Indispensable gutter layers in thin-film composite membranes for carbon capture

Industrial thin-film composite(TFC)membranes achieve superior gas separation properties from high-performance selective layer materials,while the success of membrane technology relies on high-performance gutter layers to achieve production scalability and low-cost manufacturing.However,the current literature predominantly focuses on the design of polymer architectures to obtain high permeability and selectivity,while the art of fabricating gutter layers is usually safeguarded by industrial manufacturers and appears lackluster to academic researchers.This is the first report aiming to provide a comprehensive and critical review of state-of-the-art gutter layer materials and their design and modification to enable TFC membranes with superior separation performance.We first elucidate the importance of the gutter layer on membrane performance through modeling and experimental results.Then various gutter layer materials used to obtain high-performance composite membranes are critically reviewed,and the strategies to improve their compatibility with the selective layer are highlighted,such as oxygen plasma treatment,polydopamine deposition,and surface grafting.Finally,we present the opportunities of the gutter layer design for practical applications.

In-situ Composite Based on Poly (ethylene terephthalate),Polyamide and Polyethylene with Microfibres Formed through Extrusion and Hot Stretching

In-situ composites based on dispersed poly (ethylene terephthalate) (PET) or polyamide (PA), and continuous polyethylene (PE) were prepared through a single screw extruder of Haake rheometer system with a rod-die relatively small in diameter. The extrudate was drawn at a drawing ratio of 3.1, and then quickly cooled in cold water. The specimens were obtained by injection molding at processing temperatures less than 190℃, far below the melting temperature of PET (265℃) and PA (230℃), which can maintain the solid state of PET and PA microfiber phase in the composites. Morphological observation with scanning electron microscopy (SEM) indicated that PET and PA can more or less form in-situ microfibers at compositions studied (0~20 wt pct PET or PA), and especially, PET and PA were almost deformed into fibers at the concentration of 15 wt pct. Tensile strength and modulus of the blends reinforced by PET or PA microfibers showed to be increased from the tensile test results. The most noticeable improvement of the tensile properties occurred at 15 wt pct of PET in PET/PE system, corresponding to the highest microfiber content, where the tensile strength reached 32.5 MPa, whereas only 19.5 MPa for the pure PE.

Development of Clinical Cement of Nanoapatite and Polyamide Composite

A new type of inorganic organic biomimetic bone cement consisting of nano hydroxyapatite and polyamide 66 composite was investigated. This cement can be handled as paste and easily shaped into any contour. Nanoapatite and polyamide composite cement has a reasonable setting time, excellent washout resistance, high mechanical strength and bioactivity, and it is easily handled and shaped, which can be developed as a clinical cement. It can be predicted that nanoapatite/polymer composite cement would be a new trend of biomedical material, showing a promising prospect.

A Composite of Nanocrystalline Hydroxyapatite and Polyamide

A composite of nanocrystalline hydroxyapatite(n HA) and polyamide PA was prepared by the chemical methods of co precipitation and hydrothermal treatment. Hydrothermal treatment not only conduced to the formation of n HA but also enabled PA to be connected with n HA tightly. Using these methods, a dense composite powder containing high n HA /PA ratio (>50%) was obtained.

Injectable Premixed Cement of Nanoapatite and Polyamide Composite

A new type of injectable premixed bone cement consisting of nano hydroxyapatite (n HA) and polyamide 66(PA66) composite is investigated. This cement can be handled as paste and easily shaped, which can set in air, in physiological saline solution and in blood. The setting time, injectability and compressive strength of the cement largely depend on the ratio of liquid to powder (L/P). Moreover, the content of n HA in composite also affects the compressive strength and injectability of the cement. The premixed composite cement can remain stable in the package for a long period and harden only after delivery to the defects site. The results suggest that injectable premixed cement has a reasonable setting time, reasonable viscosity for injecting, excellent washout resistance and high mechanical strength, which can be developed for root canal filling, sealing and various bone defects augmentation.

Substrate matters:The influences of substrate layers on the performances of thin-film composite reverse osmosis membranes

Thin-film composite(TFC) reverse osmosis(RO) membranes are playing the dominating role in desalination.Tremendous efforts have been put in the studies on the polyamide selective layers. However, the effect of the substrate layers is far less concerned. In this review, we summarize the works that consider the impacts of the substrates, including pore sizes, surface hydrophilicity, on the processes of interfacial polymerization and consequently on the morphologies of the active layers and on final RO performances of the composite membranes. All the works indicate that the pore sizes and surface hydrophilicity of the substrate evidently influence the RO performances of the composite membranes. Unfortunately, we find that the observations and understandings on the substrate effect are frequently varied from case to case because of the lack of substrates with uniform pores and surface chemistries. We suggest using track-etched membranes or anodized alumina membranes having relatively uniform pores and functionalizable pore walls as model substrates to elucidate the substrate effect.Moreover, we argue that homoporous membranes derived from block copolymers have the potential to be used as substrates for the large-scale production of high-performances TFC RO membranes.

High-permeance crosslinked PTMSP thin-film composite membranes as supports for CO_2 selective layer formation

In the development of the composite gas separation membranes for post-combustion CO_2 capture, little attention is focused on the optimization of the membrane supports, which satisfy the conditions of this technology. The primary requirements to the membrane supports are concerned with their high CO_2 permeance. In this work, the membrane supports with desired characteristics were developed as high-permeance gas separation thin film composite(TFC) membranes with the thin defect-free layer from the crosslinked highly permeable polymer, poly[1-(trimethylsilyl)-1-propyne](PTMSP). This layer is insoluble in chloroform and can be used as a gutter layer for the further deposition of the CO_2-selective materials from the organic solvents. Crosslinking of PTMSP was performed using polyethyleneimine(PEI) and poly(ethyleneglycol) diglycidyl ether(PEGDGE) as crosslinking agents. Optimal concentrations of PEI in PTMSP and PEGDGE in methanol were selected in order to diminish the undesirable effect on the final membrane gas transport characteristics. The conditions of the kiss-coating technique for the deposition of the thin defect-free PTMSP-based layer, namely, composition of the casting solution and the speed of movement of the porous commercial microfiltration-grade support, were optimized. The procedure of post-treatment with alcohols and alcohol solutions was shown to be crucial for the improvement of gas permeance of the membranes with the crosslinked PTMSP layer having thickness ranging within 1-2.5 μm. The claimed membranes showed the following characteristics: CO_2 permeance is equal to 50—54 m^3(STP)/(m^2 h bar)(18,500—20,000 GPU), ideal CO_2/N_2 selectivity is 3.6-3.7, and their selective layers are insoluble in chloroform. Thus, the developed highpermeance TFC membranes are considered as a promising supports for further modification by enhanced CO_2 selective layer formation.

Coordination of thin-film nanofibrous composite dialysis membrane and reduced graphene oxide aerogel adsorbents for elimination of indoxyl sulfate

The protein-bound uremic toxins,represented by indoxyl sulfate(IS),have been associated with the progression of chronic kidney disease and the development of cardiovascular disease in the presence of impaired renal function.Herein,we proposed a novel strategy of thin-film nanofibrous composite(TNFC)dialysis membrane combined with reduced graphene oxide(rGO)aerogel adsorbents for clinical removal of IS as well as high retention of proteins.The TFNC membrane was prepared by electrospinning in conjunction with coating-reaction method and proved to have good selectivity and permeability.To further improve the removal rate of toxins,we used a medium hydrothermal method following by freeze-drying treatment to obtain the r GO aerogel adsorbents.It exhibited excellent adsorption for IS with a maximum adsorption capacity of 69.40 mg·g^(-1)throughπ-πinteraction and hydrogen bonding interaction based on Langmuir isotherm models.Time-dependent absorption experiments showed that it reached adsorption equilibrium within 4 h,which was matched with the hemodialysis time.The coordination was significantly exhibited by introducing r GO aerogel blocks into the dialysate for absorbing the diffused free IS during hemodialysis.Taking the advantages of the TFNC dialysis membrane and the rGO aerogel,the volume of dialysate for hemodialysis was only one-tenth of that without adsorbent blocks but with very comparable dialysis performance(the clearance of IS at 51.8%and the retention of HSA over 98%),which could lighten conventional hemodialysis effectively and be benefit to realize the miniaturization of the hemodialysis equipment.Therefore,the coordination of the TFNC dialysis membrane and rGO aerogel adsorbents would open a new path for the development of portable artificial kidney.

CO2/CH4 separation using inside coated thin film composite hollow fiber membranes prepared by interfacial polymerization

Carbon dioxide(CO_2) is greenhouse gas which originates primarily as a main combustion product of biogas and landfill gas. To separate this gas, an inside coated thin film composite(TFC) hollow fiber membrane was developed by interfacial polymerization between 1,3–cyclohexanebis–methylamine(CHMA) and trimesoyl chloride(TMC). ATR-FTIR, SEM and AFM were used to characterize the active thin layer formed inside the PSf hollow fiber. The separation behavior of the CHMA-TMC/PSf membrane was scrutinized by studying various effects like feed gas pressure and temperature. Furthermore, the influence of CHMA concentration and TMC concentration on membrane morphology and performance were investigated. As a result, it was found that mutually the CHMA concentration and TMC concentration play key roles in determining membrane morphology and performance. Moreover, the CHMA-TMC/PSf composite membrane showed good CO_2/CH_4 separation performance. For CO_2/CH_4 mixture gas(30/70 by volume) test, the membrane(PD1 prepared by CHMA 1.0% and TMC 0.5%) showed a CO_2 permeance of 25 GPU and the best CO_2/CH_4 selectivity of 28 at stage cut of 0.1. The high CO_2/CH_4 separation performance of CHMA-TMC/PSf thin film composite membrane was mostly accredited to the thin film thickness and the properties of binary amino groups.

The Development of Thermal Conductive Polymer Composites for Heat Sink

The thermal and mechanical properties of the polyamide 6/boron nitride and polyphenylene sulfide/graphite composites have been investigated as a function of composition and size of fillers. The addition of highly thermal conductive h-BN and graphite gives rise to large increase （about 2 times） of thermal conductivity of individual polymer. In PPS/graphite system, the higher conductivity value was obtained when smaller graphites were added. Meanwhile, the tensile and flexural strength are reduced upon increasing filler loading.

STUDY ON THE DESALINATION BEHAVIORS OF PA/PSF THIN FILM COMPOSITE

A polypiperazine amide （PA）/polysulfone （PSF） thin film composite （TFC） was prepared by interracial polymerization （IP） using a trimesoyl chloride hexane solution as the oil phase and a piperazine aqueous solution as the water phase on a porous polysulfone hollow fiber substrate. Its separating behaviors were investigated systematically to various salts such as NaCl KCl, Na2SO4, MgCl2, CaCl2 and MgSO4, showing the highest rejection rate to Na2SO4, the second to MgSO4 the third to MgCl2 and CaCl2, and the lowest to KCI, NaCl, being 99%, 98%, 70%, 60%, 15% and 10% respectively. Under an increasing pressure or with time, the rejection rate of the TFC rises to a plateau. To various concentration of the feed, the rejection rate reduced gradually with the higher concentration.

STUDIES ON THE CRIMP BEHAVIOR OF SIDE-BY-SIDE BICOMPONENT POLYAMIDE FIBERS

The supermolecular structure and mechanical properties as well as the crimp behavior of theside-by-side polyamide (PA 66-C710) fibers are studied by means of density gradient method,sonic measurement,X-ray,diffractometry,differential scanning calorimetry,crimp tester etc.fortheir as-spun fibers,drawn fibers,and boiling-water treated fibers.The effects of the processingand treatment conditions on the formation of the supermolecular structure and the crimp behaviorof the fibers are investigated and discussed in detail,also the crimp mechanism of the side-by-sidebicomponent fibers is proposed.From these results,it is shown that by adopting suitable spinningfinish,reasonable processing technology and optimal heat treatment conditions the side-by-sidebicomponent polyamide fibers with excellent crimp property,close to that of nylon texturizedstretch yarns,can be obtained.

Silicon-Basing Ceramizable Composites Containing Long Fibers

Ceramization is a phenomenon which assures compactness of polymer-based composites in the case of their thermal degradation caused by open fire or exposure at high temperatures. This phenomenon is based on preventing volatiles of thermal decomposition of silicone rubber from evacuation by creation of ceramic layer. This ceramized structure is composed of mineral filer particles, connected by fluxing agent—glassy phase. The ceramic barrier created during firing is aimed to protect copper wire inside the cable from melting, being additionally strong enough to maintain integrity of electrical circuit. The paper presents experimental data on mechanical properties of silicone rubber composites strengthened additionally with long fibers of different types—aluminosilicate and polyamide (Kevlar) ones. Fibers were introduced into composites in oriented way. Mechanical properties were investigated taking into account fiber orientation anisotropy. Ceramization process of composites was described by observation of morphology and strengthen measurements of samples fired at 1000°C.

Thickness Effect on (La_(0.26)Bi_(0.74))_2Ti_4O_(11) Thin-Film Composition and Electrical Properties

Highly oriented（00l）（La_（0.26）Bi_（0.74））_2Ti_4O_（11 ）thin films are deposited on（100） SrTiO_（3 ）substrates using the pulsed laser deposition technique.The grains form a texture of bar-like arrays along Sr Ti O_3110directions for the film thickness above 350 nm,in contrast to spherical grains for the reduced film thickness below 220 nm.X-ray diffraction patterns show that the highly ordered bar-like grains are the ensemble of two lattice-matched monoclinic（La,Bi）_4Ti_3O_（12 ）and TiO_（2 ）components above a critical film thickness.Otherwise,the phase decomposes into the random mixture of Bi_2Ti_2O_（7 ）and Bi_4Ti_3O_（4 ）spherical grains in thinner films.The critical thickness can increase up to 440 nm as the films are deposited on LaNiO_3-buffered SrTiO_（3 ）substrates.The electrical measurements show the dielectric enhancement of the multi-components,and comprehensive charge injection into interfacial traps between（La,Bi）_4Ti_3O_（12 ）and TiO_（2 ）components occurs under the application of a threshold voltage for the realization of high-charge storage.

Viscoelastic Properties and Creep-Fatigue Behavior of PA2200/HA Composites Manufactured by Selective Laser Sintering

Porous(polyamide/hydroxyapatite)composites were manufactured via SLS(selective laser sintering)process.Specimens with different PA2200/HA contents(100/0;95/5;90/10 and 80/20)were sintered at relative low laser energy density.The porous composite specimens were characterized for dynamic-mechanical analysis.The dynamic-mechanical properties changed as a function of the composition of the composite materials.Storage and loss modulus vary from 1,050 to 215 MPa and 35 to 5 MPa,respectively.

静电纺聚酰胺6/聚苯乙烯复合纳米纤维膜制备及其空气过滤性能

针对空气过滤纤维材料的过滤效率、阻力和使用寿命难以平衡的问题,采用多喷头静电纺丝技术,制备了不同直径、形貌纤维及不同纤维沉积顺序的聚酰胺6/聚苯乙烯(PA6/PS)复合纳米纤维膜,测试了复合膜的平均孔径及孔隙率,建立了纤维结构与过滤效率及阻力的构效关系;结合扫描电镜表征探讨了不同形貌、直径纤维的叠加次序对过滤寿命及细颗粒物沉积行为的影响,系统研究了过滤风速、细颗粒物尺寸对过滤性能的影响。结果表明:在5.33 cm/s的风速下,以多喷头静电纺丝方式制备的PA6/PS复合膜具有更好的抵抗风速变化的能力,在长期使用中阻力增加较缓慢,其具有93.13%的过滤效率,30.67 Pa的过滤阻力和0.0889 Pa-1的品质因子,综合过滤性能优于同等条件下H10等级(过滤效率>90%)的商业玻璃纤维过滤膜。

维生素E黏胶/石墨烯锦纶/蚕丝复合功能交织物的制备与研究

高附加值、多功能纺织品成为纺织研究界探索的重要领域。本文通过将蚕丝、维生素E黏胶和石墨烯锦纶进行复合,设计织造了15种织物,对其进行抗氧化性、远红外性能、抗紫外性能与抗静电性能的测试研究。采用响应面分析技术(RSM)研究了投纬比例和组织结构对功能性表达的影响关系,结合模糊多准测决策法(F-MCDM)对最佳工艺参数进行了评估。结果表明:两种纬纱的投纬比和织物组织对织物的功能性表达都有不同程度的影响,且影响是交互的复杂作用。当纬纱中维生素E黏胶和石墨烯锦纶的投纬比为1︰1、织物组织为八枚缎纹时,织物试样的四种功能性表达最好。

凹凸棒石增强PA6复合线材制备及3D打印研究

为提高聚酰胺6(PA6)3D打印样件的力学性能,以凹凸棒石(ATP)为增强填料,通过γ-氨丙基三乙氧基硅烷(KH-550)表面改性ATP,采用熔融共混制备PA6/ATP复合材料并通过单螺杆挤出形成3D打印线材,研究了ATP在3D打印过程中的取向行为及其对PA6力学性能的影响,探讨了填料的增强机制。结果表明,适量的ATP能显著提升PA6的力学性能,拉伸强度和杨氏模量分别为73.8 MPa和3.11 GPa,较纯PA6提升35%和27%,ATP在PA6基体中有序取向。

玻纤增强PA6焊机外壳性能的影响因素数值模拟

深入探讨了玻璃纤维增强聚酰胺6在焊机外壳应用中的性能表现,并基于ANSYS软件平台,进行了静力学仿真和落球冲击仿真分析,旨在揭示玻纤含量、玻纤长径比以及玻纤取向等关键参数对焊机外壳性能的影响。静力学分析显示,当外壳承受2500 N的拉力时,玻纤含量的增加对焊机外壳应力强度的影响较小,但能够降低了外壳变形程度。当玻纤质量分数超过25%时,等效应力趋于稳定(约51 MPa)。此外,玻纤的取向对焊机外壳性能具有显著影响。当纤维沿X轴和Z轴取向且各占50%时(方向向量为a2),外壳的等效应力达54.6 MPa,同时变形量最小,仅为0.5 mm,这一性能与玻纤质量分数为40%的外壳相当。而玻纤长径比的增加对等效应力的影响并不显著,但有助于减少变形。进一步,通过落球冲击分析发现,随着玻纤含量的增加,外壳的等效应力逐渐增大,变形逐渐减小,这一趋势与静力学分析结果高度一致。当玻纤质量分数低于20%时,焊机外壳在冲击下易出现破裂;然而,当玻纤质量分数为20%~35%时,外壳表现出了优异的冲击性能,未出现开裂现象。

聚酰胺酸大分子偶联剂乳液的合成及其在回收玻璃纤维增强高温尼龙的界面改性中的应用

为提升回收玻璃纤维(Recycled glass fiber,rGF)在增强高温尼龙复合材料中的应用价值,制备用于rGF表面处理的耐高温型玻璃纤维浸润剂。以4,4′-联苯醚二酐(ODPA)为二酸酐单体、4,4′-二氨基二苯醚(ODA)为二胺单体,合成聚酰胺酸(PAA),然后与γ-氨丙基三乙氧基硅烷(KH550)反应得到聚酰胺酸大分子偶联剂(PAA-KH550);通过调控ODPA与ODA单体比例,制备得到稳定分散的自乳化PAA-KH550乳液。通过激光粒度分析仪、傅里叶变换红外光谱仪及热失重分析仪对乳液的粒径、化学结构及PAA-KH550乳液固化膜的耐高温性能进行测试;并采用扫描电子显微镜、单纤维强力机、全自动表面张力仪及复合材料界面评价装置对乳液涂覆的GF进行形貌观察、单丝性能测试、浸润性测试及与聚酰胺46(PA46)的界面剪切强度测试。结果表明:乳液平均粒径均为110~125 nm,且粒径分布较小;PAA-KH550乳液固化膜耐高温性能优于PAA乳液固化膜,其5%热分解温度(T_(d5))在350℃以上;制得的乳液能在rGF表面均匀成膜,有效弥补纤维表面缺陷,从而提升rGF的力学性能。此外,乳液涂敷固化后在纤维表面形成的涂层可有效提高纤维表面能,有助于改善GF与PA46的界面结合性能;实验测得经PAA-KH550乳液处理的GF/PA46复合材料的界面剪切强度(IFSS)最高达到(31.29±6.39)MPa,相比未经乳液处理的样品提高了37%。制备的水体系分散稳定的PAA乳液和PAA-KH550乳液,将其应用于rGF表面可有效恢复rGF的综合性能,同时可改善与PA46的界面结合,提高rGF/PA46复合材料的耐高温性能及力学性能,为rGF在高性能复合材料中的应用提供了新方案。