIR characterization.It provides a new way to prepare PVDF membranes with piezoelectric properties.

Synergistic action of non-solvent induced phase separation in preparation of poly(vinyl butyral) hollow fiber membrane via thermally induced phase separation

A systematic study of air gap distance effects on the structure and properties of poly(vinyl butyral)hollow fiber membrane via thermally induced phase separation(TIPS)has been carried out.The results show that the hollow fiber membrane prepared at air gap zero has no skin layer; the pore size near the outer surface is larger than that near the inner surface; and the special pore channel-like structure near the outer surface is formed,which is quite different with the typical sponge-like structure caused by TIPS and the finger-like structure caused by non-solvent induced phase separation(NIPS),because of the synergistic action of non-solvent induced phase separation at air gap zero.The pore size gradually decreases from outer surface layer to the intermediate layer,but increases gradually from intermediate layer to the inner surface layer.With the increase of air gap distance,the pore size near the outer surface gets smaller and a dense skin layer is formed,and the pore size gradually increases from the outer surface layer to the inner surface layer.Water permeability of the hollow fiber membrane decreases with air gap distance,the water permeability decreases sharply from 45.50×10-7 to 4.52×10-7 m3/(m2·s·kPa)as air gap increases from 0 to 10 mm at take-up speed of 0.236 m/s,further decreases from 4.52×10-7 to 1.00×10-8 m3/(m2·s·kPa)as the air gap increases from 10 to 40 mm.Both the breaking strength and the elongation increase with the increase of air gap distance.The breaking strength increases from 2.25 MPa to 4.19 MPa and the elongation increases from 33.9% to 132.6% as air gap increases from 0 mm to 40 mm at take-up speed 0.236 m/s.

Effects of coagulation bath temperature on structure and performance of poly(vinyl butyral) hollow fiber membranes via thermally induced phase separation

Poly （vinyl butyral） （PVB） hollow fiber membranes were fabricated via thermally induced phase separation （TIPS）. The effects of coagulation bath temperature （CBT） on the structure and performance of membranes were investigated in detail. The morphologies of the membranes were studied by scanning electron microscopy （SEM）, the performances of water permeability, rejection, breaking strength and elongation were measured, respectively. The results indicate that all the membranes have the asymmetric morphology and the thickness of the skin layer decreases and the pore size of the outer layer increases with the increase of CBT. The permeability of membranes prepared at air gap 1.0 cm and take-up speed 0.253 m/s increases from 1.047×10-7 to 5.909×10-7 m3/（m2·s-kPa） with the CBT increasing from 20 ℃ to 40℃, and sharply increases to 35.226×10 7 m3/（m2.s.kPa）once the CBT arrives at 50 ℃. While the carbonic ink rejections have no significant decrease, totally exceed 98%, but that of acid-maleic acid copolymer greatly decreases with the increase of CBT. Both the breaking strength and elongation decrease with the increase of CBT.

Effect of Extractant and Cold-drawing on the Structure and Performance of HDPE Hollow Fiber Membranes Fabricated via Thermally Induced Phase Separation Method

Microporous polyolefin hollow fiber membranes were prepared from high density polyethylene （HDPE）-paraffin solution via thermally induced phase separation （TIPS） method. Effects of extraction and cold-drawing condition on membrane structure and performance were investigated.Five volatile solvents were used as extractant. Dimension of hollow fiber and gas permeation rate of membrane were measured. Mierostructure of membrane was examined by Scanning Electronic Microscope （SEM）. The results show that the membrane treated by pentane possesses a higher porosity, nitrogen permeability and lower shrinkage than those of membranes extracted by other three extractants. It is also found that the membrane stretched 133% shows the highest porosity and gas permeability in this study.

Fabrication of Poly(vinylidene fluoride) /Polysulfone Flat Blend Membranes via Thermally Induced Phase Separation Process for Water Treatment

Poly(vinylidene fluoride) /polysulfone(PVDF/PSF) flat blend membrane was prepared via thermally induced phase separation(TIPS) technique.The membrane formation mechanism and membrane structure were investigated and the effects of PSF/PVDF weight ratio on morphology,crystallinity,porosity,and mechanical properties of the membrane were discussed.The relationship between membrane structure and performances,such as pure water flux and the rejection of carbonic black,was also discussed.It was found that solid-liquid(S-L) phase separation occurred for the PVDF/PSF/diluent system.The addition of PSF influences structure and crystallinity of the membrane,which in turn influences mechanical properties and performances of the membrane.The results reveal that it is possible to obtain network structure via S-L phase separation by blending the polymer,which has a partial compatibility with PVDF.

基于RTIPS法的聚醚砜/TiO_(2)-多巴胺复合微孔膜的制备及过滤性能

基于逆热致相分离(RTIPS)工艺制备聚醚砜(PES)微孔膜,探究纳米TiO_(2)和多巴胺对PES微孔膜分离性能的影响。结果显示,80℃凝固浴工艺下得到的微孔膜均呈现100%海绵结构,复合膜表皮最小孔径为300 nm。添加0.5%纳米TiO_(2)的复合膜(MTN-0.5)对亚甲基蓝的去除率最高,为99.1%,流量恢复率95.3%;额外添加1%多巴胺(MTN-0.5/1)的复合膜对牛血清蛋白(BSA)分离率最高,为82.2%,流量恢复率96.6%。改性后复合膜的防污性能得到明显提高。

Formation of microporous polymeric membranes via thermally induced phase separation： A review

A review of recent research related to micro- porous polymeric membranes formed via thermally induced phase separation （TIPS） and the morphologies of these membranes is presented. A summary of polymers and suitable diluents that can be used to prepare these microporous membranes via TIPS are summarized. The effects of different kinds of polymer materials, diluent types, cooling conditions, extractants and additive agents on the morphology and performance of TIPS membranes are also discussed. Finally new developments in TIPS technology are summarized.

用TIPS法成型超高分子量聚乙烯微孔材料的机理分析

超高分子量聚乙烯 (UHMW- PE)微孔材料是以 UHMW- PE为聚合物基体的新型功能性材料 ,根据其特点 ,热致相分离 (TIPS)方法被用于 UHMW- PE微孔材料的成型。文中简要分析了 TIPS方法的热力学机理 ,借助 UHMW- PE/溶剂二元体系相图综述了相分离过程。

TIPS法iPP中空纤维膜的拉伸性能研究

通过熔融共混等规聚丙烯(iPP)/邻苯二甲酸二丁酯(DBP)/邻苯二甲酸二辛酯(DOP)体系,采用热致相分离法(TIPS)制备iPP中空纤维膜,且在不同的拉伸温度及拉伸比下对中空纤维膜进行拉伸研究.对膜结构与透过性能进行了表征.采用环境扫描电子显微镜(SEM)对膜的内、外表面以及截面结构进行观测,发现拉伸后膜外表面的皮层以及膜结构得到有效改善.使用电子式万能试验机对中空纤维膜的拉伸强度进行了测试.随着拉伸温度和拉伸比的增加,膜的孔隙率、纯水通量以及拉伸强度均呈现先增大后减小的趋势.膜的孔隙率最大可提高35.3%,纯水通量提高了286.9%,拉伸强度可提高至6.86 MPa.nano-SiO2(纳米SiO2)添加的杂化膜经过拉伸后,孔隙率增大了46.8%,纯水通量提高了416.1%,拉伸强度提高了181.9%.研究表明:通过对iPP中空纤维膜进行拉伸处理,可以优化膜结构,并改善了膜表面皮层以及透过性能.

Poly(vinylidene fluoride-co-hexafluoro propylene) membranes prepared via thermally induced phase separation and application in direct contact membrane distillation

A non-toxic and environmentally safe diluent,acetyl tributyl citrate,was employed to prepare poly(vinylidene fluoride)-co-hexafluoropropylene membranes via thermally induced phase separation.Effects of the polymer concentration on the phase diagram,membrane morphology,hydrophobicity,pore size,porosity and mechanical properties(tensile stress and elongation at break)were investigated.The results showed that the pore size and porosity tended to decrease with increasing polymer concentration,whereas the contact angle,liquid entry pressure and mechanical properties showed the opposite trend.In direct contact membrane distillation operation with 3.5 wt-%sodium chloride solution as the feed solution,the prepared membranes performed high salt rejection(>99.9%).Furthermore,the prepared membranes retained excellent performance in long-term stability tests regarding the permeate flux and salt rejection. ne distillation.

STRUCTURE AND PERFORMANCE OF POLYAMIDE-6 MEMBRANES PREPARED BY THERMALLY INDUCED PHASE SEPARATION

The asymmetric polyamide-6 （PA6） membranes were prepared by thermally induced phase separation. From the scanning electron microscopy （SEM） images, it is observed that with the increase of silicon dioxide （SiO2） content the structure of obtained membranes gradually varied from cellular structure to large ball-shaped cluster aggregates. Subsequently, with the addition of SiO2, pure water flux increased first and then decreased, while rejection showed the opposite trend. Besides, raising the coagulation bath temperature was favorable to increase pure water flux. Consequently, different membrane morphologies and performance were obtained by changing SiO2 content and coagulation bath temperature.

稀释剂对TIPS法等规聚丙烯中空纤维微孔膜孔径及其连通性的影响

Isotactic polypropylene(iPP) hollow fiber microporous membranes were prepared via thermally induced phase separation(TIPS)method.The mixture of di-n-butyl phthalate(DBP)and dioctyl phthalate(DOP)was used as diluent.The effects of α(DBP mass fraction in mixed diluent)and β(iPP mass fraction in polymer solution)on pore size distribution of the membrane were investigated by N2-liquid displacement measurement.The connectivity of the membrane was evaluated with membrane tortuosity.It is noted that resulting membrane is apt to possess a narrow pore size distribution.For same β,the mean pore size and connectivity of resulting membrane decrease with increasing α.For α=0.20,with increasing β,mean pore size of resulting membrane increases with subsequent decreasing,while resulting membrane connectivity increases slightly.For α=0.35 or α=0.50,the mean pore size and connectivity of resulting membrane decrease with increasing β.It is indicated that the change of connectivity is attributed to the difference of the membrane topology.It is shown that membrane pore size and connectivity can be controlled effectively by choosing proper α and β.

TIPS法制备聚偏氟乙烯平板微孔膜及其表征

以邻苯二甲酸二甲酯(DMP)为稀释剂,采用热致相分离法(TIPS)制备了聚偏氟乙烯(PVDF)平板微孔膜。利用差示扫描量热仪分析了不同PVDF/DMP体系的结晶性能;通过测试纯水通量、孔隙率、泡点、平均孔径、拉伸强度等对膜进行了表征。结果表明:DMP含量增大,结晶温度向低温方向移动,膜拉伸强度降低,当DMP的质量分数为0.70时膜拉伸强度有明显拐点;PVDF/DMP体系冷却发生固-液相分离;PVDF含量增大,膜水通量、孔隙率、最大孔径和平均孔径均减小。

聚丙烯MI及成核剂添加量对TIPS法多孔膜结构与透过性能的影响

研究了等规聚丙烯(iPP)/邻苯二甲酸二丁酯(DBP)/邻苯二甲酸二辛酯(DOP)/成核剂TM-1体系的热致相分离(TIPS)行为,采用熔融指数(MI)较低的聚丙烯T30S与MI较高的F401作对比研究.采用示差扫描量热仪(DSC)测定成核效应,采用光学显微镜观察iPP成核与晶粒生长.经过加热模压并控制冷却速率制备iPP多孔膜,对膜结构及其透过性能进行了表征.结果表明:相比于F401/DBP/DOP体系,TM-1对T30S/DBP/DOP体系表现出更强的成核效应;不同MI聚丙烯制备的多孔膜结构明显不同,加入成核剂后,T30S型iPP多孔膜结构由紧密融合、内含胞腔孔的球晶结构转变为晶粒组成胞腔壁、相对开放的胞腔孔结构,而F401型iPP多孔膜的结构仍为紧密融合、内含胞腔孔的球晶结构,只球晶尺寸变小;相同成核剂添加量下,用T30S制备的多孔膜透过性能更好.