Influence of accelerated curing on the compressive strength of polymer-modified concrete

In recent building practice, rapid construction is one of the principal requisites. Furthermore, in designing concrete structures, compressive strength is the most significant of all parameters. While 3-d and 7-d compressive strength reflects the strengths at early phases, the ultimate strength is paramount. An effort has been made in this study to develop mathematical models for predicting compressive strength of concrete incorporating ethylene vinyl acetate (EVA) at the later phases. Kolmogorov-Smirnov (KS) goodness-of-fit test was used to examine distribution of the data. The compressive strength of EVA-modified concrete was studied by incorporating various concentrations of EVA as an admixture and by testing at ages of 28, 56, 90, 120, 210, and 365 d. An accelerated compressive strength at 3.5 hours was considered as a reference strength on the basis of which all the specified strengths were predicted by means of linear regression fit. Based on the results of KS goodness-of-fit test, it was concluded that KS test statistics value (D) in each case was lower than the critical value 0.521 for a significance level of 0.05, which demonstrated that the data was normally distributed. Based on the results of compressive strength test, it was concluded that the strength of EVA-modified specimens increased at all ages and the optimum dosage of EVA was achieved at 16% concentration. Furthermore, it was concluded that predicted compressive strength values lies within a 6% difference from the actual strength values for all the mixes, which indicates the practicability of the regression equations. This research work may help in understanding the role of EVA as a viable material in polymer-based cement composites.     

Brönsted方程动力学模型研究ZSM-5催化乙烯齐聚及芳构化活性和酸强度分布之间的定量关系

乙烯催化齐聚和芳构化是烯烃高值化和合成液体燃料的关键过程，采用NH₃-TPD谱图分析计算方法得到的探针分子脱附活化能作为催化剂的酸位点强度分布的参数，结合线性自由能理论在Br?nsted方程中引入酸强度对反应的影响因子γ作为动力学方程参数关联探针分子脱附活化能与反应活化能，明确固体酸酸强度的基准在催化动力学方程中的物理意义。建立同为MFI拓扑结构 Si /Al摩尔比为12.5、19、25、60、70的ZSM-5分子筛催化剂上不同酸强度位和乙烯齐聚及芳构化中氢转移、齐聚、芳构化各单元步骤以及对应的烷烃、低碳烯烃和芳烃产物分布的定量关系。根据拟合得到动力学参数γ可以发现不同强度的酸位点对乙烯齐聚及芳构化具有不同的作用系数。氨脱附活化能(DAE)为90 kJ·mol^-1的酸位点是氢转移反应的主要活性位点，而对于乙烯齐聚反应中主要的活性酸位点为DAE 90 kJ·mol^-1和124 kJ·mol^-1，DAE为150 kJ·mol^-1的酸位点是芳构化反应的主要活性位点。     

Synthesis of Ionic Ultramicroporous Polymers for Selective Separation of Acetylene from Ethylene

The design of highly stable and efficient porous materials is essential for developing breakthrough hydrocarbon separation methods based on physisorption to replace currently used energy-intensive distillation/absorption technologies. Efforts to develop advanced porous materials such as zeolites, coordination frameworks, and organic polymers have met with limited success. Here, a new class of ionic ultramicroporous polymers (IUPs) with high-density inorganic anions and narrowly distributed ultramicroporosity is reported, which are synthesized by a facile free-radical polymerization using branched and amphiphilic ionic compounds as reactive monomers. A covalent and ionic dual-crosslinking strategy is proposed to manipulate the pore structure of amorphous polymers at the ultramicroporous scale. The IUPs exhibit exceptional selectivity (286.1–474.4) for separating acetylene from ethylene along with high thermal and water stability, collaboratively demonstrated by gas adsorption isotherms and experimental breakthrough curves. Modeling studies unveil the specific binding sites for acetylene capture as well as the interconnected ultramicroporosity for size sieving. The porosity-engineering protocol used in this work can also be extended to the design of other ultramicroporous materials for the challenging separation of other key gas constituents.     

乙烯、丙烯中微量水含量的分析

采用便携式微量水分析仪和库仑法微量水分析仪测定了乙烯、丙烯试样中的微量水含量,对试样的传输系统、进样量的控制、液体试样的气化和水标准气体的制备方法进行了改进,优化了测试条件。以低吸附惰性管线和小死体积单进单出的不锈钢减压器为试样传输系统,缩短了测试时间。采用液态烃闪蒸气化取样进样器气化液体试样并准确控制试样的进样量,可避免液体试样渐次气化对水含量测定结果的影响及对采样钢瓶大小的限制。采用渗透管发生器制备水标准气体,可验证分析结果的准确度。采用库仑法微量水分析仪测定水含量时,试样流量选择600 m L/min较适宜,开封保存15 d之内的卡尔·费休试剂对测定结果无影响。采用便携式微量水分析仪测定水含量时,选择试样流量在400~800 m L/min之间较适宜。两种仪器的测量结果相近,稳定性好,准确度高,回收率在102%~107%之间,相对偏差小于10%。     

The Interplay of Modulus,Strength, and Ductility in Adhesive Design Using Biomimetic Polymer Chemistry

High‐performance adhesives require mechanical properties tuned to demands of the surroundings. A mismatch in stiffness between substrate and adhesive leads to stress concentrations and fracture when the bonding is subjected to mechanical load. Balancing material strength versus ductility, as well as considering the relationship between adhesive modulus and substrate modulus, creates stronger joints. However, a detailed understanding of how these properties interplay is lacking. Here, a biomimetic terpolymer is altered systematically to identify regions of optimal bonding. Mechanical properties of these terpolymers are tailored by controlling the amount of a methyl methacrylate stiff monomer versus a similar monomer containing flexible poly(ethylene glycol) chains. Dopamine methacrylamide, the cross‐linking monomer, is a catechol moiety analogous to 3,4‐dihydroxyphenylalanine, a key component in the adhesive proteins of marine mussels. Bulk adhesion of this family of terpolymers is tested on metal and plastic substrates. Incorporating higher amounts of poly(ethylene glycol) into the terpolymer introduces flexibility and ductility. By taking a systematic approach to polymer design, the region in which material strength and ductility are balanced in relation to the substrate modulus is found, thereby yielding the most robust joints.     

超支化镍系催化剂构效关系及催化乙烯齐聚机理

采用1.0G超支化大分子（1.0G）、3-取代水杨醛和NiCl₂·6H₂O为原料，依次经席夫碱反应和络合反应合成了3种新型具有不同取代基位阻的超支化水杨醛亚胺配体及其镍系催化剂，利用红外光谱（FTIR）、核磁共振氢谱（¹H NMR）、紫外光谱（UV-vis）、电喷雾质谱（ESI-MS）及电感耦合等离子体质谱（ICP-MS）等方法对合成出产物的结构进行表征。考察了配体空间位阻、溶剂种类、助催化剂种类及反应条件对催化乙烯齐聚性能的影响。研究结果表明，配体空间位阻对催化乙烯齐聚性能有较大的影响，当以甲苯为溶剂、甲基铝氧烷（MAO）为助催化剂，在最佳反应条件下，超支化邻苯基水杨醛亚胺镍系催化剂催化乙烯齐聚的活性为2.81×10⁵g/(mol Ni·h)，对高碳烯烃（C₁₀₊）的选择性为34.28%。此外，在超支化水杨醛亚胺镍系催化剂催化性能评价的基础上，对其催化乙烯齐聚的机理进行研究。     

Thermodynamic analysis of ethanol synthesis from hydration of ethylene coupled with a sequential reaction

Coal-based ethanol production by hydration of ethylene is limited by the low equilibrium ethylene conversion at elevated temperature. To improve ethylene conversion, coupling hydration of ethylene with a potential ethanol consumption reaction was analyzed thermodynamically. Five reactions have been attempted and compared: (1) dehydration of ethanol to ethyl ether ({\mathrm{2C}}_{\mathrm{2}}{\mathrm{H}}_{\mathrm{5}}\mathrm{OH}\iff{\mathrm{C}}_{\mathrm{2}}{\mathrm{H}}_{\mathrm{5}}{\mathrm{OC}}_{\mathrm{2}}{\mathrm{H}}_{\mathrm{5}}{\mathrm{+H}}_{\mathrm{2}}\mathrm{O}), (2) dehydrogenation of ethanol to acetaldehyde ({\mathrm{C}}_{\mathrm{2}}{\mathrm{H}}_{\mathrm{5}}\mathrm{OH}\iff {\mathrm{CH}}_{\mathrm{3}}{\mathrm{CHO+H}}_{\mathrm{2}}), (3) esterification of acetic acid with ethanol ({\mathrm{C}}_{\mathrm{2}}{\mathrm{H}}_{\mathrm{5}}{\mathrm{OH+CH}}_{\mathrm{3}}\mathrm{COOH}\iff {\mathrm{CH}}_{\mathrm{3}}{\mathrm{COOC}}_{\mathrm{2}}{\mathrm{H}}_{\mathrm{5}}{\mathrm{+H}}_{\mathrm{2}}\mathrm{O}), (4) dehydrogenation of ethanol to ethyl acetate ({\mathrm{2C}}_{\mathrm{2}}{\mathrm{H}}_{\mathrm{5}}\mathrm{OH}\iff {\mathrm{CH}}_{\mathrm{3}}{\mathrm{COOC}}_{\mathrm{2}}{\mathrm{H}}_{\mathrm{5}}{\mathrm{+2H}}_{\mathrm{2}}), and (5) oxidative dehydrogenation of ethanol to ethyl acetate ({\mathrm{2C}}_{\mathrm{2}}{\mathrm{H}}_{\mathrm{5}}{\mathrm{OH+O}}_{\mathrm{2}}\iff {\mathrm{CH}}_{\mathrm{3}}{\mathrm{COOC}}_{\mathrm{2}}{\mathrm{H}}_{\mathrm{5}}{\mathrm{+2H}}_{\mathrm{2}}\mathrm{O}). The equilibrium constants and equilibrium distributions of the coupled reactions were calculated and the effects of feed composition, temperature and pressure upon the ethylene equilibrium conversion were examined. The results show that dehydrogenation of ethanol to acetaldehyde has little effect on ethylene conversion, whereas for dehydrogenation of ethanol to acetaldehyde and ethyl acetate, ethylene conversion can be improved from 8% to 12.8% and 18.5%, respectively, under conditions of H₂O/C₂H₄ = 2, 10 atm and 300°C. The esterification of acetic acid with ethanol can greatly enhance the ethylene conversion to 22.5%; in particular, ethylene can be actually completely converted to ethyl acetate by coupling oxidative dehydrogenation of ethanol.     

Electrocatalytic Reduction of CO2 to Ethylene by Molecular Cu‐Complex Immobilized on Graphitized Mesoporous Carbon

The electrochemical reduction of carbon dioxide (CO₂) to hydrocarbons is a challenging task because of the issues in controlling the efficiency and selectivity of the products. Among the various transition metals, copper has attracted attention as it yields more reduced and C2 products even while using mononuclear copper center as catalysts. In addition, it is found that reversible formation of copper nanoparticle acts as the real catalytically active site for the conversion of CO₂ to reduced products. Here, it is demonstrated that the dinuclear molecular copper complex immobilized over graphitized mesoporous carbon can act as catalysts for the conversion of CO₂ to hydrocarbons (methane and ethylene) up to 60%. Interestingly, high selectivity toward C2 product (40% faradaic efficiency) is achieved by a molecular complex based hybrid material from CO₂ in 0.1 m KCl. In addition, the role of local pH, porous structure, and carbon support in limiting the mass transport to achieve the highly reduced products is demonstrated. Although the spectroscopic analysis of the catalysts exhibits molecular nature of the complex after 2 h bulk electrolysis, morphological study reveals that the newly generated copper cluster is the real active site during the catalytic reactions.