Carbon molecular sieve membranes derived from Matrimid® polyimide for nitrogen/methane separation

A commercial polyimide, Matrimid® 5218, was pyrolyzed under an inert argon atmosphere to produce carbon molecular sieve (CMS) dense film membranes for nitrogen/methane separation. The resulting CMS dense film separation performance was evaluated using both pure and mixed N₂/CH₄ permeation tests. The effects of final pyrolysis temperature on N₂/CH₄ separation are reported. The separation performance of all CMS dense films significantly exceeds the polymer precursor dense film. The CMS dense film pyrolyzed at 800 °C shows very attractive separation performance that surpasses the polymer membrane upper bound line, with N₂ permeability of 6.8 Barrers and N₂/CH₄ permselectivity of 7.7 from pure gas permeation, and N₂ permeability of 5.2 Barrers and N₂/CH₄ permselectivity of 6.0 from mixed gas permeation. The temperature dependences of permeabilities, sorption coefficients, and diffusion coefficients of the membrane were studied, and the activation energy for permeation and diffusion, as well as the apparent heats of sorption are reported. The high permselectivity of this dense film is shown to arise from a significant entropic contribution in the diffusion selectivity. The study shows that the rigid ‘slit-shaped’ CMS pore structure can enable a strong molecular sieving effect to effectively distinguish the size and shape difference between N₂ and CH₄.     

Carbon molecular sieve dense film membranes derived from Matrimid® for ethylene/ethane separation

Development of dense film carbon molecular sieve (CMS) membranes for ethylene/ethane (C₂H₄/C₂H₆) separation is reported. A commercial polyimide, Matrimid®, was pyrolyzed under vacuum and inert argon atmosphere, and the resultant CMS films were characterized using pure C₂H₄ and C₂H₆ permeation at 35 °C, 50 psia feed pressure. The effects on C₂H₄/C₂H₆ separation caused by different final vacuum pyrolysis temperatures from 500 to 800 °C are reported. For all pyrolysis temperatures separation surpassed the estimated ‘upper bound’ solution processable polymer line for C₂H₄ permeability vs. C₂H₄/C₂H₆ selectivity. C₂H₄ permeability decreased and selectivity increased with increasing pyrolysis temperature until 650–675 °C where an optimum combination of C₂H₄ permeability ～14–15 Barrer with C₂H₄/C₂H₆ selectivity ～12 was observed. A modified heating rate protocol for 675 °C showed further increase in permeability with no selectivity loss. CMS films produced from argon pyrolysis showed results comparable to vacuum pyrolysis. Further, mixed gas (63.2 mol% C₂H₄ + 36.8 mol% C₂H₆) permeation showed a slightly lower C₂H₄ permeability with C₂H₄/C₂H₆ selectivity increase rather than a decrease that is often seen with polymers. The high selectivity of these membranes was shown to arise from a high ‘entropic selection’ indicating that the ‘slimmer’ ethylene molecule has significant advantage over ethane in passing through the rigid ‘slit-shaped’ CMS pore structure.     

Structure–performance characterization for carbon molecular sieve membranes using molecular scale gas probes

Understanding the relationship between carbon molecular sieve (CMS) pore structure and corresponding gas separation performance enables optimization for a given gas separation application. The final pyrolysis temperature and starting polymer precursor are the two critical parameters in controlling CMS performance. This study considers structure and performance changes of CMS derived from a commercially available polymer precursor at different pyrolysis temperatures. As reviewed in this paper, most traditional characterization methods based on microscopy, X-ray diffraction, spectroscopy, sorption-based pore size distribution measurements etc. provide limited information for relating separation performance to the CMS morphology and structural changes. A useful alternative approach based on different sized gases as molecular scale probes of the CMS pore structure was successfully used here in conjunction with separation data to provide critical insights into the structure–performance relationships of the engineered CMS.     

Crystallographic characterization of silicon nitride ceramics sintered with Y2O3–Al2O3 or E2O3–Al2O3 additions

Silicon nitride ceramics were sintered using Y₂O₃–Al₂O₃ or E₂O₃–Al₂O₃ (E₂O₃ denotes a mixed oxide of Y₂O₃ and rare-earth oxides) as sintering additives. The intergranular phases formed after sintering was investigated using high-resolution X-ray diffraction (HRXRD). The use of synchrotron radiation enabled high angular resolution and a high signal to background ratio. Besides the appearance of β-Si₃N₄ phase the intergranular phases Y₃Al₅O₁₂ (YAG) and Y₂SiO₅ were identified in both samples. The refinement of the structural parameters by the Rietveld method indicated similar crystalline structure of β-Si₃N₄ for both systems used as sintering additive. On the other hand, the intergranular phases Y₃Al₅O₁₂ and Y₂SiO₅ shown a decrease of the lattice parameters, when E₂O₃ was used as additive, indicating the formation of solid solutions of E₃Al₅O₁₂ and E₂SiO₅, respectively.     

Influence of Al2O3 whisker concentration on flexural strength of Al2O3(w)–ZrO2 (TZ-3Y) composite

On investigating the possibility of using alumina whisker reinforced 3 mol% Yttria stabilized Tetragonal Zirconia (TZ-3Y) composite for bioceramic applications, presented here is the influence of varying whisker concentration (2, 5, 10, 15 and 20 wt%) on flexural strength of the composite. Whiskers of hydrothermally synthesized Ammonium Aluminum Carbonate Hydroxide (AACH) were used for composite synthesis. These whiskers transformed in situ into alumina during sintering. It was found that with addition of alumina whiskers, strength was increased and reached a maximum value of 1212±60 MPa and 1325±65 MPa, in pure and 1 wt% CTAB added samples respectively, at a concentration of 10 wt% Al₂O₃ whiskers. The strength values of the synthesized composite can compete well with commercially available materials for dental applications.     

Beyond graphene oxides: Emerging 2D molecular sieve membranes for efficient separation☆

Recent decades witnessed the significant progress made in the research field of 2D molecular sieve membranes.In comparison with their 3D counterparts, 2D molecular sieve membranes possessed several unique advantages like significantly reduced membrane thickness(one atom thick in theory) and diversified molecular sieving mechanisms(in-plane pores within nanosheets interlayer galleries between nanosheets). M. Tsapatsis first carried out pioneering work on fabrication of lamellar ZSM-5 membrane. Since then, diverse 2D materials typically including graphene oxides(GOs) have been fabricated into membranes showing promising prospects in energy-efficient gas separation, pervaporation, desalination and nanofiltration. In addition to GOs, other emerging 2D materials, including 2D zeolites, 2D metal–organic frameworks(MOFs), 2 D covalent-organic frameworks(COFs), layered double hydroxides(LDHs), transition metal dichalcogenides(TMDCs), MXenes(typically Ti_3C_2TX), graphitic carbon nitrides(typically g-C_3N_4), hexagonal boron nitride(h-BN) and montmorillonites(MT) are showing intriguing performance in membrane-based separation process. This article summarized the most recent developments in the field of 2D molecular sieve membranes aside from GOs with particular emphasis on their structure–performance relationship and application prospects in industrial separation.     

Spinelisation and properties of Al2O3–MgAl2O4–C refractory: Effect of MgO and Al2O3 reactants

The effect of particle size of MgO and Al₂O₃ on the spinel formation associated with permanent linear change on reheating (PLCR) and microstructure of Al₂O₃–MgAl₂O₄–C refractory is investigated as a function of heating cycle at 1600 °C with 2 h holding at each cycle. It was found that rate of spinel formation and associated volume expansion is very much dependent on the reactivity and particle size of the reactant. When the reactants are very fine and reactive there is considerable amount of spinel formation, whereas coarser reactants with lower reactivity show negligible formation of spinel phase and associated expansion. Magnesia and alumina with moderate reactivity develops optimum PLCR of the refractory. It continuously increases with the number of heating cycles. The SEM photomicrographs show that in Al₂O₃–MgAl₂O₄–C refractory the spinel phase is formed in between the calcined bauxite grain and the EDX analysis indicates that the spinel phase formed is stoichiometric in nature.     

Pressureless sintered Al2O3–SiC nanocomposites

Al₂O₃ + 5 vol% SiC composite ceramics were prepared via a conventional powder processing route followed by pressureless sintering. Commercially available Al₂O₃ and SiC powders were milled together in an aqueous suspension. The slurry was freeze granulated, and green bodies were obtained by cold isostatic pressing of the granules. Pressureless sintering was carried out in a nitrogen atmosphere at 1750 and 1780 °C. Near full density (>99%) was achieved at 1780 °C. Densification at the lower sintering temperature was promoted by smaller additions of MgO. Vickers hardness and indentation fracture toughness varied around 18 GPa and 2.3 MPa m^1/2 after sintering at 1780 °C. Transmission electron microscopy revealed that the SiC particles were located predominantly to the interior of the matrix grains and well distributed throughout the composite microstructures. The intragranular particles had sizes in the range 50–200 nm while the intergranular particles were larger, typically 200–500 nm in diameter.     

Bi2O3对K2O–B2O3–SrO–Al2O3–Nb2O5–SiO2玻璃陶瓷介电储能性能的影响

随着电力电子系统的不断发展,高功率脉冲电容器的需求增多。电介质电容器因具有放电功率大、充放电速度快及性能稳定等优点,在电力系统、电子器件、脉冲电源等方面发挥着重要作用,广泛应用于民用领域及军事领域。通过熔融压延制备玻璃基体,采用可控结晶工艺研究了不同含量的Bi₂O₃ (x=0.0%、1.0%、2.0%、4.0%,摩尔分数)对K₂O–B₂O₃–Sr O–Al₂O₃–Nb₂O₅–SiO₂玻璃陶瓷物相演化、微观结构、介电和储能性能的影响。在该玻璃陶瓷中,KSr₂Nb₅O₁₅为主要析出晶相,当Bi₂O₃的加入量为x=2.0%(摩尔分数)时,热处理温度为950℃时,玻璃陶瓷样品的储能密度最大可达到1.27 J/cm³,室温下介电常数可达342,是热处...     

Al2O3-3Al2O3·2SiO2-ZrO2耐火材料的相组成

Al2O3-SiO2-ZrO2系耐火材料应用范围广,特别被用作陶瓷辊,具有力学强度高、抗热震性能优良、耐碱类化合物侵蚀和高温蠕变率低的特性。Al2O3-SiO2-ZrO2系耐火材料性能很大程度上取决于其结晶相和玻璃相的总量和化学成分,采用定量XRPD和XRF研究了原料中Al2O3/SiO2比和氧化铝颗粒尺寸分布对结晶相和玻璃相的总量及其化学成分的影响。耐火材料由莫来石、刚玉、ZrO2的多晶体和总量各异的玻璃相组成。莫来石含量及其晶胞参数和成分随烧成温度改变,但主要受原料中Al2O3/SiO2比的影响。     

Effects of liquid phases on densification of TiO2-doped Al2O3–ZrO2 composite ceramics

This study investigated the densification behaviors and microstructural evolution of Al₂O₃–ZrO₂ (3Y) composite ceramics doped with four different amounts of TiO₂ (0, 1, 4, and 8 wt%; denoted as 0T, 1T, 4T, and 8T, respectively) to clarify the effect of TiO₂ dopants on densification. The shrinkage rate during densification increased with the increase in the amount of TiO₂. The development of grain boundary feature was also examined. The undoped ceramic showed clean grain boundaries. Thin liquid grain boundary phases were observed in 1T, whereas large liquid phases were found on the grain boundary and at the junction pockets in 4T and 8T. The results were discussed in terms of the relationship between densification and grain boundary feature.     

多组元BaO–SrO–CaO–MgO–Al2O3–2SiO2环境障涂层的制备与抗CaO–MgO–Al2O3–SiO2腐蚀性能

采用固相法制备不同摩尔 Ba、Sr、Ca、Mg 配比的 Ba O–Sr O–Ca O–Mg O–Al₂O₃–SiO₂ （BSCMAS）陶瓷材料,研究多组元陶瓷的制备工艺、显微结构及其抗 CMAS 腐蚀性能。结果表明：通过调控 MgO 的含量,在 1 400 ℃条件下制备了Ba_0.3Sr_0.3Ca_0.35Mg_0.05Al₂Si₂O₈ (B_0.3S_0.3C_0.35M_0.05AS)单相多组元陶瓷材料。在 1 250、1 300 ℃和 1 350 ℃对 B_0.3S_0.3C_0.35M_0.05AS 进行 CMAS 腐蚀实验,相比于 Ba_0.5Sr_0.5Al     

Al2O3/Fe2O3吸附剂脱除硫化氢的性能

采用共沉淀法制备了氧化铝改性的氧化铁吸附剂,并采用比表面积(BET)、X射线衍射(XRD)技术对吸附剂进行了表征。在固定吸附床上,考察了制备条件及吸附条件对吸附剂脱除硫化氢性能的影响。结果表明,引入氧化铝能显著提高氧化铁对硫化氢的吸附净化能力。氧化铁与氧化铝质量比为1∶0.5,造孔剂十六烷基三甲基溴化铵(CTAB)质量分数为2%,焙烧温度500℃时,采用共沉淀法的负载氧化铝吸附剂的吸附效果最好。在气速20 mL/min,吸附温度80℃时,脱硫率和穿透硫容可分别达到99.3%和105 mg/g,其穿透硫容比未经改性的活性氧化铁提高了49.8 mg/g。     

添加Al2O3溶胶改善Al2O3-MA浇注料的抗侵蚀性

以铝酸钙水泥(CAC)为结合剂的传统Al2O3-MA浇注料在热处理过程中生成CA6,导致浇注料产生膨胀而降低其抗渣性能。巴西研究人员制备了氧化铝溶胶(ColAlu)结合的Al2O3-MA浇注料,以提高其抗渣侵蚀性,并与水合氧化铝(HA)结合和铝酸钙水泥结合的Al2O3-MA浇注料进行了对比。     

钛合金熔炼用Y2O3–Al2O3–MgO–CaO系耐火材料的设计与制备

坩埚耐火材料对钛合金熔炼的质量非常重要,为开发高性能新型坩埚材料,以工业Y₂O₃和Al₂O₃–MgO–CaO系粉末(AMC)为原料,制备出Y₂O₃–Al₂O₃–MgO–CaO系复合耐火材料,研究了烧结温度(1 500℃、1 600℃)和AMC含量(0、25%、50%、75%和100%,质量分数)对所制备耐火材料的物相组成、烧结性能(线收缩率、体积收缩率、显气孔率、体积密度)、常温耐压强度、抗热震性能和显微结构的影响。结果表明：相对于Y₂O₃和AMC材料,复合材料的性能均有所提高;提高烧结温度,其性能更佳;且随着AMC含量的提高,复合材料的线收缩率、体积收缩率、体积密度和常温耐压强度随之增大,显气孔率降低;当AMC的质量含量为75%时,1 500℃烧结3 h制得复合材料的综合性能最优,其显气孔率为4.37%,常温耐压强度为274.99 MPa,3次水冷热震后残余强度为16...     

Eutectic crystallization in the UO2–Al2O3–HfO2 ceramic phase diagram

In the frame of the Generation IV Sodium Fast Reactor (SFR) safety studies, a core catcher with a sacrificial material could be placed at the bottom of the nuclear reactor. Its role is to dilute the (U, Pu)O₂ molten fuel in case of a hypothetical core meltdown accident. A Al₂O₃–HfO₂ ceramic is a candidate for the sacrificial material. To understand how the molten fuel would mix with this sacrificial material, the UO₂–Al₂O₃–HfO₂ system was investigated at CEA Cadarache PLINIUS corium platform. The eutectic position of the UO₂–Al₂O₃–HfO₂ was determined: the eutectic temperature is 1728±22 °C (2001±22 K) and the eutectic composition is 30 wt% UO₂–35 wt% Al₂O₃–35 wt% HfO₂. Then, the pseudo-binary UO₂–(50 wt% Al₂O₃–50 wt% HfO₂) phase diagram has been proposed.     

Multiferroic ceramics in BaO–Y2O3–Fe2O3–Nb2O5 system

Multiferroic ceramics in BaO–Y₂O₃–Fe₂O₃–Nb₂O₅ system were synthesized and their dielectric, ferroelectric and magnetic properties were evaluated. XRD results showed that the ceramic composite consists of a major phase of tetragonal tungsten bronze structured Ba₂YFeNb₄O₁₅, and minor phases of monoclinic YNbO₄ and hexagonal Ba₃Fe₂Nb₆O₂₁. Three dielectric relaxations were observed in the temperature range from 125 to 575 K. The relaxor dielectric behavior in the temperature range from 125 to 350 K was attributed to the random occupation of Fe³⁺ and Nb⁵⁺ ions at B site of the tungsten bronze structure. The electrode polarization and the inhomogeneous structure contributed to the high-temperature and middle-temperature dielectric relaxations, respectively. Both the ferroelectric hysteresis loop and the magnetic hysteresis loop were measured, which suggested that the synthesized ceramic composite was a promising candidate of multiferroics.     

Phase transformation and gas–solid reaction of Al2O3 during high-energy ball milling in N2 atmosphere

Al₂O₃ powders were milled in N₂ atmosphere using an attritor ball mill. The phase transformation and gas–solid reaction of Al₂O₃ during high-energy ball milling in N₂ atmosphere were investigated. It is found that the γ-Al₂O₃ transform to α-Al₂O₃ as milling time increases. Milled for 20 h in N₂ atmosphere, Al₂O₃ becomes partially amorphous and the gas–solid reaction between Al₂O₃ and N₂ takes place. A new phase with cubic aluminum nitride (AlN) structure forms during milling which is different from normal hexagonal AlN produced by carbon thermal reduction processing. As milling energy increases, the amount of this new phase with cubic AlN structure increases. The amount of this new phase is as high as 72% when Al₂O₃ is milled in N₂ atmosphere at 650 rpm for 40 h.     

电熔镁砂在CaO–Al2O3–SiO2熔渣中的溶解行为

作为镁质耐火材料的重要原料,电熔镁砂在低密度高强钢精炼用CaO–Al₂O₃–SiO₂系熔渣中的溶解是影响炉衬使用寿命及钢质量的重要因素。本工作采用高温激光共聚焦显微观测系统研究了1 600℃下镁砂在该熔渣中的溶解行为,探究了镁砂颗粒的形状、质量及熔渣CaO和SiO₂质量分数比(即C/S)对其溶解行为的影响。结果表明：镁砂主要形状对其溶解速率影响较小;溶解速率随质量增大呈近线性下降,随C/S的增加而先降低后增加;镁砂颗粒的溶解曲线受质量影响更大,其溶解模型n值分别对应1/2、2/3、3/5,这为深入理解镁质耐火材料的渣蚀行为和提质优化提供指导。     

Fe2O3/Ni2O3/Al2O3催化剂制备及其催化氧化靛蓝废水研究

以三氧化二铝为载体,采用浸渍沉淀法制备系列Fe2O3/Ni2O3/Al2O3催化剂。采用TG-DTA,XRD及ESEM等技术对催化剂进行表征,确定催化剂的最佳焙烧温度为460℃。以次氯酸钠为氧化剂,同时考察m(三氧化二镍)/m(三氧化二铝)、m(三氧化二铁)/m(三氧化二镍)、m(次氯酸钠)∶m(靛蓝废水)、pH对印染靛蓝废水处理的影响。结果表明:m(三氧化二镍)/m(三氧化二铝)=0.3,m(三氧化二铁)/m(三氧化二镍)=0.04,m(次氯酸钠)∶m(靛蓝废水)=1∶11,pH=7,反应温度为20℃,常压反应时间为2 h时,COD的去除率为95.3%。