机械化学法制备金属-有机骨架及其复合物研究进展

金属-有机骨架(MOFs)是由金属离子/簇和多齿状有机配体通过配位键桥联而形成的多孔晶态材料。MOFs材料具有孔隙率高、比表面积大、尺寸可调、结构易修饰、功能多样化等特点,使其在气体吸附、分离和催化等方面都具有潜在应用价值。到目前为止,在MOFs合成的几种常见方法中,机械化学法(即在无溶剂或极少量溶剂的情况下研磨固体反应物进行的反应)作为一种清洁、绿色、高效的合成手段逐渐引起人们的关注。本综述总结了近年来机械化学合成MOFs及其复合物的典型进展,目的是为机械化学法合成MOFs及其复合材料提供一个通用而易于理解的概述。目前的研究进展表明,机械化学法是一种实用且环境友好的合成方法,为低成本、宏量生产MOFs及其复合物提供了可能。     

无机纳米与多孔材料合成中的凝聚态化学

所谓凝聚态,一般意义上是指液态和固态,而凝聚态化学,即是在固相和液相中的各种化学过程。在无机材料,特别是无机纳米与多孔材料的合成制备中,凝聚态化学过程贯穿其中,几乎无处不在。在固相材料合成过程中,通过液相中的各种化学反应以获得目标固体材料的所需组分和物相,也许就是无机材料合成中一个最基本的凝聚态化学问题;而多孔如微孔或介孔材料合成中,更涉及伴随组分和物相形成过程中的孔结构形成与调控;进一步,在制备面向实际应用如催化剂和药物载体时,则在以上的各项要求之外,还必须考虑材料的表面活性位、缺陷等关键因素,以及颗粒尺寸、分散性和形貌等几何和物理特性。本文以无机氧化物为对象,讨论了无机材料在凝聚态化学合成过程中的几个侧面,包括纳米颗粒和粉体的化学合成方法,多孔材料的合成和多孔复相结构的合成调控,以及多级孔结构沸石的合成制备与催化性能,以期能加深对材料合成中凝聚态化学过程的认识,并期待以凝聚态化学为指导,进一步推动无机材料特别是纳米多孔材料合成的发展。     

Room temperature thermoelectric performance of Methyl Ammonium Lead Iodide Perovskite and their MWCNT-PANI composites

The excellent properties of Methyl Ammonium Lead Iodide (MAPI) have already created an extensive research interest in photovoltaic applications. However, their utility in thermoelectric application is still not realized thoroughly by researchers. By continuing this interest, we have explored the formation of low dimensional CH₃NH₃PbI₃ (MAPI) perovskite in presence of Polyaniline (PANI) and Multi-Walled Carbon Nanotubes (MWCNT) and its thermoelectric performance. For this purpose, a two stage, in-situ synthesis method was developed to prepare various composites such as MAPI-PANI, MWCNT-MAPI and MWCNT-PANI-MAPI. The as-formed MWCNT-PANI-MAPI composite revealed p-type conductivity with enhanced ZT (up to ~20,000 times) and power factor (3000 times) at room temperature as compared to pristine MAPI sample. Finally, we have demonstrated a proto-type thermoelectric power generator (TE device) fabricated using the best performing composite sample and measured its power output and efficiency at varied δT.     

Multiobjective Optimization of Fabrication Parameters of Jute Fiber/Polyester Composites with Egg Shell Powder and Nanoclay Filler

In the present study, a model is presented to optimize the fabrication parameters of natural fiber reinforced polyester matrix composites with dual fillers. In particular, jute fiber mat was chosen as reinforcement and eggshell powder (ESP) and montmorillonite nanoclay (NC) were selected as fillers. The weight per square meter (GSM) of the fiber, the weight percentage of ESP and NC have been chosen as independent variables and the influence of these variables on tensile, flexural and impact strength of the composite has been inspected. The permutations of the different combinations of factors are intended to accomplish higher interfacial strength with the lowest possible number of tested specimens. The experiments were designed by the Taguchi strategy and a novel multi-objective optimization technique named COPRAS (COmplex PRoportional ASsessment of alternatives) was used to determine the optimal parameter combinations. Affirmation tests were performed with the optimal parameter settings and the mechanical properties were evaluated and compared. Experimental results show that fiber GSM and eggshell powder content are significant variables that improve mechanical strength, while the nanoclay appears less important.     

Study on structure and performance of surface‐metallized carbon fibers reinforced rigid polyurethane composites

The simultaneous promotion in mechanical and electrical properties of rigid polyurethane (RPU) is an important task for expanding potential application. In this work, carbon fibers (CFs) reinforced RPU composites were prepared with the goal of improving mechanical and electrical properties. Metallized CFs meet our performance requirements and can be easily achieved via electrodeposition. However, the weak bonding strength in fiber‐metal‐RPU interface restricts their application. Inspired by the reducibility and wonderful adhesion of dopamine (DA), we proposed a new and efficient electrochemical method to fabricate metallized CFs, where DA polymerization was simultaneously integrated coupled with the reduction of metal ions (Ni²⁺). The characterization results helped us to gain insight about the reaction mechanism, which was never reported as far as we know. Compared with pure RPU, the tensile, interlaminar shear and impact strength of polydopamine (PDA)‐nickel (Ni) modified CFs/RPU composites were improved by 11.2%, 21.0%, and 78.0%, respectively, which attributed to the strong interfacial adhesion, including mechanical interlocking and chemical crosslinking between treated CFs and RPU. In addition, the PDA‐Ni surface treatment method also affected the dispersion of short CFs in the RPU, which increased the possibility of conductor contact and reduced insulator between fibers networks, resulting in higher electrical conductivity.     

Multicomponent Organic Metal Halide Hybrid with White Emissions

Zero‐dimensional (0D) organic metal halide hybrids, in which organic and metal halide ions cocrystallize to form neutral species, are a promising platform for the development of multifunctional crystalline materials. Herein we report the design, synthesis, and characterization of a ternary 0D organic metal halide hybrid, (HMTA)₄PbMn_0.69Sn_0.31Br₈, in which the organic cation N‐benzylhexamethylenetetrammonium (HMTA⁺, C₁₃H₁₉N₄⁺) cocrystallizes with PbBr₄^2?, MnBr₄^2?, and SnBr₄^2?. The wide band gap of the organic cation and distinct optical characteristics of the three metal bromide anions enabled the single‐crystalline “host–guest” system to exhibit emissions from multiple “guest” metal halide species simultaneously. The combination of these emissions led to near‐perfect white emission with a photoluminescence quantum efficiency of around 73 %. Owing to distinct excitations of the three metal halide species, warm‐ to cool‐white emissions could be generated by controlling the excitation wavelength.     

纤维增强金属基复合材料整体蠕变性能的细观力学分析

高温下金属基复合材料的蠕变主要由基体蠕变和界面扩散蠕变两部分构成,以往的研究中常常只考虑其中一种蠕变机理,从而导致得到的规律具有较大的局限性．本文提出了一种可预测金属基复合材料整体蠕变性能的细观力学方法,同时考虑了基体蠕变和界面扩散蠕变两种蠕变机理,导出了具有张量形式并满足不可压缩性的界面扩散蠕变应变表达式．采用Mori-Tanaka法和自洽法二者结果的平均以便更准确地计算纤维中的应力,揭示了两种蠕变机理相互影响的竞争关系．研究了恒定双轴荷载下的总体蠕变和固定位移约束下的应力松弛这两种常见蠕变问题,探究了基体蠕变与界面扩散蠕变两种蠕变机理在总蠕变中发挥的作用,考察了不同加载条件和不同纤维体积分数对复合材料整体蠕变行为的影响．     

Enhanced Reproducibility of Positive Temperature Coefficient Effect of CB/HDPE/PVDF Composites with the Addition of Ionic Liquid

Developing an effective method for improving the reproducibility of positive temperature coefficient(PTC) effect is of great significance for large-scale application of polymer based PTC composites, owing to its contribution to the security and reliability. Herein, we developed a carbon black(CB)/high density polyethylene(HDPE)/poly(vinylidene fluoride)(PVDF) composite with outstanding PTC reproducibility, by incorporating 1-octyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide([OMIm][NTf_2]) into the composite. After multiple repeated temperature cycles, the PTC performance of as-prepared material keeps almost unchanged and the varition of resistance at room temperature is less than 7%. Our studies revealed that [OMIm][NTf2] contributes to the improvement of PTC reproducibility in two ways:(i)it acts as an efficient plasticizer for refining the co-continuous phase morphology of HDPE/PVDE blends;(ii) it inhibits the crystallization of PVDF through the dilution effect, leading to more overlaps of the volume shrinkage process of HDPE and PVDF melt which results in the decrease of interface gap between HDPE and PVDF. This study demonstrated that ionic liquids as the multifunctional agents have great potential for improving the reproducibility in the application of the binary polymer based PTC composites.