热致相分离法iPP中空纤维微空膜结构与性能--稀释剂的作用

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.     

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 as β phase by XRD and FTIR characterization. It provides a new way to prepare PVDF membranes with piezoelectric properties.     

Preparation and properties of poly (vinylidene fluoride) membranes via the low temperature thermally induced phase separation method

Tensile strength is of paramount importance to poly (vinylidene fluoride) (PVDF) membranes in expanding their industrial application. In this paper, porous PVDF membranes with higher tensile strength were prepared by the low temperature thermally induced phase separation (LT-TIPS) method. The effects of mixed diluents (MD) composition on the morphology, polymorphism, and tensile strength of such prepared flat sheet membranes were investigated. The competition of membrane formation mechanisms between the nonsolvent induced phase separation (NIPS) and TIPS was demonstrated by observing the membrane morphology in the LT-TIPS process. It was found that the tensile strength was improved by suppressing the formation of finger-like macrovoids and spherulitic morphologies through adjusting the composition of MD. PVDF crystallized into α phase for all the investigated cases, and as the MD became poorer, the total crystallinity increased slightly. Based on these experimental results, PVDF hollow fiber membranes were fabricated via LT-TIPS. The influences of MD composition and polymer concentration on the morphology, water permeability and tensile strength of the formed hollow fiber membranes were studied. The properties of optimized hollow fiber membranes associated with the surface and cross-section morphologies were promising and the performance can be further enhanced in future work.     

Effects of nucleating agents on the morphologies and performances of poly(vinylidene fluoride) microporous membranes via thermally induced phase separation

The effects of nucleating agents on the morphology and performance of poly(vinylidene fluoride) (PVDF) microporous membranes via thermally induced phase separation were investigated. The nucleating agents studied were dicyclohexyl benzene amide (TMB‐5), 2,2‐methylene bis(4,6‐tertiary butyl phenol) sodium phosphate (TMP‐1), and 1,3 : 2,4‐di‐p‐methylbenzylidene sorbitol (DM–LO). Light transmittance experiments and differential scanning calorimetry (DSC) were performed to obtain phase diagrams of PVDF/tributyl citrate/di(2‐ethylhexyl) phthalate/nucleating agent doped solutions. The morphology and performance of the prepared PVDF microporous membranes were characterized with scanning electron microscopy and microfiltration experiments. The results show that the thermodynamics of liquid–liquid phase separation were not affected by the addition of the nucleating agents, but solid–liquid phase separation was influenced. The system with 0.3 wt % TMB‐5 had the fastest crystallization rate and a better nucleation ability. The PVDF microporous membranes had a partly closed, lacy bicontinuous structure with TMP‐1 and DM–LO, whereas the membrane with 0.3 wt % TMB‐5 had an interconnected bicontinuous structure. The pore size distribution became narrower with the addition of nucleating agent. With 0.3 wt % TMB‐5, the membrane had the minimum mean pore size (0.095 μm), a porosity of 80.3%, and a pure water flux of 270 L·m^?2·h^?1; these values were higher than those of the pure PVDF membrane. The performances of the membranes decreased with additions of TMB‐5 of greater than 0.3 wt %. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Effect of solvents on morphology and polymorphism of polyvinylidene fluoride membrane via supercritical CO2 induced phase separation

Poly vinylidene fluoride (PVDF) membranes were prepared via supercritical CO₂ induced phase separation. The effects of solvent power on PVDF membrane morphology and polymorphism were investigated using N‐N‐dimethylformamide (DMF), triethyl phosphate (TEP), and their mixture respectively. The morphology evolution including cross‐section and surfaces were thoroughly studied by scanning electron microscope (SEM) and atomic force microscopy (AFM). The differences of solubility parameters between the solvent and PVDF affected the phase separation and the resultant morphology. The various crystalline phases of the membranes were mainly investigated by Fourier transform infrared spectroscopy (FTIR) and X‐ray diffractometer (XRD). Solvent with larger dipole moment tended to form polar β phase. Decreasing the difference of solubility parameters favored the formation of α phase. Furthermore, the effects of salt additive on PVDF membrane morphology and crystalline form were studied as well. Results turned out that lithium chloride (LiCl) induced a porous top surface and boosted the formation of β phase. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 41065.     

Formation of a bicontinuous structure membrane of polyvinylidene fluoride in diphenyl ketone diluent via thermally induced phase separation

The polyvinylidene fluoride (PVDF)‐diphenyl ketone (DPK) mixture was studied as a new system to prepare PVDF membranes via thermally induced phase separation (TIPS). The phenomena of liquid–liquid phase separation was found in this mixture when the temperature of mixture was decreasing and the PVDF concentration was less than 30 wt %. Using DPK as diluent, PVDF membrane with bicontinuous structure was obtained without necessity to add a nonsolvent or a stretching process further. The phase diagram of PVDF‐DPK system was also constructed to help investigate the effect of PVDF concentration and coarsening temperature on morphology of resulting membrane. The experiments showed that high coarsening temperatures and low PVDF concentrations resulted in the formation of the large pore size membrane. The strength of the wet membrane was decreasing with decreasing PVDF concentration. On condition that the PVDF concentration was larger than 30 wt %, thermally induced solid–liquid separation occurred and bicontinuous structure disappeared. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Crystallization behavior of PVDF in PVDF‐DMP system via thermally induced phase separation

The crystallization behavior of PVDF (poly (vinylidene) fluoride) in PVDF‐dimethylphthalate(DMP) system was investigated in the liquid–liquid (L–L) phase separation region, solid–liquid (S–L) phase separation region and different quenching conditions via thermally induced phase separation (TIPS). Differential scanning calorimetry (DSC) indicated the crystallinity of PVDF in PVDF‐DMP system increased in the early stage of phase separation and polymer‐rich phase crystallized completely in the late stage of phase separation. The scanning electron microscopy (SEM) showed the different quenching temperatures had effects on the spherulite size of polymer rich phase and the ultimate membrane structure in the different phase separation regions. The wide angle X‐ray diffraction (WAXD) was used to quantify the crystal structure of PVDF in PVDF‐DMP system. The α‐phase PVDF was obtained when the system quenched to different temperatures above 40°C, and the area of diffraction peaks changed when quenching temperatures changed. While the β‐phase PVDF was formed when PVDF‐DMP system was quenched form liquid nitrogen and crystallized for 24 h in 25°C water bath. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 3714–3719, 2006     

凝固浴组成和温度对PVDF疏水微孔膜结构与性能的影响

利用非溶剂相转化法(NIPS),以聚偏氟乙烯(PVDF)/磷酸三乙酯(TEP)-N,N-二甲基乙酰胺(DMAc)为铸膜液体系,乙醇水溶液为凝固浴制备高性能的PVDF疏水微孔膜。考察了凝固浴中乙醇(EtOH)含量及凝固浴温度对PVDF成膜分相速率、膜结构和膜疏水性的影响。实验结果表明,在20℃的凝固浴温度下,凝固浴中乙醇含量的升高减慢了铸膜液体系的分相速率,提高了PVDF膜的孔隙率;在凝固浴中添加60%(wt)的乙醇,可形成表面荷叶状结构和截面对称的海绵状结构,膜表面的接触角为130.3°,呈很强的疏水性,并具有较优的膜强度。     

制膜基底对非溶剂致相转化法PVDF膜结构与性能的影响

以聚偏氟乙烯(PVDF)/N,N-二甲基乙酰胺–辛醇/水为制膜体系,采用干、湿相转化法制膜。考察了制膜基底对膜结构、表面浸润性和透过性能的影响。对膜样品的XRD测试表明,具有一定粗糙度的砂纸基底对液态膜具有粘附限制作用,在成膜过程中的液–固分相与液–液分相的竞争中占据更大优势。在适当粗糙度的砂纸基底上可以制得底面高度疏水且透过性能良好的PVDF微孔膜。     

玄武岩纤维增强PVDF/PP/PETG共混物及性能的研究

通过熔融共混法制备了聚偏氟乙烯/聚丙烯/聚对苯二甲酸乙二醇1,4环己二醇酯（PVDF/PP/PETG）共混物,利用玄武岩纤维对其进行增强改性,并采用扫描电子显微镜、转矩流变仪、维卡软化点测试仪等测试仪器对共混物的形态、黏度、耐热性和力学性能等进行了研究。结果表明,230 ℃时,共混物中PVDF、PP和PETG属两两不相容体系,PVDF和PP呈现连续相结构,而PETG则以球状形态分散在体系中;经玄武岩纤维增强改性后,复合材料的拉伸强度和弯曲强度随着玄武岩纤维含量的增加而增大,且当其含量为30 %（质量分数,下同）时,复合材料的拉伸强度和弯曲强度分别增加到44.0 MPa和67.9 MPa;共混物的维卡软化点从126.7 ℃提高到141.7 ℃。     

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

热致相分离（TIPS）法制备等规聚丙烯（iPP）中空纤维微孔膜,邻苯二甲酸二丁酯（DBP）与邻苯二甲酸二辛酯（DOP）的混合溶剂作为制膜稀释剂。干/湿氮气流量法测定了α（稀释剂中DBP的质量分数）和β（铸膜液中聚合物的质量分数）对膜样品的平均孔径及其分布的影响,并采用膜孔曲折因子定量表达膜孔连通性。发现全部膜样品均体现窄孔径分布特征。对于相同的β, α增加导致平均孔径及膜孔连通性下降。α=0.20时,β增加,膜的平均孔径先增加后降低,膜孔曲折因子稍下降; α=0.35或0.50时,β增加,膜的平均孔径降低,膜孔曲折因子下降。膜孔连通性体现了膜内部的拓扑结构,共溶剂组成和铸膜液固含量能够调节iPP中空纤维微孔膜的孔径及其连通性。     

Porous structure of crystalline polymers by exclusion effect of carbon dioxide

We investigated the morphology of high-density polyethylene (HDPE) and poly(vinylidene fluoride) (PVDF) crystallized under carbon dioxide (CO₂) by light scattering measurements and microscopic observations. The crystallization of HDPE was delayed and the ordering of the spherulite was smaller by dissolving CO₂ rather than air at ambient pressure. A fine-layered porous structure having a size of 500 nm was obtained in HDPE, while a large rod-like porous structure radiating in the spherulite was obtained in PVDF. Such a characteristic porous structure is attributed to the exclusion of CO₂ from the crystal growth front to the intercrystalline amorphous region and the growth of bubbles by the supersaturation of CO₂ in the constrained amorphous region. The exclusion effect is covered by the Keith-Padden theory through consideration of the self-diffusion in polymer-CO₂ systems; the exclusion and the growth of bubbles occur as lamellar stacks in HDPE whereas they occur as bundles of lamellar stacks in PVDF.     

用拟二元方法研究iPP-DBP-DOP三元体系的热致相分离热力学

采用拟二元方法研究等规聚丙烯（iPP）‐邻苯二甲酸二丁酯（DBP）‐邻苯二甲酸二辛酯（DOP）三元聚合物溶液的热致相分离热力学,得出了拟二元相图的数学关联方法.采用光学显微镜法测定浊点温度, 采用差式扫描量热法（DSC）测定熔点、动态结晶温度.利用浊点测定数据回归聚合物-共溶剂的交互作用参数 χ的表达式,χ是共溶剂配比和温度的函数,以此为基础计算的拟二元相图与实验数据吻合较好.发现共溶剂中DBP份数增加,相分离类型由单纯固液分相形式转变为液液分相、固液分相依次发生形式,共溶剂配比能调控拟二元相图结构.研究表明,只需测定一个较低冷却速率下几种共溶剂配比的拟二元溶液的浊点温度、分别测定几个冷却速率下iPP–DOP二元溶液的动态结晶温度即可掌握该三元溶液热致相分离热力学的全部信息.其可用来指导制膜过程,并能准确预测形成的膜结构形貌.     

相转化法制备PVDF超滤膜及其亲水化改性研究进展

综述了聚偏氟乙烯(PVDF)超滤(UF)膜在相转化制备方法和亲水化改性两方面的最新研究进展。在相转化制备方法中,介绍了聚合物用量、溶剂的选择、添加剂的种类和用量及凝固浴组成和温度对膜结构和性能的影响;在PVDF超滤膜亲水化改性方面,介绍了共混改性、共聚改性、辐照接枝改性、等子体改性等方法的机理、特点和近年来的研究进展,指出了共混改性是今后亲水改性的主要方向。     

PVDF porous matrix with controlled microstructure prepared by TIPS process as polymer electrolyte for lithium ion battery

Poly(vinylidene fluoride) (PVDF) microporous matrix of polymer electrolyte for lithium ion battery was prepared via the thermally induced phase separation (TIPS) process using diluent mixture of dibutyl phthalate (DBP) and di(2-ethylhexyl) phthalate (DEHP). Since this method has only one parameter, namely the DBP/DEHP ratio in diluent mixture, the membrane microstructure is easily and conveniently controlled. With the assistance of a pseudo-binary temperature-DBP ratio phase diagram of the PVDF-diluent mixture system, the membrane formation mechanism for different microstructures of membranes was proposed. In addition to studying the different microstructures available in TIPS process, the relationship between performance of membrane, electrochemical property of polymer electrolyte and final microstructure has been investigated in this paper.     

Poly(vinylidene fluoride)–acrylic rubber partially miscible blends: Phase behavior and its effects on the mechanical properties

A phase diagram of poly(vinylidene fluoride) (PVDF) and acrylic rubber (ACM) was plotted, and the effects of the extent of miscibility on the mechanical properties of the polymer blends were examined. A compressible, regular solution model was used to forecast the phase diagram of this blend. The model prediction, the lower critical solution temperature (LCST) over the upper critical solution temperature (UCST), was done qualitatively according to the experimentally determined phase diagram by differential scanning calorimetry (DSC), optical microscopy, and rheological analysis. These experimental methods showed that this system was miscible in ACM‐rich blends (>50% ACM) and partially miscible in PVDF‐rich blends. A wide‐angle X‐ray diffraction study revealed that PVDF/ACM blends such as neat PVDF had a characteristic α‐crystalline peak. The partially miscible blends displayed up to 350% elongation at break; this was a significant increment of this parameter compared to that of neat PVDF(20%). However, the miscible blends showed elongation of up to 1000% [again, a remarkable increase compared to chemically crosslinked ACM (220%)] and displayed excellent mechanical properties and tensile strength and a large elongation at break. For the miscible and partially miscible blends, two different mechanisms were responsible for this improvement in the mechanical properties. It was suggested that in the partially miscible blends, the rubbery depletion layer between the spherulite and the conventional rubber cavitations mechanism were responsible for the increase in the elongation at break, whereas for the miscible blends, the PVDF spherulite acted as a crosslinking junction. The stretched part of the tensile samples in the partially miscible blends showed characteristic β‐crystalline peaks in the Fourier transform infrared spectra, whereas that in the miscible blends showed α‐crystalline peaks. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 1247‐1258, 2013     

Influences of contents and molecular weights of LDPE on DOP plasticization of PVC

Influences of contents and molecular weights of low‐density polyethylene (LDPE) on dioctyl phthalate (DOP) plasticization in the poly(vinyl chloride) (PVC) plastisol (PVC/DOP/AO = 100/30/6.5) were investigated using DMA and DSC. The plasticization effects of DOP on the PVC plastisol were found to decrease with increasing LDPE content. A negligible plasticization effect of DOP on the PVC plastisol was found when the LDPE content was equal to or higher than 75 parts per 100 parts by weight of LDPE and PVC together. Based on thermal fractionation experiments, a favorable interaction between LDPE and DOP was developed during melt blending of LDPE and the PVC plastisol. The present interaction enabled the incorporation of DOP into LDPE and decreased the plasticization effects of DOP on the PVC plastisol. A further decrease in the plasticization effects of DOP on the PVC plastisol by the presence of LDPE was found with increasing LDPE molecular weights. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 2548–2555, 2002     

Hollow fibers for seawater desalination from blends of PVDF with different molecular weights: Morphology,properties and VMD performance

In this work, different PVDF grades were used for producing hollow fibers for application in seawater desalination by membrane distillation (MD). In particular, PVDF Solef^® homopolymers, with increasing molecular weight and different crystallinity, were used, also in blend, for preparing polymeric dopes. The effect of PVDF molecular weight on the dope viscosity was investigated. Then, a group of six polymeric dopes, having the same additive composition and the same viscosity (about 7000 mPa s), but containing different PVDF types was selected. Spinning experiments were carried out under the same conditions to highlight the effect of PVDF type on the produced hollow fibers’ morphology and properties. It was evidenced that polymer concentration plays a major role in determining the final membrane morphology; in particular, the formation of macrovoids is more affected by polymer concentration than dope viscosity. Fibers’ mechanical properties, porosity and pore size were found to be also strongly affected by polymer concentration. Finally, the produced hollow fibers were tested in a membrane distillation unit working under vacuum (VMD). Tests were carried out both feeding pure water and synthetic seawater. It was found that VMD performance, both in terms of flux (J) and solute separation factor (α), being connected to fibers’ morphology and porosity, is also clearly dependent on polymer concentration.     

High-flux PVDF/PVP nanocomposite ultrafiltration membrane incorporated with graphene oxide nanoribbones with improved antifouling properties

A novel polyvinylidene fluoride (PVDF) nanocomposite membrane containing graphene oxide nanoribbones (GONRs) as a new nanofiller and polyvinylpyrrolidone (PVP) as pore former agent was prepared via phase inversion method. GONRs were prepared by oxidative unzipping of multi-walled carbon nanotubes (MWCNTs) via chemical approach. Chemical vapor deposition method was used to synthesis MWCNTs. The effects of adding GONRs and PVP into the casting solution on morphology, hydrophilicity and pure water flux (PWF) of the prepared nanocomposite membranes were explored. Antifouling experiments were also performed. It was found that compared to the neat PVDF membrane, PWF of the PVDF/PVP, PVDF/(0.5GONRs) and PVDF/(0.5GONRs)/PVP membranes were improved 80%, 44.9%, and 241.6%, respectively. The obtained results showed that GONRs and PVP exhibit synergistic effects in controlling the membrane properties. This work shows that GONRs can be suitable as nanofiller for preparation of high performance PVDF ultrafiltration membranes with improved antifouling properties.     

Preparation of polyvinylidene fluoride membrane via a thermally induced phase separation using a mixed diluent

Polyvinylidene fluoride (PVDF) membranes were prepared via a thermally induced phase separation method with a mixed diluent (dibutylphthalate/dioctyl phthalate). The effects of PVDF concentration and cooling bath temperature (CBT) on the structure and properties of the membranes were investigated. Scanning electron microscopy photos showed that the cross‐section of all the membranes, regardless of PVDF concentration and CBT, presented a bi‐continuous structure with the spherulitic pattern; moreover, the spherulitic patterns became clear gradually from the top surface to the bottom surface, and the top surface was denser than the bottom surface. As a result, all the membranes exhibited an asymmetric structure. The membrane property measurement indicated that, as PVDF concentration increased from 25 to 35 wt %, the pure water flux (PWF) decreased from 342 to 80 L m^?2 h^?1, and the porosity decreased slightly, whereas the minimum bubble point pressure (BPP) increased, which indicates maximum pore size decreased. In addition, with the increase in CBT, the PWF increased, but, the minimum BPP and porosity decreased. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009