Influence of α′‐/α‐crystal polymorphism on properties of poly(l‐lactic acid)

Poly(l ‐lactic acid) (PLLA) is a biodegradable and biocompatible thermoplastic polyester produced from renewable sources, widely used for biomedical devices, in food packaging and in agriculture. It is a semicrystalline polymer, and as such its properties are strongly affected by the developed semicrystalline morphology. As a function of the crystallization temperature, PLLA can form different crystal modifications, namely α′‐crystals below about 120 °C and α‐crystals at higher temperatures. The α′ modification is therefore of special importance as it may be the preferred polymorph developing at processing‐relevant conditions. It is a metastable modification which typically transforms into the more stable α‐crystals on annealing at elevated temperature. The structure, kinetics of formation and thermodynamics of α′‐ and α‐crystals of PLLA are reviewed in this contribution, together with the effect of α′‐/α‐crystal polymorphism on the properties of PLLA. © 2018 Society of Chemical Industry     

Description of the thermodynamic properties and fluid-phase behavior of aqueous solutions of linear,branched, and cyclic amines

The SAFT-γ Mie group-contribution equation of state is used to represent the fluid-phase behavior of aqueous solutions of a variety of linear, branched, and cyclic amines. New group interactions are developed in order to model the mixtures of interest, including the like and unlike interactions between alkyl primary, secondary, and tertiary amine groups (NH₂, NH, N), cyclic secondary and tertiary amine groups (cNH, cN), and cyclic methine-amine groups (cCHNH, cCHN) with water (H₂O). The group-interaction parameters are estimated from appropriate experimental thermodynamic data for pure amines and selected mixtures. By taking advantage of the group-contribution nature of the method, one can describe the fluid-phase behavior of mixtures of molecules comprising those groups over broad ranges of temperature, pressure, and composition. A number of aqueous solutions of amines are studied including linear, branched aliphatic, and cyclic amines. Liquid–liquid equilibria (LLE) bounded by lower critical solution temperatures (LCSTs) have been reported experimentally and are reproduced here with the SAFT-γ Mie approach. The main feature of the approach is the ability not only to represent accurately the experimental data employed in the parameter estimation, but also to predict the vapor–liquid, liquid–liquid, and vapor–liquid–liquid equilibria, and LCSTs with the same set of parameters. Pure compound and binary phase diagrams of diverse types of amines and their aqueous solutions are assessed in order to demonstrate the main features of the thermodynamic and fluid-phase behavior.     

Material design and development: From classical thermodynamics to CALPHAD and ICME approaches

This paper presents an overview and examples of material design and development using (1) classical thermodynamics; (2) CALPHAD (calculation of phase diagrams) modeling; and (3) Integrated Computational Materials Engineering (ICME) approaches. Although the examples are given in lightweight aluminum and magnesium alloys for structural applications, the fundamental methodology and modeling principles are applicable to all materials and engineering applications. The examples in this paper have demonstrated the effectiveness and limitations of classical thermodynamics in solving specific problems (such as nucleation during solidification and solid-state precipitation in aluminum alloys). Computational thermodynamics and CALPHAD modeling, when combined with critical experimental validation, have been used to guide the selection and design of new magnesium alloys for elevated-temperature applications. The future of material design and development will be based on a holistic ICME approach. However, key challenges exist in many aspects of ICME framework, such as the lack of diffusion/mobility databases for many materials systems, limitation of current microstructural modeling capability and integration tools for simulation codes of different length scales.     

Nb和时效时间对热轧中锰TRIP钢中P偏聚的影响

热轧态中锰TRIP钢首先经650 ℃退火2 h,随后在550 ℃进行等温时效热处理,采用场发射扫描电镜(FE-SEM)研究该钢中P的偏聚和时效析出行为的变化情况。结果表明,中锰TRIP钢中P在晶界的偏聚是一种非平衡偏聚现象,临界时间约为50 h,与理论计算结果48 h较为吻合。在局部偏聚区域内,C与P存在共偏聚的关系,即P偏聚量高的地方,C含量也高。而合金元素Nb具有抑制P偏聚的效果,在20~70 h时效时间内,可以相对降低6.57%~19.5%的最大P偏聚量。根据电子背散射衍射(EBSD)菊池线分析,P偏聚量低于2.28at%时,P为固溶状态,高于2.28at.%时,P为析出状态。     

A model for multicomponent diffusion in oxide melts

A general flux equation for multicomponent diffusion in oxide melts is presented. An explicit method was developed to calculate the gradients of single-ion activities from those of oxides with the constraints of local equilibrium and electroneutrality. This resolves ambiguity in quantifying the thermochemical driving force for ionic diffusion. A model equation for multicomponent ionic diffusion was derived within the framework of non-equilibrium thermodynamics by de Groot and Mazur. The proposed model takes empirically measurable quantities as input variables, so the diffusion calculations are consistent with thermochemical data, as furnished by the CALPHAD (CALculation of PHAse Diagrams) method, as well as ionic mobility measurements. Although the model is derived for oxides, it can be applied to diffusion in other concentrated liquid electrolytes, such as chloride and fluoride melts. Formulas for multicomponent ionic diffusion in various reference frames are presented with respect to mole fraction.     

Kinetic,thermodynamic parameters and in vitro digestion of tannase from Aspergillus tamarii URM 7115

Tannase is an enzyme used in various industries and produced by a large number of microorganisms. The aim of this study was to evaluate tannase production to determine the biochemical, kinetic, and thermodynamic properties and to simulate tannase in vitro digestion. The tannase-producing fungal strain was isolated from “jamun” leaves and identified as Aspergillus tamarii. Temperature at 26°C for 67?h was the best combination for maximum tannase activity (6.35-fold; initial activity in Plackett–Burman design—15.53?U/mL and average final activity in Doehlert design—98.68?U/mL). The crude extract of tannase was optimally active at 40°C, pH 5.5 and 6.5. Moreover, tannase was stimulated by Na⁺, Ca²⁺, Mg²⁺, and Mn²⁺. The half-life at 40°C lasted 247.55?min. The free energy of Gibbs, enthalpy, and entropy, at 40°C, was 81.47, 16.85, and ?0.21?kJ/mol?·?K, respectively. After total digestion, 123.95% of the original activity was retained. Results suggested that tannase from A. tamarii URM 7115 is an enzyme of interest for industrial applications, such as gallic acid production, additive for feed industry, and for beverage manufacturing, due to its catalytic and thermodynamic properties.     

综合高速效应的凝析气藏流入动态

当井底压力低于露点压力时,凝析液在近井地带开始析出并不断聚集产生凝析油堵塞现象。因此,在制定凝析气井工作制度时,通常以控制生产压差为指导思想,往往忽略高速流动下凝析气液相变的非平衡特征。对于凝析气体系,当外界温压变化速度超过凝析气液的相平衡速度时,凝析气体系相变滞后,开始呈现非平衡特征,即凝析液的析出量随着压降速度的增加而减小。凝析气在向井筒流动的过程中,近井区高速流动使凝析气产生非平衡相变,凝析气在比较高的压降速度下流入井筒,使得凝析液来不及析出。在分析非平衡相变规律与近井地带凝析气渗流参数分布的基础上,评价凝析气液流动过程中的非平衡特征,给出了考虑非平衡相变的凝析液饱和度分布计算公式,并进行了产能预测结果对比。实例分析表明,可以通过适当放大生产压差,增加凝析气液相变非平衡特征,减小井筒附近的凝析液饱和度,提高气井产能与气藏开发效果。     

在经典极限下量子斯特林制冷机的优化

经济利润率是评价一个实际热力装置的主要指标之一。将有限时间热力学，非平衡量子统计理论和yong经济学相结合，导出了量子斯特林制冷机的最大利润率以及对应的性能界限，其结果与实际斯特林制冷机的优化设计和模型评估提供了一个最佳的预选方案。     

高压脉冲放电处理含氰废水的影响因素探讨

焦化废水中含有大量的氰化物,必须采取有效措施进行去除,传统去除方法运行成本高、操作复杂。提出了用高压毫微秒脉冲产生的非平衡等离子体处理含氰废水的方法,对其影响因素pH值、放电时间、气流量、放电条件等进行了大量的实验研究,结果表明:溶液初始pH值为9.09,放电2 h,放电电压46 kV时氰化物的去除率最高可达93.2%,氰化物质量浓度可降至0.26 mg/L。实验对比了放电与不放电氰化物的去除效果:相同条件下放电后氰化物的去除率大大提高,为焦化废水中氰化物的去除提出了一种新的方法。     

Upper bounds for solar thermophotovoltaic efficiency

The main components of thermophotovoltaic (TPV) devices are the primary lens (or mirror), the absorber, the PV cell, and a photon recuperator system. A theory integrating all these components is used in this paper to analyse a particular type of TPV device (plane disk absorber and PV cell). The TPV efficiency is maximized by using three optimization parameters, namely absorber, PV cell temperatures, and cell voltage. Almost ideal operation conditions are envisaged and upper bounds are obtained for the TPV efficiency. They are strongly dependent on PV cell bandgap and radiation concentration. Preliminary results suggest the existence of an optimum solar radiation concentration ratio. The improvement in thermal design quality allows the usage of PV cells based on wide bandgap semiconductors.