MIL-101(Fe)对草甘膦的吸附行为研究

采用溶剂热法制备MIL-101(Fe)用作吸附材料,借助XRD、SEM、XPS及氮气吸脱附测试对所制材料的形貌及结构进行表征,研究了溶液pH值、反应时间、溶液浓度以及温度对其吸附草甘膦行为的影响。结果表明,当pH为3时,MIL-101(Fe)对草甘膦的吸附效果最佳,且随着温度的升高,MIL-101(Fe)对草甘膦的吸附速率明显增加,吸附过程符合拟二级动力学,等温吸附实验数据符合Langmuir和Temkin模型。MIL-101(Fe)吸附草甘膦属自发吸热的化学吸附反应,MIL-101(Fe)的中心金属Fe与草甘膦中O的配位在吸附过程中起主要作用。     

LiF-NaF-KF体系的相图计算

基于CALPHAD技术首先评估了LiF-NaF和LiF-KF两个二元熔盐体系,液相和端际固溶体Halite相均采用RedlichKister多项式置换熔体模型描述,模型参数的优化选取实验相平衡数据和热化学数据以及本文根据第一性原理预测的数据.结合文献中已报道的NaF-KF体系的热力学参数,用Muggianu模型扩展至LiF-NaF-KF三元体系,根据三元共晶点的实验数据调整三元交互参数.最终的相图计算结果与绝大部分实验数据和第一原理计算数据吻合较好,由此获得了一套自洽且可靠的热力学参数,其能够准确描述LiF-NaF-KF体系的相平衡与热力学性质.     

Computational thermodynamics,computational kinetics,and materials design

Computational thermodynamics, known as CALPHAD method when dawned in 1950s, aimed at cou- pling phase diagrams with thermochemistry by computa- tional techniques. It eventually evolves toward kinetic simulations integrated with thermodynamic calculations, i.e., computational kinetics, including diffusion-controlled phase transformation, precipitation simulation, and phase- field simulation. In the meantime, thermodynamic, mobility, and physical property databases for multi-component and multi-phase materials, served as basic knowledge for materials design, are critically evaluated by CALPHAD approach combining key experiments, first-principles cal- culations, statistic methods, and empirical theories. The combination of these computational techniques with their conjugated databases makes it possible to simulate phase transformations and predict the microstructure evolution in real materials in a foreseeable future. Further links to micro- and macro-scale simulations lead to a multi-scale compu- tational framework, and aid the search for the quantitative relations among chemistry, process, microstructures, and materials properties in order to accelerate materials devel- opment and deployment. This is a new route of materials and process design pursued by Integrated Computational Materials Engineering （ICME） and Materials Genome Ini- tiative （MGI）. This article presents a review on the basic theories and applications, the state of the art and perspective of computational thermodynamics and kinetics.     

Computational diffusion kinetics and its applications in study and design of rare metallic materials

Computational diffusion kinetics(CDK),with a spirit of and being coupled with the computational thermodynamics(CT,or called as the CALPHAD technique),plays increasingly important role in the alloy design/optimization and microstructure control during the processing of advanced metallic materials.This paper is to highlight recent progress of CDK in research with great focus on novel Ti and Zr alloys,which was largely performed in the authors’group.It ends with one representative example of the applications of CDK,coupled with CT,quantitative phase field,and three-dimensional(3D)statistical calculation,in designing the heattreatment schedule for the dual phase(αβ)Ti–6Al–4V alloys.     

The optimal configuration of reciprocating engine based on maximum entransy loss

A class of two-heat-reservoir heat engine model with heat leakage,finite heat capacity high-temperature source and infinite heat capacity low-temperature heat sink,is researched with the finite-time thermodynamic theory and the entransy theory.The optimal configuration based on the minimum entropy generation and the maximum entransy loss under the given cycle is searched,which are compared with the optimal configuration based on the maximum output work,and all the heat transfer in the model is assumed to obey the Newton’s law.The results show that,for the infinite heat capacity high-temperature source,the optimal configuration does not change whether heat leakage exists or not;however,for the finite hightemperature reservoir,the optimal configuration is different among which based on the minimum entropy generation,the maximum entransy loss,and the maximum output work when the heat leakage exists.     

磁性碳纳米管对水中低浓度罗红霉素的吸附特性研究

碳纳米管是各方面性能优异的新型纳米材料,其吸附性能优于活性炭.采用化学共沉淀方法制备磁性MWCNTs.利用红外光谱和Zeta电位对磁性MWCNTs和MWCNTs进行表征分析.吸附实验探讨pH值、温度等因素对磁性MWCNTs吸附罗红霉素的影响,采用准一、二级动力学模型和Freundlich、Langmuir等温线方程拟合曲线,分析吸附质可能的吸附机理.结果表明:磁性MWCNTs对罗红霉素最佳吸附pH值为1,罗红霉素的最大吸附量为39.6 mg/g.用准一、二级动力学模型和Langmuir等温线方程能较好地拟合罗红霉素吸附过程,相关系数均在0.95以上.标准吸附焓变△Ho为9.284 kJ/mol,吸附自由能变△G在-60.812 ～-58.640 kJ/mol之间,△S＞0,吸附是自发的吸热过程.     

喷雾热解法制备氢氧化镧

以H2O2为助剂,对氯化镧溶液通过喷雾热解法制备氢氧化镧的工艺进行了研究,首先通过热力学分析获得了H2O2与氯化镧反应的起始温度为288℃,并进一步研究了热解温度、氯化镧溶液质量浓度、H2O2添加量及载气压力对氢氧化镧转化率的影响.通过氯含量测定,XRD及SEM分析,获得了优化的工艺条件为:热解温度600℃,氯化镧溶液质量浓度400 g/L,H2O2加入量5%,载气压力0.4 MPa,在此条件下得到了转化率为99.96%的碎片状La(OH)3.     

荔枝壳对Cr(VI)的吸附性能研究

为考察荔枝壳对废水中Cr(VI)的吸附性能,用电镜对荔枝壳进行表征,并考察了p H、吸附剂用量、时间和温度对吸附性能的影响。结果表明荔枝壳表面粗糙、凹凸不平,对Cr(VI)具有较强的吸附能力。在温度25℃下,震荡吸附3 h,荔枝壳对Cr(VI)去除率可达91.5%。荔枝壳对Cr(VI)吸附的动力学和热力学研究结果表明,该吸附过程符合准二级吸附动力学模型和Langmuir等温方程。     

纳米TiO_2对沉积物吸附氨氮的影响及其机制探讨

纳米TiO2在生产使用过程中不可避免地大量进入水环境,并影响到其他传统污染物质(如氨氮)的迁移转化.氨氮在沉积物上的吸附和解吸附是水环境中氮素循环的关键过程之一.本研究测定了受纳米TiO2污染沉积物、常规TiO2污染沉积物和未受TiO2污染沉积物的零电荷点,并通过氨氮吸附热力学和吸附动力学实验,研究了纳米TiO2对沉积物吸附氨氮的影响.得出如下结论:(1)研究中的三组沉积物与NH4+-N之间没有静电吸引力;(2)修改后的Freundlich和修改后的Langmuir模型对氨氮吸附的拟合效果都比较好,且后者拟合度更高;(3)纳米TiO2的添加降低了氨氮的吸附—解吸平衡浓度,减小了沉积物向上覆水中释放氨氮的趋势;(4)抛物线扩散模型能较好地拟合三组沉积物吸附氨氮的动力学过程,结果显示纳米TiO2对沉积物吸附氨氮的动力学特征(快慢)没有影响,但增强了沉积物吸附氨氮的强度.     

热动力学框架内的RPC材料弹塑性各向异性损伤本构建模研究

考虑材料刚度的退化,不可恢复应变,非弹性体胀及单边效应,建立了RPC材料的弹塑性各向异性损伤本构关系.采用有效应力张量的正负分解,拉压不同的塑性硬化法则和拉压不同的损伤演化法则对RPC材料的单边效应进行了建模.采用张量型的损伤变量来描述损伤的各向异性,通过四阶损伤效应张量和应变等效假设建立有效构形和损伤构形中的物理量之间的关系.在热动力学框架内,建立了RPC材料的状态势和耗散势,由状态律给出了与状态变量共轭的热动力学广义力与状态变量之间的关系,由动力律给出了状态变量的演化关系,由塑性加载条件,损伤准则和一致性条件给出了塑性乘子和损伤乘子的大小,最终推导出弹塑性损伤切线刚度张量,为数值方法的实施典定基础,讨论了材料参数确定的方法和模型的局限性,为进一步的工作指明了方向.