Effect of Dispersed Multi-Walled Carbon Nanotubes on Mixed Matrix Membrane for O2/N2 Separation

Mixed matrix membranes (MMMs) consisting of multiwalled carbon nanotubes (MWCNTs) embedded within polyetherimide were prepared. Surfactants of different charges were utilized to disperse the nanotubes through a simple non-covalent approach. The characterization results suggest that proper selection of the dispersing agent contributed to better dispersion of nanotubes. The MMMs exhibited improved thermal stability and mechanical strength, which indicate the improvement of dispersion and compatibility within the polymer matrix. The resulting membrane exhibited permeance improvement of O₂ and N₂ as much as 87.7% and 120% respectively compared to that of neat polyetherimide. The results implied that Triton-X100 treated MWCNTs is a promising filler to enhance gas permeability.     

Preparation of a Facilitated Transport Membrane Composed of Carboxymethyl Chitosan and Polyethylenimine for CO2/N2 Separation

The miscibility of carboxymethyl chitosan/polyethylenimine (CMCS/PEI) blends was analyzed by FT-IR, TGA and SEM. Defect-free CMCS/PEI blend membranes were prepared with polysulfone (PSf) ultrafiltration membranes as support layer for the separation of CO₂/N₂ mixtures. The results demonstrate that the CMCS/PEI blend is miscible, due to the hydrogen bonding interaction between the two targeted polymers. For the blended membrane without water, the permeability of CO₂ gas is 3.6 × 10⁻⁷ cm³ cm⁻² s⁻¹ cmHg⁻¹ and the corresponding separation factor for CO₂ and N₂ gas is about 33 at the pressure of 15.2 cmHg. Meanwhile, the blended membrane with water has the better permselectivity. The blended membrane containing water with PEI content of 30 wt% has the permeance of 6.3 × 10⁻⁴ cm³ cm⁻² s⁻¹ cmHg⁻¹ for CO₂ gas and a separation factor of 325 for CO₂/N₂ mixtures at the same feed pressure. This indicates that the CO₂ separation performance of the CMCS/PEI blend membrane is higher than that of other facilitated transport membranes reported for CO₂/N₂ mixture separation.     

Improving Mechanical Properties of Carbon/Epoxy Composite by Incorporating Functionalized Electrospun Polyacrylonitrile Nanofibers

Electrospun functionalized polyacrylonitrile grafted glycidyl methacrylate (PAN‐g‐GMA) nanofibers are incorporated between the plies of a conventional carbon fiber/epoxy composite to improve the composite's mechanical performance. Glycidyl methacrylate (GMA) is successfully grafted onto polyacrylonitrile (PAN) polymer powder via a free radical mechanism. Characterization of the electrospun PAN and PAN‐g‐GMA nanofibers indicates that the grafting of GMA does not significantly alter the tensile properties of the PAN nanofibers but results in an increase in the diameter of nanofibers. Statistical analysis of the mechanical characterization studies on PAN‐carbon/epoxy hybrid composites conclusively shows that the composite reinforced with functionalized PAN nanofibers has greater mechanical properties than that of both the neat PAN nanofiber enriched hybrid composite and control composite (without nanofibers). The improved performance is attributed to the grafted glycidyl groups on PAN, leading to stronger interactions between the nanofibers and the epoxy matrix. PAN‐g‐GMA nanofiber reinforced composite outperforms their neat PAN counterparts in tensile strength, short beam shear strength, flexural strength, and Izod impact energy absorption by 8%, 9%, 6%, and 8%, respectively. Compared to the control composite, the improvements resulting from the PAN‐g‐GMA nanofiber incorporation are even more pronounced at 28%, 41%, 32%, and 21% in the corresponding tests, respectively.

     

Efficient CO2 Separation Using a PIM-PI-Functionalized UiO-66 MOF Incorporated Mixed Matrix Membrane in a PIM-PI-1 Polymer

Metal–organic framework (MOF) incorporated mixed–matrix membranes (MMMs) attract great interest for gas separation applications because they overcome limitations faced by typical polymer membranes, including permeability–selectivity trade-off, aging effect, and plasticization phenomenon. However, optimal MOF–polymer interface compatibility is the key challenge in fabricating defect-free high-performance gas-separation MMMs. Here, a surface modification strategy of the UiO-66-NH₂ MOF using a covalently bound PIM-PI-oligomer is developed to engineer interface compatibility with the polymer that has an identical chemical structure (PIM-PI-1) in the MMMs. A series of MMMs are prepared with different loadings of homogeneously distributed PIM-PI-functionalized MOFs (PPM). Significant improvements in CO₂/N₂ and CO₂/CH₄ selectivity and permeability are achieved with these MMMs, ranging from 5 to 10 wt% of the PPM loadings. The MMM with 10 wt% loading (PPM-10@MMM) shows a CO₂ permeability of 3827.3 Barrer and a CO₂/N₂ and CO₂/CH₄ selectivity of 24 and 13.4, respectively. This surpasses the 2008 Robeson upper bound for CO₂/N₂ and is very close to the 2008 upper bound for CO₂/CH₄. The experimental results are further compared using Maxwell's equation for MMMs. The resulting MMMs show a plasticization resistance against CO₂ up to 25 atm pressure and anti-aging performance for 180 h.     

Effect of Raw Multi-Wall Carbon Nanotubes on Morphology and Separation Properties of Polyimide Membranes

Raw multi wall carbon nanotubes (r-MWCNTs) were embedded as fillers inside the polyimide (PI) matrix and PI/r-MWCNTs mixed matrix membranes were fabricated by the phase inversion method. The TEM images and permeation results using helium as test gas showed that r-MWCNTs were generally closed ended and acted as impermeable nano particles. Gas permeation tests using CO₂ and CH₄ showed that the addition of r-MWCNTs into the dope solution increased the CO₂/CH₄ separation factor while decreasing the carbon dioxide and methane permeances. When the r-MWCNTs content was increased from 0% to 6 wt.%, permeance of CO₂ in the flat sheet mixed matrix membranes decreased from 9.15 GPU to 5.49 GPU and CO₂/CH₄ separation factor increased from 19.05 to 45.75. Identical to flat sheet mixed matrix membranes, the addition of 2 wt.% r-MWCNTs into a spinning dope increased the CO₂/CH₄ separation factor from 46.61 to 72.20. The glass transition temperature of the mixed matrix flat sheet membranes increased with an increase in the r-MWCNTs content. This implies a good segmental-level attachment between the two phases that forms a rigidified polymer region at the polymer/r–MWCNTs interface. FESEM images showed well dispersed r-MWCNTs in the polymer matrix at a loading of 2 wt% r-MWCNTs.     

纳米TiO2/丝素复合膜的制备及其光催化性能

采用复合法制备了纳米TiO2/丝素复合膜,并用AFM、EDS和IR对复合膜进行了表征,考察了复合膜的光催化甲基橙行为。结果表明,复合膜制备方法合理,当w(TiO2)=0.1%时,它以粒径50 nm左右均匀分散于复合膜中,复合膜与普通丝素膜仅存在细微的构象差异,因纳米TiO2存在,复合膜对甲基橙降解率达91%,催化性能符合Langmu ir-H im shelwood模型。     

CO_2/CH_4分离膜研究进展

介绍ＣＯ２／ＣＨ４分离膜的开发背景及发展历史;ＣＯ２／ＣＨ４分离膜材料及相应的成膜技术,并提出ＣＯ２／ＣＨ４分离膜的发展方向。     

纳米SiC增韧Al_2O_3陶瓷复合材料的制备、表征及力学性能研究

以SiC和Si微米粉为添加剂,采用无压烧结工艺制备了纳米SiC增韧的Al2O3陶瓷复合材料,探讨了SiC含量、烧结气氛和烧结温度对复合材料的烧成收缩率、微观形貌、抗弯强度、维氏硬度及断裂韧性的影响。结果显示：SiC的添加使复合材料的烧成收缩率下降,惰性气氛下复合材料的收缩率要大于氧化气氛和还原气氛时的收缩率。在氧化性气氛下烧结时,当SiC添加量为4%时,复合陶瓷的体积密度为3.80 g·cm^-3,抗弯强度、断裂韧性及维氏硬度均达到最大值,分别为480 MPa、5.12 MPa·m1/2、16.2 GPa。添加SiC后所得复合材料的基体颗粒为椭圆状,粒径为2μm左右,颗粒与颗粒之间结合紧密,颗粒形状的改变可能是因为烧结机理发生变化所致。纳米SiC颗粒位于晶界处,形成了由Al2O3-SiC-Al2O3搭桥联结的晶界,提高了晶界强度,导致裂纹只能在晶内传播。     

PEBA/氮硫共掺杂多孔碳球混合基质膜的制备及CO2分离性能研究

为了获得高性能的混合基质膜,有效捕集烟道气中的CO₂,设计了对CO₂有优异的扩散选择性和吸附选择性的氮硫共掺杂多孔碳球添加剂,实现了烟道气中CO₂/N₂的高效分离。选用表面含氧基团丰富的葡萄糖作为碳源,硫脲作为氮源和硫源,通过水热法制备了氮硫共掺杂碳球（NSC）,并用KOH活化,获得了具有多孔结构的氮硫共掺杂碳球（NSPC）,再加入聚醚嵌段酰胺（PEBA）中制备出PEBA/NSPC混合基质膜。采用FTIR、XRD和BET表征了材料的化学结构和孔结构,借助力学性能表征了膜的两相界面相容性。系统研究了PEBA/NSPC混合基质膜中葡萄糖与硫脲的质量比、NSC和KOH的质量比、NSPC的添加量、操作压力、操作温度,以及模拟烟道气条件对膜CO₂渗透性、CO₂/N₂选择性的影响。结果表明：NSPC材料成功实现了氮、硫元素的共掺杂,而且具有较好的孔结构。在操作温度25℃、操作压力0.2 MPa的条件下,混合基质膜中NSPC添加量为3%（质量）时气体分离性能最优,CO₂渗透系数和CO₂/N₂选择性分别为589 Barrer和64,相比纯PEBA膜分别提高了244%和139%。这是因为多孔碳球的微孔结构显著提高了CO₂的扩散选择性,同时氮、硫元素的掺杂因为酸碱相互作用和良好亲和性有效提高了CO₂的吸附选择性。稳定性实验表明,PEBA/NSPC混合基质膜在360 h连续运行过程中气体分离性能稳定,具有较好的工业应用前景。     

Synthesis and Characterization of Polyimide Mixed Matrix Membranes

Polyimides of Matrimid 5218 and P84 as backbone and different fillers including silica aerosil, zeolite 4A, carbon nanotubes, and carbon molecular sieves were used to synthesize flat mixed matrix membranes (MMMs). Effects of different polymer types and concentrations, different filler types and contents, and fabrication procedure were investigated. Scanning Electron Microscopy (SEM) analysis showed acceptable connections between the two phases and the MMMs performed higher performance compared to the polymeric membranes. Thermal treatment of the MMMs, as a defect repairing technique, was found very effective. Performed pervaporation and gas permeation experiments showed better separation performances of the MMMs with respect to those of the neat polymeric membranes. The results showed up to seven and two times increment in separation factors of MMMs regarding to neat polymeric membranes for pervaporation and gas separation experiments, respectively, while permeation rates nearly remained constant indicating effectiveness of the proper filler incorporation within polymer matrices approach.     

Effect of Feed Composition on the Gas Separation Performance of Binary and Ternary Mixed Matrix Membranes

Binary and ternary component mixed matrix membranes comprised of zeolite 4A and p-nitroaniline (pNA) in the polycarbonate (PC) matrix were prepared and appraised in gas separation. For comparison, homogenous membranes of PC and PC/pNA membranes were also investigated. The membranes were utilized to separate binary mixtures of CO₂/CH₄, H₂/CH₄, and CO₂/N₂. The effect of feed composition on the separation performance of membranes was investigated. Separation factors and ideal selectivities were similar for the PC membrane. A similar trend was also observed with the PC/pNA membrane. The separation factors of the PC/pNA membrane for CO₂/CH₄ were almost twice as high as those of the PC membrane regardless of the feed composition. The ideal selectivities were, however, higher than separation factors for PC/zeolite 4A and PC/pNA/zeolite 4A membranes. The PC/ pNA/zeolite 4A membrane has separation factors of 18 for 77% CO₂/ 23% CH₄ mixture, and 40 for 20% CO₂/ 80% CH₄ mixture, respectively. The separation factors of the mixed matrix membranes depended on the feed composition strongly. The PC/ pNA/zeolite 4A membrane had higher separation factors and lower permeabilities than the PC/zeolite 4A membrane. pNA assisted to eradicate partly the detrimental effects of interfacial voids and improved the molecular sieving effect of zeolite 4A dispersed in the PC.     

炭膜的二氧化碳吸附扩散性能的研究

以商业化的Kapton型聚酰亚胺为前驱体制备炭膜,采用容量法研究了不同炭化温度制备的炭膜CO2吸附和扩散行为,并利用Sips模型对实验数据进行拟合,DA方程计算炭膜的孔结构参数,Fick扩散模型求取CO2在炭膜内的扩散系数,采用XRD分析探讨了炭膜的炭结构。结果表明,炭膜孔结构随着热解炭化温度的提高,孔径收缩,且当炭化温度从600℃升高到800℃,炭膜的微孔体积随炭化温度的升高而增大,而800℃以后,微孔体积随炭化温度的升高而下降。CO2在不同炭膜中的扩散系数约为1.04×10-13~8.56×10-12m2·s-1,在实验测定的压力范围内扩散系数随着平衡压力的增大呈现出先增大后减小的规律。     

渗透汽化分离DMF/水混合物的PVA-g-AAm膜的制备和表征

使用聚乙烯醇及丙烯酰胺这两种材料,合成了不同枝度的共聚物(PVA-g-AAm),并对两种渗透汽化复合膜(PVA-g-AAm)进行制备。黏均分子量是运用用黏度法测定的,而表征则分别由接触角,红外光谱(FT-IR)和热重(TGA)等方法进行测定。而DMF/水混合体系的渗透汽化分离主要是复合膜的运用,并对膜分离的影响因素进行分析。实验结果显示,分离性能最好的是接枝度为90%的PVA。而PVA的渗透量随着DMF质量分数的增加而减少,PVA的通量最小时是在0.25~0.65 kg/(m~2·h)之间,在0.2~而膜的分离因子达到最大时DMF质量分数为33%。而温度的增加可是渗透量增大,分离因子减小。     

Single and Binary CO2/CH4 Separation of a Zeolitic Imidazolate Framework‐8 Membrane

The performance of a zeolitic imidazolate framework‐8 (ZIF‐8) membrane in single and binary CO₂/CH₄ gas separation was investigated by means of a gas transport model that included generalized Maxwell‐Stefan and binary friction models. The model concerns gas diffusion through the membrane layer, gas flow through membrane intercrystalline pores, and resistance of the support layer. The effective membrane area considering the actual area for the gas permeated through the membrane was also introduced in this model. The selective ZIF‐8 membrane was successfully synthesized using a microwave‐assisted solvothermal method on an α‐alumina support pre‐attached with ZIF‐8 seeds by solvent evaporation. The simulated data agreed well with the experimental data. The model revealed that the membrane intercrystalline pores and its effective area significantly affected the CO₂/CH₄ gas permeation and separation performance.     

Thermal‐Insulation,Electrical, and Mechanical Properties of Highly‐Expanded PMMA/MWCNT Nanocomposite Foams Fabricated by Supercritical CO2 Foaming

Foaming behavior of poly(methyl methacrylate) (PMMA)/multi‐walled carbon nanotubes (MWCNTs) nanocomposites and thermally‐insulating, electrical, and mechanical properties of the nanocomposite foams are investigated. PMMA/MWCNT nanocomposites containing various amounts of MWCNTs are first prepared by combining solution and melt blending methods, and then foamed using CO₂. The foaming temperature and MWCNT content are varied for regulating the structure of PMMA/MWCNT nanocomposite foams. The electrical conductivity measurement results show that MWCNTs have little effect on the electrical conductivity of foams with large expansion ratio. Thermal conductivities of both solid and foamed PMMA/MWCNT nanocomposites are measured to evaluate their thermally insulating properties. The gas conduction, solid conduction, and thermal radiation of the foams are calculated for clarifying the effects of cellular structure and MWCNT content on thermal insulation properties. The result demonstrates that MWCNTs endowed foams with enhanced thermal insulation performance by blocking thermal radiation. Moreover, the compressive testing shows that MWCNTs improve the compressive strength and rigidity of foams. This research is essential for optimizing environmentally friendly thermal insulation nanocomposite foams with enhanced thermal‐insulation and compressive mechanical properties.     

EP/BMI树脂基碳纤维复合材料的制备与性能表征

以环氧树脂(EP)、双马来酰亚胺(BMI)、4,4’-二氨基二苯砜(DDS)和短切碳纤维(SCF)等为主要原料制备了EP/BMI/DDS/SCF复合材料,并研究了SCF添加量对复合材料力学性能和热性能的影响。结果表明,当SCF添加量为0.25 %(质量分数,下同)时,EP/BMI/DDS/SCF复合材料的力学性能提高最大,其拉伸强度、弯曲强度、弯曲模量和缺口冲击强度比未添加SCF时的EP/BMI/DDS复合材料分别提高了48.52 %、32.15 %、25.77 %以及150.91 %;此外,SCF的加入有助于提高复合材料的热性能。     

Synthesis of dual-functionalized mixed matrix membrane with amino-GO-Bent/PVDF for efficient separation of CO2/CH4 and CO2/N2

Mixed matrix membranes (MMMs), which combine the characteristics of inorganic nanofillers and organic matrices, have received wide attention because of their good permeability and selective performance for separating CO₂ from industrial waste gases. In this work, the amino-GO-loaded bentonite (amino GO-Bent) was prepared by loading  NH₂ on the GO surface with a large number of functional sites. Firstly, by introducing  NH₂ on the surface of GO and then interacting with bentonite (Bent) organically modified by silane coupling agents through amide bonding. Mixed matrix membranes (MMMs) with an area of 623.7 cm² and homogeneous texture were prepared using amino-GO-Bent as inorganic filler to improve the membrane selectivity for CO₂/N₂ and CO₂/CH₄ separation. The results show that the introduction of amino GO-Bent in MMMs can greatly improve the CO₂ permeability and obtain high CO₂ permeation performance: 2.67945 × 10⁻⁷ cm³ (STP)·cm/s/cm²/cmHg, and the selectivity of CO₂/N₂ and CO₂/CH₄ can reach 307.28 and 325.97, respectively. The two selective values were 14 and 18 times higher than those of pure PVDF membranes, and the performance of MMMs far exceeded the Robeson upper limit in 2008, respectively.     

C/C复合材料表面羟基磷灰石/聚丙烯酰胺梯度复合涂层的制备与表征(英文)

以丙烯酰胺单体和声化学法制备的纳米羟基磷灰石(hydroxyapatite,HAp)粉为原料、异丙醇为分散介质,采用水热电泳聚合沉积法在C/C复合材料表面制备HAp/聚丙烯酰胺(polyacrylamide,PAM)梯度复合涂层。用电导率仪、X射线衍射仪、扫描电子显微镜、能谱仪、Fourier变换红外分析仪和万能材料试验机等对悬浮液的电导率以及涂层的物相组成、结构、断面微观形貌和结合强度进行了研究,结果表明:异丙醇中碘的浓度为8g/L时,所制备的涂层由HAp和PAM两相组成;HAP被包裹在黏度较大的PAM中,涂层表面均匀,涂层与基体之间结合紧密,未发现明显的裂纹;涂层中元素沿基体–界面方向呈梯度分布;涂层与基体结合强度最大值达到19.10MPa。     

Various Techniques for Preparation of Thin‐Film Composite Mixed‐Matrix Membranes for CO2 Separation

The application of thin‐film composite mixed‐matrix membranes (TFC‐MMMs) for gas separation is widely considered as an efficient separation technology. The principal methods for the preparation of TFC‐MMMs are dip‐coating, phase inversion, and interfacial polymerization comprising different types of support layers. These methods influence the CO₂ permeation over the selective and support layers. A comprehensive review is provided for capturing new details of progress achieved in developing TFC‐MMMs with detailed performance of gas separation in the previous few years. Various preparation techniques of TFC‐MMMs and their effect on the gas separation performance of the prepared membranes are described.     

Preparation and Properties of Carbon/Zeolite Composites with Corrugated Structure

Composites of carbon/zeolite with corrugated structures were prepared by carbonization, steam activation and/or hydrothermal treatment of corrugated paper. No zeolite formation resulted from conventional hydrothermal treatment of the carbonized and activated samples in NaOH solution but zeolite Na P1 was formed by addition of silica to the solution. By contrast, zeolites Na P1 and Na A were formed by the in-situ crystallization method (hydrothermal treatment of solid samples impregnated with NaOH solution). With higher impregnating NaOH concentrations, longer reaction times and higher reaction temperatures, the products changed to sodalite- and cancrinite-type compounds. Hydrothermal treatment was effective in increasing the specific surface area of the products by the formation of zeolite from amorphous calcium aluminosilicate, and also increased the mechanical strength by gluing together the carbon fibers in the samples. The resulting samples showed enhanced adsorption for polar molecules such as ammonia, water vapor and methanol due to the formation of composites of activated carbon with hydrophilic zeolites.