硅溶胶补强PDMS-PA复合膜的性能

以疏水纳米二氧化硅溶胶作硅橡胶的补强材料,制成了硅橡胶-聚酰胺(PDMS-PA)复合膜;用扫描电镜观察了其断面形态,考察了复合膜对醇-水溶液的渗透蒸发分离效果及耐用性,并与气相法白炭黑补强PDMS-PA复合膜进行了比较.结果表明,与气相法白炭黑补强PDMS-PA复合膜相比,硅溶胶补强的PDMS-PA复合膜的PDMS皮层和PA支撑层之间的结合更紧密,但分离因子和渗透通量下降.在相同条件下进行醇-水分离实验后,气相法白炭黑补强PDMS-PA复合膜出现PDMS皮层与PA支撑层分离现象;而硅溶胶补强PDMS-PA复合膜的PDMS皮层与PA支撑层结合完好.表明用硅溶胶作107硅橡胶的补强填料时能在PDMS-PA复合膜的渗透汽化性能略有下降的情况下改善PDMS皮层与PA支撑层之间的结合,提高复合膜的耐用性,使其具有工业使用价值.     

改性Silicalite-1填充聚酰胺反渗透复合膜的研究

为改善分子筛Silicalite-1与聚酰胺(PA)之间的相容性,减少膜内非选择性的缺陷,采用双酚A型环氧树脂(BE188)对分子筛纳米颗粒表面进行改性,并将其添加到PA层中制备分子筛杂化膜。TEM表征结果证明:分子筛经表面改性后,不但提高了在PA基质中的分散性,而且与PA基质之间的相容性也明显改善,从而减少了界面缺陷。将所制备的膜用于2 g/L氯化钠水溶液反渗透脱盐,发现改性分子筛杂化膜的分离性能优于未改性分子筛杂化膜。且当改性分子筛的添加量为1 mg/mL时,膜的水通量为38.72 L/(m2.h),约为PA膜的1.5倍,同时膜的截留率也有所提高。     

纳米白炭黑填充硅橡胶复合膜的制备与渗透汽化分离性能

制备以聚酯(PET)为支撑层,白炭黑填充的聚二甲基硅氧烷(PDMS107)为皮层的硅橡胶复合膜,并以乙醇水物系为料液,对比分析白炭黑增强硅橡胶复合膜的渗透蒸发分离性能,分离因子比空白膜有所提高,在乙醇浓度为3%～5%时,分离因子可达16.09,渗透通量为75.39 g/m2·h;测定填充白炭黑硅橡胶复合膜的拉伸强度,结果表明:拉伸强度可达1.828 MPa,相当于空白膜(0.368 MPa)的5倍.     

多层聚酰胺复合膜的制备及其特性

聚酰胺（PA）具有特定的反渗透（RO）淡化海水和渗透汽化（PV）分离有机物混合物的优良性能。本研究采用水相含单体间苯二胺（m-PDA）和有机相含单体均苯三甲酰氯（TMC）体系,通过多次界面缩聚（IPC）工艺,制成了以RO用的PA复合膜作为多孔支撑膜的多层PA（ML-PA）复合膜。分别用原子力显微镜（AFM）和扫描电子显微镜（SEM）观察了ML-PA膜的微结构。ML-PA膜的厚度、PA高分子微囊聚集的致密程度、平均面粗糙度,都随着IPC反应次数的增加而显著提高。改变制备工艺参数,例如水相中单体和有机相中交联剂的浓度、IPC反应的温度和时间、以及IPC反应的次数,可以得到不同分离性能的ML-PA复合膜。当在m-PDA浓度为2．0％的水溶液中浸渍20min,然后在TMC浓度为0．5％的正己烷溶液中浸渍20s,IPC反应5次,每次反应温度均为40℃,获得的ML-PA复合膜在室温（25℃）下PV分离浓度为88．2％的异丙醇（IPA）水混合物时,渗透通量接近30．0g／m^2·h,渗透物中的水含量大于99．0％。     

基于聚二甲基硅氧烷的渗透气化膜改性技术研究进展

介绍了近年来对PDMS分离层的改性方法，包括填充、共混、交联、共聚和表面改性，旨在研究新型PDMS疏水性膜材料，实现有机物的高效分离，同时提出目前PDMS分离膜在应用中存在的问题和未来的发展方向。     

纳米白炭黑在硅橡胶膜铸膜液中分散性能的研究

制备了以聚对苯二甲酸乙二醇酯(PET)为支撑层,白炭黑填充的聚二甲基硅氧烷(PDMS)为皮层的硅橡胶复合膜,研究了纳米白炭黑在铸膜液中分散性能的影响因素。结果发现,体系中加入适量正硅酸乙酯有助于提高纳米白炭黑的分散性;正庚烷与硅橡胶的配比为10：1（质量比,下同）时,白炭黑的分散速度最快。并测试了5 %（质量分数,下同）白炭黑填充硅橡胶复合膜的拉伸强度,结果表明,其拉伸强度可达1.828 MPa,相当于未填充白炭黑的硅橡胶膜（0.368 MPa）的5倍。     

碳纳米管填充PDMS膜的渗透汽化性能

将碳纳米管（CNTs）填充到PDMS中制备出CNTs/PDMS杂化膜,并将其用于乙醇/水体系的分离,发现由多壁碳纳米管制备的膜分离性能优于单壁碳纳米管填充膜,在40℃下,进料乙醇浓度为5%（质量分数）时,膜的分离因子可由8.3提高到10.0,渗透通量为206.2 g·（m²·h）^-1;采用十二烷基三氯硅烷对多壁碳纳米管进行修饰,并对修饰前后碳纳米管的性能进行表征,研究表明修饰后碳纳米管表面形成疏水层,碳纳米管的疏水性增强;将修饰后的碳纳米管填充到PDMS中,可进一步提高杂化膜对乙醇的选择性,膜的分离因子可提高到11.3,渗透通量为130.9 g·（m²·h）^-1。     

SiO_2-PEBAX/PAN膜渗透汽化分离吡啶

以聚醚共聚酰胺(PEBAX)为分离膜材料,聚内烯腈(PAN)超滤膜为支撑层,纳米气相二氧化硅(n-Si O2)颗粒为填充物,分别制备了PEBAX/PAN复合膜及n-Si O2-PEBAX/PAN填充型复合膜,旨在通过渗透汽化分离吡啶。采用扫描电镜(SEM)、X射线衍射(XRD)、傅里叶红外光谱(FT-IR)对复合膜进行表征,表明n-Si O2与聚合物只是物理混合。以吡啶/正庚烷混合物为模拟溶液,考察膜的溶胀及渗透汽化分离性能。溶胀实验结果表明:膜溶胀度随料液吡啶含量及温度的增加而增大。渗透汽化实验结果表明:n-Si O2填充量为10‰(wt)时总渗透通量最大,填充量为5‰(wt)时分离因子最大。总渗透通量和分离因子都随料液吡啶浓度增大而增加;渗透汽化操作温度升高,总渗透通量增大,而分离因子减小。当填充量为5‰(wt)、温度为30℃、以及料液吡啶含量为5000?g?g?1时,Pn5膜的总渗透通量为5.05 kg?m?2?h?1,分离因子为3.39。研究结果表明,Si O2-PEBAX/PAN复合膜对吡啶有较好的富集作用。     

聚环糊精填充PDMS渗透蒸发膜分离苯酚水溶液

以聚二甲基硅烷为预聚体,正硅酸乙酯为交联剂,二丁基二月桂酸锡为催化剂,三氯甲烷或正庚烷为溶剂,通过相转化法制备得到了空白聚二甲基硅氧烷（PDMS）膜和聚环糊精（CDP）填充PDMS（CDP-f-PDMS）膜.考察了空白PDMS膜和CDP-f-PDMS膜对苯酚水溶液的渗透蒸发分离性能,证明填充膜优于空白膜.还分别考察了溶剂类型、填充剂用量等制膜因素和操作温度、原料液流量、原料液浓度等操作因素对PDMS膜的渗透蒸发分离性能的影响.当温度为60℃,CDP填充量为1%（质量）时,CDP-f-PDMS膜的渗透通量和分离因子分别可达32.0 g•m-²•h^-1和7.2.     

硬脂酸改性γ-Al_2O_3填充PEBAX膜渗透汽化分离苯胺

利用硬脂酸对纳米γ-Al_2O_3改性,分别制备了聚醚共聚酰胺(PEBAX)均质膜、填充膜、复合膜以及填充型复合膜四种分离膜,探讨了膜在苯胺/正庚烷体系中的溶胀性能和渗透汽化性能。利用FT-IR、XRD分别考察了改性前后γ-Al_2O_3颗粒官能团和晶体结构的变化情况,通过SEM观察膜的形貌结构。溶胀实验结果表明:随着料液中苯胺浓度和料液温度的升高,溶胀度均持续增大,在48 h时达到溶胀平衡,填充量为2%(wt)时填充膜的溶胀效果最好;渗透汽化实验结果表明:膜的渗透通量和分离因子均随料液中苯胺浓度和料液温度的升高而持续增大,填充型复合膜的综合性能最优,其填充量为2%(wt)时分离性能最佳,当苯胺浓度为5000μg×g~(-1)、温度为70℃时,膜的渗透总通量为5.64 kg×m~(-2)×h~(-1),分离因子为3.07。     

Influence of binding interface between active and support layers in composite PDMS membranes on permeation performance

Effect of the binding interfaces of composite polydimethylsiloxane (PDMS) membranes on their pervaporation performance was studied. The membranes were made up of PDMS as active skin layer and polysulfone (PSF) or polyamide (PA) as supporting layer. PDMS‐PSF membrane was numbered 1, and PDMS‐PA membrane numbered 2. The pervaporation experiments were carried out by using the composite membranes and dilute ethanol–water mixture. The experimental measurements for the permeation performance under various operating conditions (e.g., feed concentration and temperature) showed that the specific permeation rate of membrane 2 was over membrane 1 by seven times at least. A resistance‐in‐series model was applied to formularize the transport of the permeants. Influence of the binding interfaces between the active skin layer and support layers in these membranes on pervaporation performance was analyzed. The cross section morphology of the membranes and chemical element distribution along membrane thickness were examined by using SEM and EDS. It was found that, although the PDMS intrusion layer into PSF near the interface was only about 2 μm, it gave significant effect on the permeation performance. It implied that the resistance produced by the intrusion layer into PSF was apparently larger than that of PDMS intruding PA and over intrinsic PDMS resistance. These should be probably attributed to structures and formation of the binding interfaces. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 2468–2477, 2007     

Preparation and pervaporation performances of fumed‐silica‐filled polydimethylsiloxane–polyamide (PA) composite membranes

Fumed‐silica‐filled polydimethylsiloxane (PDMS)–polyamide (PA) composite membranes were prepared by the introduction of hydrophobic fumed silica into a PDMS skin layer. The cross‐sectional morphology of these filled composite membranes was observed with scanning electron microscopy. Their pervaporation performances were tested with aqueous ethanol solutions at 30, 35, and 40°C. Increasing the amount of the fumed silica resulted in significantly enhanced ethanol permeability of the membranes. When the content of the fumed silica in the PDMS skin layer was 20 wt %, the ethanol permeability increased to nearly twice that of the unfilled PDMS–PA composite membrane. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

A new technique for preparation of PDMS/ceramic nanocomposite membrane for gaseous hydrocarbons separation

A novel composite membrane using polydimethylsiloxane (PDMS) as a top active layer and ceramic nanocomposite as the support layer was developed for the gaseous hydrocarbons separation. For the fabrication of hybrid membranes, nanocomposite technology applied for manufacturing ceramic supports with controllable microstructures. Also, a new method was used for coating a uniform and no penetrated polymeric layer. Top layer of ceramic support with nanocomposite microstructures was fabricated using 5 wt % α‐Al₂O₃‐SiO₂ bidispersed suspensions with optimum weight fraction of second phase (SiO₂) based on the fractional collision frequency theory. PDMS selective layer was coated on the outer surface of the porous ceramic nanocomposite support by dip‐coating method. In this respect, the effect of several parameters such as pretreatment temperature, PDMS solution concentration, and number of coated polymeric layers on prepared layers morphology and hybrid membrane performance in the separation of condensable hydrocarbons (iso and n‐butane) from hydrogen were investigated. The results showed that the membranes fabricated at 140°C as pretreatment temperature and three polymeric layers by 7, 15, and 15 wt % PDMS concentration, respectively, had a high selectivity (>25 at 2 bar)) in C₄H₁₀/H₂ separation. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

支撑层对硅橡胶复合膜渗透汽化分离性能的影响

引言 为了扩大渗透汽化技术的应用领域,科研工作者需要进一步增强渗透汽化膜的分离性能.从工业化的观点而言,用于实际应用的渗透汽化膜大多是复合膜,它由选择层(或分离层)和支撑层组成.一般认为,选择层决定着复合膜的选择性和通量,支撑层起支撑和机械稳定作用.Nijhuis[1]在从甲苯-水体系中分离甲苯的过程中对均质膜和以聚砜为支撑层的复合膜的分离性能进行了比较;Sturken[2]分别用聚醚酰亚胺和聚偏氟乙烯为支撑层的硅橡胶膜从二氯乙烷-水体系中提取二氯乙烷,他们得到了相同的结论:支撑层的影响可以忽略.然而Scholz[3],Heinzelmann[4],Rautenbach[5],Borges[6],Vankelecom[7],Farooq[8],Lipnizki[9]等均在各自研究中发现,由于基膜和分离层的物理化学性质以及制膜方法等众多因素的存在使得支撑层在一定程度上影响复合膜的分离性能;Feng[10]对均质硅橡胶膜和有微孔支撑层的硅橡胶复合膜的分离性能进行了比较,发现均质硅橡胶膜优先透过异丙醇,而有微孔亲水性支撑层的硅橡胶复合膜则优先透过水,这表明在一定的情况下,支撑层甚至起主导作用并能够决定复合膜的分离性能.因此,通过系统研究以不同多孔材料为支撑层的复合膜对有机物-水溶液的分离性能的影响,能够找到最优的复合膜支撑层,从而能够提高复合膜的分离性能.然而,至今关于支撑层对渗透汽化膜分离性能影响的系统研究仍相当少.     

Effects of coating solvent and thermal treatment on transport and morphological characteristics of PDMS/Torlon composite hollow fiber membrane

A new approach for formation of the polydimethylsiloxane (PDMS) layer on Torlon polyamide‐imide hollow fiber (PAI‐HF) support has been developed by directly after fiber spinning without the need to undergo the final conventional solvent exchange and drying step, thereby saving postspinning processing steps. The produced PDMS/PAI‐HF composite membranes were found to have high CO₂ permeance (i.e., 1100 GPU) and exhibited good CO₂/N₂ selectivities of 8–10 which is close to 90% of that of a PDMS dense film. The effects of coating solution, rewetting and crosslinking temperature on the PAI‐HF morphological features, that is, gas transport, skin thickness, skin integrity, and substructure resistance are investigated. The rewetting and thermal treatment of the PAI‐HF caused the densification of the skin layer and reduced the pore sizes on the top layer. In addition, the potential use of the PAI‐HF support with polymers that are insoluble in hexane is also considered. Effects of water, methanol, and hexane exposure of PAI‐HF to these solvents are considered. This evaluation calls attention to issues that must be addressed in any eventual use of the PAI‐HF with water‐soluble or methanol‐soluble selective layer polymers, rather than simple hexane‐soluble polymers such as PDMS. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45418.     

Influence of support layer and PDMS coating conditions on composite membrane performance for ethanol/water separation by pervaporation

A systematic study was performed on the combination of support properties and polydimethylsiloxane (PDMS) coating conditions for the lab‐scale preparation of a defect‐free, thin film composite membrane for organophilic pervaporation. Support layers having comparable surface porosities were prepared from three polymers with different chemical composition (PVDF, PSF, PI). Their exact role on the deposition of the PDMS coating (i.e., wetting and intrusion) and the final membrane performance (i.e., effect on mass transfer of the permeants) was studied. The crosslinking behavior of dilute PDMS solutions was studied by viscosity measurements to optimize the coating layer thickness, support intrusion and wetting. It was found essential to pre‐crosslink the PDMS solution for a certain time prior to the coating. Dip time for coating the PDMS solution on the supports was varied by using automated dip coating machine. The performance of the synthesized membranes was tested in the separation of ethanol/water mixtures by pervaporation. Both flux and selectivity of the membranes were clearly influenced by the support layer. Resistance of the support layers increased by increasing the polymer concentration in the casting solutions of the supports. Increasing the dip time of the PDMS coating solution led to increased selectivity of the composite membranes. Scanning Electron Microscopy analysis of the composite membranes showed that this leads to a minor increase in the thickness of the PDMS top layer. Top layer thickness increased linearly with the square root of the dip time (t^0.5) at a constant withdrawal speed of the support. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43670.     

A new approach to polymer/montmorillonite nanocomposites

A novel method for preparation of exfoliated/intercalated nanocomposites is reported based on two steps, i.e. preparation of treated-montmorillonite (MMT) solution and solution blending with polymers. After in situ polymerization of dimethyldichlorosilane between layers and separation of most polydimethylsiloxane (PDMS), the treated-MMT solution shows good storage stability. Although elemental analyzer shows no residue PDMS, NMR proves residue PDMS still exists in the solution. The residue PDMS is believed to graft onto the MMT layer surface via condensation of hydroxyl groups of PDMS and those that existed on MMT surface. Lower relaxation time of end-capped CH₃ of alkyl ammonium grafted onto layer surface via ion exchanging in the solution shows that the layer spacing was increased significantly or even exfoliated. When the solution was blended with some polar polymers, exfoliated nanocomposites were found. When it was blended with some nonpolar polymers, however, intercalated nanocomposites were obtained. The reason was explained in the light of compatibility between polymer matrix and MMT as well as alkyl ammonium and PDMS grafted on the layer surface. For intercalated nanocomposites, different layer spacing corresponds to different chain flexibility and the presence of multi-peaks is caused by the processing of these blends.     

Organic–inorganic hybrids containing polyimide,organically modified clay and in situ formed polydimethylsiloxane

A series of organic–inorganic hybrid consisting of polyimide (PI) prepared from pyromellitic dianhydride (PMDA) and 4,4′-oxydianiline (ODA), organically modified montmorillonite (OMMT) and polydimethylsiloxane (PDMS) were successfully prepared by in situ sol–gel process. OMMT was prepared by surface treatment of montmorillonite (MMT) with hexadecyltrimethylammonium bromide. X-ray diffraction (XRD) analysis showed that the OMMT layers were exfoliated into the polymer matrix at 2% of OMMT content. The PI–OMMT–PDMS hybrids at 2% of OMMT content were transparent when PDMS content was less than 5%. The PI–OMMT–PDMS hybrid showed better tensile modulus, strength and elongation at break than that of pristine PI due to the reinforcement effect of OMMT and toughening effect of PDMS. The thermal stability of hybrids such as the decomposition temperature and weight residue at 800 °C also increased with the increase of PDMS content as evidenced by thermogravimetric analysis (TGA).     

Modulation of Adhesion at Silicone Elastomer-Acrylic Adhesive Interface

To characterize the role of small silica like nanoparticles (MQ resins) in the modulation of adhesion at polydimethyl siloxane (PDMS) elastomers-acrylic adhesive contacts, we have designed systems in which the roles of MQ resins in enhancing interactions at the interface and in increasing viscoelastic dissipations in the elastomer layer could be separated. First, the contact between elastomers with various MQ resin contents and PDMS layers made of densely grafted short chains has been investigated through Johnson-kendall-Roberts (JKR) tests, in order to characterize how the dissipations in the elastomer depend on the resin content. The same elastomers in contact with thin-surface-anchored acrylic layers were then tested through JKR tests to determine the role of enhanced interactions in the modulation of adhesion at the interface due to the resins. In these experiments, the thickness of the acrylic layer was kept small enough so that dissipations in the acrylic adhesive could be neglected. Both G₀, the adhesive strength at zero fracture velocity, and G( V), the velocity-dependent fracture toughness, strongly depend on the MQ resin content and on the contact time, suggesting the progressive building of strong interactions between acrylic and elastomer chains.     

PVDF中空纤维换热管超疏水表面强化蒸气滴状冷凝传热

为了提高塑料换热管的传热性能，通过两步涂覆法制备了具有超疏水表面的复合塑料换热管。首先采用多孔PVDF中空纤维膜为支撑层，以导热材料纳米ZnO填充聚二甲基硅氧烷（PDMS）为皮层，制备了具有致密外表皮层的复合塑料换热管。其次为了强化蒸气的滴状冷凝传热，通过考察正硅酸乙酯含量，氨水含量等条件的影响，制备出了具有超疏水表面的PVDF复合塑料换热管。结果表明，所制备的换热管表面接触角可达154°，与熔融法及NIPS法制备的换热管相比，总传热系数可提高85.3%～147.3%。