A five-parameter fractional derivative temperature spectrum model for polymeric damping materials

To capture viscoelastic behavior of polymeric damping materials based on limited dynamic mechanical analysis tests, a simple fractional temperature spectrum model representing the viscoelastic materials is proposed in this paper and experimental tests aims at stressing the validity of the model. The storage modulus, the loss modulus, and the loss factor, are established based on the five-parameter fractional derivative model and the time–temperature superposition principle. The dynamic mechanical tests of two polymeric materials are carried out to verify this temperature spectrum model. Results indicate a good agreement between the temperature spectrum model and experimental tests at various temperature conditions. Furthermore, thermodynamic coupling of the viscoelastic material is investigated by temperature rise calculation and vibration experiment test. Comparison analysis shows that the temperature rise model can simulate the temperature rise process for the shear vibration of the constrained damping, which provide references for the damping capability, thermal damage and failure of viscoelastic material.     

Mechanistic details of metal-free cyclization reaction of organophosphorus oxide with alkynes mediated by 2,6-lutidine and Tf2O

Theoretical investigations have elucidated the mechanism of metal-free electrophilic phosphinative cyclization of alkynes reaction reported by Miura and coworkers. Two competitive mechanisms I and II were explored without or with 2,6-lutidine. Both of I and II involve transformation of P(V) to P(III), electrophilic addition, ring opening and cyclization/cyclization, hydrogen-transfer, and oxidation. The rate-determining step of mechanism I and competitive less-step II is electrophilic [2 + 1] cycloaddition and electrophilic addition via single C P bond formation with activation barrier of 13.5 and 10.6 kcal/mol, respectively. Our calculation results suggested that the cumulative effect of the isomer of 2,6-lutidine and Tf₂O as well as TfO⁻ affects the title reaction to some extent, and simultaneously activates key reaction sites and reverses the polarities of them via the formation of abundant noncovalent interactions to decrease activation barriers of TSs. In addition, the effects of two series substituents on reactivity of phosphine oxide were investigated. Therefore, our study will serve as useful guidance for more efficient metal-free synthesis of organophosphorus compounds mediated by pyridine reagents.     

Identification of decomposition reactions for HMDSO organosilicon using quantum chemical calculations

Hexamethyldisiloxane [HMDSO, (CH₃)₃-SiOSi-(CH₃)₃] is an important precursor for SiO₂ formation during flame-based silica material synthesis. As a result, HMDSO reactions in flame have been widely investigated experimentally, and many results have indicated that HMDSO decomposition reactions occur very early in this process. In this paper, quantum chemical calculations are performed to identify the initial decomposition of HMDSO and its subsequent reactions using the density functional theory at the level of B3LYP/6-311+G (d, p). Four reaction pathways—(a) Si O bond dissociation of HMDSO, (b) Si C bond dissociation of HMDSO, (c) dissociation and recombination of Si O and Si C bonds, and (d) elimination of a methane molecule from HMDSO—have been examined and identified. From the results, it is found that the barrier of 84.38 kcal/mol and Si O bond dissociation energy of 21.55 kcal/mol are required for the initial decomposition reaction of HMDSO in the first pathway, but the highest free energy barrier (100.69 kcal/mol) is found in the third reaction pathway. By comparing the free energy barriers and reaction rate constants, it is concluded that the most possible initial decomposition reaction of HMDSO is to eliminate the CH₃ radical by Si C bond dissociation.     

Adsorption performance and mechanism of Schiff base functionalized polyamidoamine dendrimer/silica for aqueous Mn(II) and Co(II)

Schiff base functionalized polyamidoamine (PAMAM) dendrimer/silica were prepared for the adsorption of aqueous Mn(II) and Co(II). The effects that influence the adsorption were investigated systematically and the adsorption mechanism was illustrated by theoretical calculation. The optimum adsorption pH are 4 and 6 for Mn(II) and Co(II). Adsorption kinetics follow pseudo-second-order model and the rate-controlling step is film diffusion process. Adsorption isotherm shows that high initial metal ion concentration facilitates the uptake of metal ions. The adsorption capacity increases first and then decreases in the temperature range of 15–35 °C. Density functional theory (DFT) calculation demonstrates that Schiff base functionalized PAMAM dendrimer tends to coordinate Mn(II) and Co(II) with the oxygen atoms of hydroxyl and carbonyl groups, nitrogen of tertiary amine and imino groups. The imino and tertiary amine groups mainly dominate the adsorption. The reproducibility of the adsorbents indicates they can be regenerated by 5% thiourea and 0.5 mol/L HNO₃ solution efficiently.     

Chromatographic study of four sesquiterpenoids in volatile oil of Curcumae Rhizoma on reverse phase stationary phase with methyl-β-cyclodextrin as mobile additive

Abstract

The elution behavior of four sesquiterpenoids in volatile oil of Curcumae Rhizoma on reverse-phase high-performance liquid chromatography with methyl-β-cyclodextrin as mobile phase additive was studied, including germacrone, curzerene, furanodiene, and β-elemene. Stoichiometric ratio and apparent formation constants of inclusion complex formed by methyl-β-cyclodextrin and each analyte were calculated by varying the concentration of the additive in the mobile phase composed of methanol and water (90:10, v/v), in which the association constant for inclusion complex formed by the organic modifier methanol and methyl-β-cyclodextrin was also determined. Results showed that the stoichiometric ratio of all the inclusion complex was 1:1 when 0–9?mmol L^?1 of methyl-β-cyclodextrin was added in the mobile phase. Unusual retention behavior of the analyte germacrone was found, which was further investigated by the calculation of thermodynamic parameters. Meanwhile, enthalpy and entropy of the inclusion complexes and solute-stationary phase interactions were determined by linear van’t Hoff plots.     

滑坡冲击铲刮变量的计算方法研究

高速远程滑坡运动过程中,冲击铲刮效应不仅增加滑坡的体积与规模,而且会增大滑坡成灾范围,风险预测与判断出现明显误差,导致灾难性事件的发生。目前对于高速滑坡的铲刮深度、铲刮范围和铲刮体积等变量计算往往是采用基于经验的铲刮率算法,其是通过体积增量来反算铲刮变量的数学方法,而实际情况中高速滑坡的冲击铲刮是滑体冲击力和地表可铲刮材料之间的力学屈服破坏作用的结果。本文基于接触力学、弹塑性力学和岩土力学,提出了地表可铲刮层在附加冲击荷载作用下铲刮变量的理论计算方法,认为竖向冲击和切向剪切是滑体冲击铲刮过程的两种主要作用方式。结合实际岩土体材料参数,发现不考虑切向荷载时,铲刮层塑性区主要以竖向破裂区为主,考虑切向荷载时,铲刮层塑性区沿切向迁移,直至塑性边界贯通至地表,符合实际情况,实现了对铲刮变量的定量化计算。     

集中载荷作用下不同边界条件的弯曲厚矩形板的受迫振动

运用边界积分法研究了四边简支、两对边固定另两对边简支、四边固定三种复杂边界条件下厚矩形板的受迫振动问题,求解过程清晰,从而给出了受迫振动控制方程和挠曲面方程。通过在Matlab平台上进行数值计算,得出了图表形式的计算结果,并与有限元模拟值进行对照。研究表明,边界积分法用于求解厚矩形板的受迫振动问题的准确性,本文推导的控制方程和挠曲面方程的正确性,进而对工程实际中的各种相关问题具有一定的现实意义,也为求解此类问题提供了一种新途径,可以直接运用到工程实际中。     

基于并行技术的机载多天线耦合快速算法

分析机载天线间的干扰情况必须首先解决电大尺寸电磁计算问题.首先讨论一种基于空域分解技术及局域网技术的并行数值算法,这种算法将一个电大尺寸散射体表面划分为一系列子域分别进行处理,在求解子域电流的过程中使用了快速多极子技术进行加速运算,然后运用这种算法对机载天线间的耦合进行分析并对算法的性能进行了总结.     

液相苯与稀乙烯变相催化分离生成乙苯的化学平衡、物料平衡和热量平衡计算

 提出了液相苯和稀乙烯变相催化分离制乙苯的反应示意图,对该烷基化反应部分的化学平衡、物料平衡和热量平衡进行了计算. 在温度185 ℃, 压力2.0 MPa, 乙烯1 mol/h, 氮4 mol/h, 新鲜苯3 mol/h的条件下, 烷基化反应后的绝热温升为175.6 ℃. 计算的温升、乙烯转化率和乙苯选择性结果与实验结果基本相符. 从反应段上部补充的35 ℃的新鲜苯与反应段流出的202.6 ℃气体进行热交换后,体系温度达到185.9 ℃, 稍高于反应温度(185 ℃). 但从反应段下部进入的35 ℃的稀乙烯与反应段流出的202.6 ℃的液体混合进行热交换时,由于稀乙烯使液体产物汽化,导致体系温度大幅度降低,平衡时体系温度仅为153.5 ℃, 远低于所要求的反应温度. 计算结果表明,需给体系提供91.5 kJ的热,或者将稀乙烯加热至523 ℃, 混合后体系平衡温度才能达到185 ℃.     

高温超导带材交流损耗的数值计算与分析

高温超导带材在许多领域得到越来越广泛的应用。交流损耗计算对于高温超导带材具有重要意义。该文介绍了两种交流损耗的数值计算模型,并以其中一种模型为例,对带材的交流损耗进行计算,与Norris公式计算结果作了比较,证明结果有效。最后提出了交流损耗数值计算中存在的问题。