双酚A-苯酚加合物结晶动力学

提出了一种新的间歇动态法,用来测定晶体成核与生长动力学参数。对粒数密度衡算方程进行变换,可测定晶体生长速率;通过建立晶体生长速率与成核速率之间的定量关系式,求得晶体成核速率。应用该方法,测定了双酚A-苯酚加合物结晶动力学参数。     

青霉素亚砜结晶生长与成核动力学

利用Mydlarz 和 Jones 模型（MJ2）,对乙酸丁酯中青霉素亚砜的成核与生长动力学进行研究。通过矩量法对MJ2模型进行处理后,利用晶体产品的粒度分布计算得到青霉素亚砜的生长速率与成核速率,然后利用最小二乘法拟合回归求解出成核与生长动力学方程参数。通过实验设计考察了过饱和度、温度与搅拌速度对青霉素亚砜晶体成核和生长过程的影响。研究表明青霉素亚砜晶体生长速率随过饱和度比的增加呈现指数型增长,确定青霉素亚砜晶体生长属于晶体表面生长控制过程。由于高速搅拌会增加青霉素亚砜晶体的破碎,促进了二次成核过程,随着搅拌速度的增加,晶体生长速率出现小幅下滑,而成核速率则明显升高。青霉素亚砜成核与生长动力学研究将有助于工业生产过程优化。     

仲钨酸铵结晶成核速率的研究

提出了仲钨酸铵（APT）蒸发结晶过程酸碱反应→仲钨酸根A－B转变→相交的成核机理.讨论了现有直接统计的方法测定APT成核速率的困难.将最终产品的粒度分布数据与一定结晶时刻晶体生长质量速率的测试结果相结合，建立了APT成核速率的研究方法.并在研究APT晶体生长机理的基础上分析了大小晶粒线生长速率的差异，以及破碎、晶粒附聚和二次成核给结果带来的可能偏差.     

内循环外冷却封闭塔盘式碳化塔碳酸氢钠结晶学动力学研究

本文对内循环我冷却封闭塔板式新型碳化塔结晶动力学问题进行研究。在内径φ７０有机玻璃模拟模内，以空气－ＮａＨＣＯ３饱和溶液为介质，探讨不同气、液流量对晶体生长速率Ｇ、成核速率Ｂ、晶浆悬浮密度ＭＴ等动力学参数的影响。并给出了不同气、液流量下的结晶的动力学关联式。     

苊冷却结晶动力学的间歇动态法研究

通过添加晶种的间歇冷却结晶实验研究了苊在乙醇中的结晶动力学。由苊晶体的粒数密度数据,通过矩量变换法按粒度无关生长模型求解粒数衡算方程,采用多元线性最小二乘法回归动力学数据,得到苊在乙醇中晶体生长及成核速率方程。对动力学方程的理论分析表明:搅拌速率对二次成核影响显著,随搅拌速率增加,晶体的成核速率明显增加。同时适宜的过饱和度及较低的悬浮密度,有利于苊晶体生长。该研究为苊冷却结晶特性的辨识、粒度分布的控制及工业放大提供了重要的理论指导。     

SAPO-34分子筛晶化机理及晶化动力学研究

对SAPO-34分子筛晶化过程中预相形成、诱导期内晶核生成、晶体生长和晶化过程的研究进行综述。SAPO-34分子筛晶化过程首先形成不稳定的层状预相结构,进而发展为具有有序排列晶格骨架的晶核。结晶热力学控制晶相结构,晶化动力学控制晶体成核和生长速率。影响晶化动力学的关键因素是温度和浓度,成核速率和晶体生长速率互相竞争控制晶粒大小。晶化过程的Si取代机理和Si分布影响分子筛酸性。晶化动力学研究结果表明,温度升高,结晶速率增加,成核时间缩短。     

氯氧化铋反应结晶动力学研究

在铋盐水解制备氯氧化铋的反应结晶过程中,控制氯氧化铋晶体成核和生长速率可影响氯氧化铋晶体的形貌、粒径和分散性。为此,选用间歇动态法研究了氯氧化铋晶体成核与生长动力学,采用矩量变换法建立了结晶过程动力学模型,并用最小二乘法对实验数据进行多元线性回归,获取了动力学模型参数。研究结果表明：当氯氧化铋晶体粒度≥3 μm时,其晶体生长速率符合粒度无关生长模型;晶浆悬浮密度和过饱和度对成核速率均有显著影响;溶液过饱和度对成核速率的影响较生长速率的影响更为显著。     

水化热抑制剂对复合胶凝材料体系早期水化动力学的影响

本文研究了水化热抑制剂(TRI)对水泥-粉煤灰-矿渣复合胶凝材料早期水化过程。通过改变矿物掺合料在胶凝材料中的质量占比以及TRI的掺量,研究了胶凝材料的水化特性,并基于Krstulovic-Dabic水化动力学模型计算了反应速率常数、几何晶体生长指数等动力学参数。结果表明,矿物掺合料和TRI复合使用会延缓胶凝材料水化并降低最大放热速率;复合胶凝材料的水化过程均有结晶成核与晶体生长、相边界反应以及扩散3个阶段,Krstulovic-Dabic水化动力学模型能较好地模拟各复合胶凝材料的水化过程;矿物掺合料和TRI会影响复合胶凝材料水化产物的结晶成核以及晶体生长,并降低复合胶凝材料各阶段的水化速率。     

MSMPR结晶器中二水硫酸钙的结晶动力学研究

应用粒数平衡技术,在MSMPR结晶器中,对二水硫酸钙结晶过程的动力学进行了研究,获得了二水硫酸钙在60℃情况下成核速率B0与晶体生长速率G之间的动力学表达式:B0=k2Gi=1.142×103G0.54,对实际工业生产具有一定的指导意义。     

Millad NX8000和Millad 3988改性1100N非等温结晶动力学研究

对山梨醇类透明成核剂NX8000和3988改性的均聚聚丙烯1100N非等温结晶动力学进行了研究,分别采用Jeziorny法和莫志森法处理了差示扫描量热法(DSC)所得的数据。结果表明:两种方法都能很好描述NX8000和3988改性1100N样品的非等温结晶动力学,成核剂对晶体生长方式改变不大,成核剂增大了体系的结晶速率。     

Investigation of the crystallization behavior of isotactic polypropylene polymerized with different Ziegler‐Natta catalysts

Detailed characterization of the crystallization behavior is important for obtaining better structure property correlations of the isotactic polypropylene (iPP), however, attributed to the complexity in ZN‐iPP polymerization, the relationship between crystallization behavior and the stereo‐defect distribution of iPP is still under debate. In this study, the crystallization kinetics of the primary nucleation, crystal growth and overall crystallization of two iPP samples (PP‐A and PP‐B) with nearly same average isotacticity but different stereo‐defect distribution (the stereo‐defect distribution of PP‐B is more uniform than PP‐A) were investigated. The results of isothermal crystallization kinetics showed that the overall crystallization rate of PP‐A was much higher than that of PP‐B; but the analysis of self‐nucleation isothermal crystallization kinetics and the polarized optical microscopy (POM) observation indicated that the high overall crystallization rate of PP‐A was attributed to the high primary nucleation rate of the resin. The stereo‐defect distribution plays an important role in determining both the nucleation kinetics and crystal grow kinetics, and thus influence the overall crystallization kinetics. A more uniform distribution of stereo‐defects restrains the crystallization rate of iPP, moreover, it has more influence on nucleation kinetics, comparing with the crystal growth. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Nucleation kinetics of emulsified triglyceride mixtures

The purpose of this study is to determine character istic nucleation parameters such as the surface free energy for nucleus formation in mixtures of fully hydrogenated palm oil (HP) in sunflower oil (SF). These parameters will be used to model the bulk crystallization kinetics of the same mixtures. This was achieved by determining the crystallization kinetics in emulsified triglyceride mixtures using differential scanning calorimetry, proton nuclear magnetic resonance, and ultrasound velocity measurements. The latter technique appeared to be very sensitive for monitoring the crystallization kinetics of fat dispersions containing triglycerides with a simple phase behavior. Isothermal crystallization of emulsified HP stabilized by sodium caseinate started at 7 K below the α clear point, and the kinetics were best fitted assuming heterogeneous nucleation. Isothermal crystallization of emulsified 10% HP in SF stabilized by caseinate started at 14 K below the α melting point, and the kinetics were best fitted assuming homogeneous nucleation. If the same dispersion was stabilized by Tween 20, crystallization started at 11 K below the α melting point, and the kinetics were fitted best using heterogeneous nucleation. Analysis of the temperature dependency of the fit parameters yielded a surface free energy of a nucleus of about 4 mJ.m⁻² in the case of homogeneous nucleation. Pre-exponential nucleation frequencies indicated that a large proportion of the triglyceride molecule should be in the right conformation to be incorporated in a nucleus.     

液相沉淀法制备纳米粒子的过程特征和原理

以制备纳米粒子为目的的液相沉淀过程 ,其成核、生长、聚结和老化等 ,均具有自身特征和规律。理想的沉淀过程是成核和生长分区或分期进行 ,在成核区或成核期 ,体系过饱和度高于均相成核临界过饱和度 ,为均相成核动力学所控制 ;在生长区或生长期 ,体系过饱和度小于成核临界过饱和度 ,为界面生长机理所控制。提出采用特征成核时间和特征扩散时间 ,判定反应沉淀过程的成核控制因素。提出粒度分布控制的技术关键 ,是将成核过程由微观混合控制转化为动力学控制     

气体水合物形成的热力学与动力学研究进展

气体水合物形成过程中涉及复杂的热力学和动力学问题.本文对水合物热力学理论模型、水合物生成动力学机理等方面的研究成果和最新进展进行了综述.热力学方面重点介绍了基于等温吸附理论 (van der Waals-Platteeuw模型)和基于双过程水合物生成机理(Chen-Guo模型)的相平衡热力学模型,同时介绍水合物结构及其转变方面的最新研究成果.动力学方面介绍了成簇成核、界面成核等成核机理模型以及成核后的水合物生长机理.另外还述及了目前水合物热力学和动力学研究中所涉及的微观、亚微观和宏观测量方法.针对目前水合物热力学和动力学研究中存在的问题,对未来的发展方向和重点提出了建议.     

Real time investigation of diamond nucleation by laser scattering

Diamond nucleation onto diamond-free substrates remains a major challenge for most diamond films applications. In order to quickly form a continuous film across a given surface, several pre-treatments of the substrate have been developed to increase the nucleation density. Amongst those, Bias Enhanced Nucleation (BEN) has been used intensively for many applications, including for instance the synthesis of ultra-thin diamond films, heteroepitaxial diamond films, or nanodiamond films. The determination of the nucleation kinetics during the BEN pretreatment is particularly relevant in order to obtain fundamental informations about plasma/surface interactions and associated nucleation mechanisms. Besides, it is a key challenge to optimise the BEN step for specific applications, such as epitaxy or high nucleation density. The sequential approach which consists of interrupting the process at different time intervals for nucleation density measurement is time consuming and not accurate enough. We propose a real time investigation of diamond nucleation by laser scattering applied to the Bias Enhanced Nucleation (BEN) pre-treatment on silicon carbide. The Microwave Plasma Chemical Vapour Deposition (MPCVD) reactor was equipped with a laser reflectometry system associated with a lock-in laser intensity measurement. In parallel, a kinetics model of nucleation was drawn based on light diffusion of diamond nanoparticles according to their size and density. The modelling results were compared to the experimental data, and characteristic kinetic parameters were worked out for diamond nucleation on silicon carbide. In this study we demonstrated that using a model based on nanoparticles laser scattering it is possible to determine in real time the kinetics of diamond nucleation.     

Mass transfer and radical flux effects in dispersed‐phase polymerization of isooctyl acrylate

The kinetics of dispersed phase polymerization of a highly water‐insoluble monomer (isooctyl acrylate) were explored in emulsion, miniemulsion, and microsuspension polymerization. The effects of monomer water solubility and choice of initiator (oil‐ vs. water‐soluble) strongly impact the final product (particle size and molecular weight distribution). For emulsion polymerization, as the surfactant concentration was increased, there was a transition from homogenous to micellar nucleation near the CMC, then a drop in nucleation rate at high surfactant concentration due to insufficient radical flux to support more nucleation. For miniemulsion polymerization, a slow rate of growth of (droplet) nucleation with surfactant concentration was found, followed (at the CMC) by an increase in the rate of nucleation with added surfactant as the mode of nucleation switched to micellar. The conversion‐time kinetics of microsuspensions could be modeled with a bulk polymerization model. IOA is sufficiently insoluble in the aqueous phase that emulsion polymerization may or may not be reaction limited. The presence of a stabilizer such a PAA, the use of an oil‐soluble initiator such as BPO, and the insolubility of IOA in the aqueous phase all push the polymerization locus toward droplet (microsuspension) nucleation and bulk kinetics.© 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 5649–5666, 2006     

Analysis of size distribution functions of diamond crystallites formed in the early stages of chemical vapour deposition

Size distribution functions of diamond particles formed in the early stages of chemical vapour deposition (CVD) can be used to distinguish between seeding and heterogeneous nucleation on the basis of their shape and of the d_max/d_min ratio, d_max and d_min being the maximum and the minimum diameters, respectively. A monomodal size distribution function with a d_max/d_min ratio much greater than 1.2–1.3 indicates diamond formation to occur via heterogeneous nucleation. In this case the nucleation kinetics can be calculated once the growth law of the crystallites has been established. The nucleation kinetics at copper substrates have been derived from distribution functions and described by a new kinetic model which includes the generation of nucleation sites.     

Effect of Crystallization Conditions on the Metastable Zone Width and Nucleation Kinetics of p-Aminobenzoic Acid in Ethanol

A detailed knowledge of the metastable zone width (MSZW) and nucleation kinetics is vital for the design of batch cooling crystallization processes. Factors such as cooling rate and impeller speed affect the MSZW and nucleation kinetics. Crystallization and dissolution temperatures were measured as a function of cooling rate and impeller speed during the batch cooling crystallization of p-aminobenzoic acid (pABA) from ethanol in a 0.5-L stirred-tank crystallizer. The polythermal experimental data were analyzed using the Nyvlt and first principles-based Kashchiev-Borissova-Hammond-Roberts (KBHR) methods. In all experimental cases, the latter model revealed that the nucleation process of pABA in ethanol was dominated by an instantaneous nucleation mechanism. The Nyvlt and KBHR analyses delivered a range of parameter values associated with a power-law model describing the nucleation rate as well as the concentration of nuclei.