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.     

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.     

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。     

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.     

A comparative thermodynamic study of sorption systems: second law analysis

As a consequence of the phasing out of CFCs, sorption systems appear to be potential candidates to replace vapour compression systems. Amongst sorption systems there exists a choice between several systems, such as liquid absorption, solid adsorption and chemical reaction heat pumps. Nevertheless, few comparative studies between these systems have been undertaken so far. It is the aim of this paper to present such a study based on combined first and second law thermodynamical analysis of the different cycles. Simple entropy generation processes explain why the basic cycles for these systems yield performances much lower than the Carnot efficiency. The possibility of operating regenerative cycles with internal heat recovery and higher efficiencies has also been considered for typical common base conditions. Different entropy generation considerations have been visualised, such as thermal coupling (external/internal), non-uniform temperature component entropy production and other irreversible processes for the COP degradation in these systems. It is found that thermal coupling irreversibilities in solid sorption systems and other internal irreversibilities in liquid sorption systems with solution heat exchanger are dominant in the actual COP degradation with respect to the reversible Carnot COP.     

β－C_2S固溶体稳定的热力学研究

从热力学理论出发，利用Ｘ射线衍射定性和定量的方法，对β－Ｃ＿２Ｓ固溶体的稳定性进行了分析和研究。经热力学理论推导得出β－Ｃ＿２Ｓ稳定的热力学条件，即掺入的微量元素的化学位μ＿ｉ须小于β－Ｃ＿２Ｓ的反应自由焓△Ｇ＿β，μ＿ｉ＜△Ｇ＿β．并定量地计算出一种微量元素稳定β－Ｃ＿２Ｓ的临界掺加量为；多种微量元素对β－Ｃ＿２Ｓ的稳定性判断条件为：     

Second-law-based thermodynamic analysis of two-stage and mechanical-subcooling refrigeration cycles

Thermodynamic analysis of HFC-134a vapor-compression refrigeration cycles is investigated by both the first and second laws of thermodynamics. Second-law analysis is carried out for both two-stage and mechanical-subcooling refrigeration cycles. The analysis is performed on each of the system components to determine their individual contribution to the overall system irreversible losses. It is found that most of the losses are due to a low compressor efficiency. Irreversibilities of expansion valves and condenser are also significant. In addition, it is shown that the optimum inter-stage pressure for two-stage and mechanical-subcooling refrigeration systems is very close to the saturation pressure corresponding to the arithmetic mean of the refrigerant condensation and evaporation temperatures. These results are compared with the existing practice in the industry. Furthermore, theoretical results of a two-stage refrigeration system performance are also compared with experimental values for a CFC-22 system.