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1.
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 相似文献
2.
Felipe A. Perdomo Siti H. Khalit Claire S. Adjiman Amparo Galindo George Jackson 《American Institute of Chemical Engineers》2021,67(3):e17194
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. 相似文献
3.
对锂辉石-氧化钙烧结过程进行热力学分析,绘制了各反应Gibbs自由能与温度的关系图。结果表明,Al2O3会优先和Na2O、Li2O、K2O反应,然后与CaO反应生成CaO·Al2O3,而且烧结温度需高于1060℃以保证LiAlSi2O6能够完成晶形转变。并探讨了锂辉石-氧化钙烧结法提锂的反应机理。考察了不同烧结条件对锂浸出率的影响并对熟料进行X射线衍射(XRD)分析表征。实验结果表明,在配料比为1∶1.25、烧结温度1150℃、烧结时间60min时,锂的浸出率达到92.14%,熟料中的主要物相为Ca2SiO4与LiAlO2。利用XRD和扫描电镜-能谱联用仪(SEM-EDS)对熟料与浸出渣的物相、显微形貌及元素分布情况进行了分析表征。为了确定烧结反应的控制性步骤,在最优烧结条件的基础上对烧结过程进行动力学分析,结果表明,锂辉石-氧化钙烧结体系属于球形颗粒三维界面化学反应控制,烧结过程的动力学拟合方程为 。 相似文献
4.
Jie Gao Zhikai Li Mei Dong Weibin Fan Jianguo Wang 《Frontiers of Chemical Science and Engineering》2020,14(5):847
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 ( ), (2) dehydrogenation of ethanol to acetaldehyde ( ), (3) esterification of acetic acid with ethanol ( ), (4) dehydrogenation of ethanol to ethyl acetate ( ), and (5) oxidative dehydrogenation of ethanol to ethyl acetate ( ). 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. 相似文献
5.
《Calphad》2015
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. 相似文献
6.
部分空间科学实验对环境温度有较高的要求,环境温度高于或低于空间科学系统能够提供的热沉温度,需要有可靠有效的加温降温处理措施。使用可靠性强的热电制冷片作为制冷制热方式和气液换热器二次换热来实现环境温度控制的需求,并对不同流体温度制冷制热效果进行分析,结果表明流体温度和目标温度差越小,热电制冷制热的效果越好。在环境温度制冷工况中,热电单元数量随电流增加先减少后增加,在制热工况中则单调递减,设计中需按照制冷工况进行热电单元数量的确定。当流体温度接近制冷制热的目标温度时,会出现整个系统总效率优于热电系统效率的区间。通过对热电单元和气液换热器的组合系统的性能计算,提供一种适于热电环控系统的计算方法和部件选型思路,对空间站环控系统的设计有重要参考意义。 相似文献
7.
《Calphad》2021
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. 相似文献
8.
Kinetic,thermodynamic parameters and in vitro digestion of tannase from Aspergillus tamarii URM 7115
Amanda Reges de Sena Tonny Cley Campos Leite Talita Camila Evaristo da Silva Nascimento Anna Carolina da Silva Catiane S. Souza Antônio Fernando de Mello Vaz 《Chemical Engineering Communications》2018,205(10):1415-1431
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. 相似文献
9.
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。 相似文献
10.
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. 相似文献