光卤石中氯化钾溶解度、介穏区、诱导期测定

采用变温溶解动态法测定了光卤石中氯化钾的溶解度,并用简化固液平衡方程对溶解度数据做了拟合。研究了搅拌速度、降温速率对介穏区宽度以及不同过饱和度对诱导期的影响。结果表明：简化固液平衡方程能够对氯化钾溶解度拟合良好;介穏区宽度随降温速率的升高而变宽,随搅拌速度增大而变窄;诱导期随过饱和度的增大而变短,且在不同温度下,相同过饱和度下的诱导期相近。应用经典Nyvlt理论方程和3D成核原理,结合实验介穏区及诱导期数据,计算了光卤石中氯化钾的成核级数为2.46~2.51,在283.15、293.15、303.15 K条件下,氯化钾在该体系中表面张力γ为0.019 8~0.556 0,表面能因子f<3,结晶连续生长。     

表面活性剂对氟硅酸钠、氟硅酸钾及二水硫酸钙的界面能的影响

从界面能方法和结晶理论入手，研究了磷酸介质中表面活性剂对氟硅酸钠、氟硅酸钾、二水硫酸钙结晶生长的影响。利用薄层浸润法测定固液间的接触角，计算上述三种物质在磷酸介质中的固液界面能，研究得知：最先析出氟硅酸钠，其次是氟硅酸钾，最后是二水硫酸钙；而且添加表面活性剂使界面能增大，其中聚乙二醇10000、OP乳化剂和十二烷基苯磺酸钠阻垢效果明显，十二烷基苯磺酸钠对首先析出的氟硅酸钠的影响最大。     

对苯二甲酸锌初级成核过程研究

为研究对苯二甲酸锌的成核过程,实验采用平衡法测量对苯二甲酸锌在苯二甲酸钠溶液中的溶解度计算成核过程的过饱和度;298.15 K下用聚焦光束发射测量仪在线监测对苯二甲酸锌反应结晶过程中诱导期,并计算临界成核半径和临界成核自由能与过饱和度的关系。结果表明:过饱和度越大,诱导期时间越短;根据经典成核理论,在过饱和度S大于8.16时,发生的是均相成核过程,过饱和度S小于6.66时,发生的是非均相成核过程;其中在均相成核中,临界成核半径和临界成核自由能都是随着过饱和度的增加不断减小。因此,提高过饱和度使成核过程更加容易进行。     

CaCO_3结垢诱导期的理论分析与实验研究

在区别结晶和结垢诱导期前提下,建立了CaCO_3在加热表面非均相成核结垢诱导期的数学模型,计算得到了该诱导期与壁面过饱和度、壁面温度、流体流速及表面性能的关系。以离子注氮的表面改性技术,制备低表面能无附加热阻的金属基新表面,实验研究了该表面对结垢诱导期的影响,发现它可延长结垢诱导期0.5～1倍以上,证实了表面性能同结垢诱导期的关系。     

表面诱导药物多晶型成核的研究进展

表面诱导成核是指在异相成核过程中,利用异质表面与溶质分子的相互作用来调控成核过程。表面诱导成核不仅可以降低成核能垒促进成核,而且可以在不改变溶剂、温度等条件下对晶型进行调控。近年来,表面诱导成核在药物新晶型的筛选和亚稳晶型的调控两方面得到了广泛研究。本文综述了异质表面影响多晶型成核的机理,介绍了用于诱导多晶型成核的四种异质表面——聚合物、有机小分子晶体、自组装单层膜（SAMs）和凝胶,总结了四种表面选择与设计的策略。最后,对目前存在的问题进行了总结,对未来的发展进行了展望。     

固体材料性质对生物垢形成的影响

从固体材料表面性质入手 ,探讨了材料的表面粗糙度、表面自由能、界面能以及材料与生物垢之间的界面能对生物垢形成的影响。实验结果表明 :在 0 2 9～ 1 82 μm内 ,材料的表面粗糙度越大越有利于生物垢的形成 ;在 11 7～ 38 3mN/m内 ,材料的表面自由能和固 -液界面能与生物垢形成之间没有简单、直接的关系 ;在 1 3～ 18 0mN/m内 ,固体材料与生物垢之间的界面能对生物垢的形成存在一个极大值 ,此时的界面能约为 3 4mN/m。     

L-酒石酸水溶液结晶介稳区和诱导期的测定

在20~60℃温度范围内,采用激光法测定L-酒石酸在水中的结晶介稳区宽度和诱导期,分别研究了饱和温度、冷却速率和搅拌速率对L-酒石酸结晶介稳区宽度的影响以及过饱和度对L-酒石酸诱导期的影响。结果表明:结晶介稳区宽度随着饱和温度、搅拌速率的增大和冷却速率的降低而变窄,并推算出表观成核级数m,给出了成核速率方程,此外实验测定结晶诱导期随过饱和度S增大而变短,基于经典成核理论和诱导期数据,计算出L-酒石酸在水中20℃和25℃下的固液界面张力。     

L-酒石酸水溶液结晶介稳区和诱导期的测定

在20~60℃温度范围内,采用激光法测定L-酒石酸在水中的结晶介稳区宽度和诱导期,分别研究了饱和温度、冷却速率和搅拌速率对L-酒石酸结晶介稳区宽度的影响以及过饱和度对L-酒石酸诱导期的影响。结果表明:结晶介稳区宽度随着饱和温度、搅拌速率的增大和冷却速率的降低而变窄,并推算出表观成核级数m,给出了成核速率方程,此外实验测定结晶诱导期随过饱和度S增大而变短,基于经典成核理论和诱导期数据,计算出L-酒石酸在水中20℃和25℃下的固液界面张力。     

功能表面材料与流体界面相互作用对垂直降液膜流动特性的影响

通过调节水温度、添加表面活性剂以及铝合金壁面表面改性处理来改变降膜流体与固体表面之间的表面自由能差值,运用JDC-2000型精密测微仪测定垂直降液膜的厚度,研究固体表面和液体间相互作用对流体垂直降膜流动特性的影响;考察了液膜雷诺数、流体温度、添加表面活性剂、固体表面材料物理化学性质等因素对垂直壁面降液膜流动特性的影响规律。实验结果表明:改变固体表面与降液膜流体的物理化学特性,即改变固液界面的相互作用能够改变流体的降膜流动特性。降液膜平均厚度随液固表面自由能差的增大而减小。     

表面活性剂的酸碱度对甲烷水合物生成的影响

针对甲烷水合物的快速制备,在初始压力7MPa和恒温2℃条件下采用脂肪醇聚氧乙烯醚硫酸钠(AES)阴离子表面活性剂和烷基多糖苷(APG1214)非离子表面活性,通过改变表面活性剂溶液的酸碱性,观察不同pH值对水合物的促进能力,并以表面活性剂分子吸附理论为基础进行分析。结果表明,在pH=3强酸条件下,水合物在气-液界面处先形成晶核,阻碍了气液继续接触,储气密度最低;在pH=11强碱性条件下,晶核在固-液界面处成核,水合物生成速率最高,储气密度最大。     

一水盐酸环丙沙星初级成核机理的研究

A general expression for the ralationship between induction period and supersaturation was developed based on polynuclear approach.Different mechanism of primary nucleation in solution can be illustrated by the expression.The results of induction period determined by laser scatering method shows that the crystallization of ciprofloxacin hydrochloride monohydrate in water/ethanol or aqueous solution is by the mechanism of primary nucleation followed by one-dimensional diffusion growth,and then one-dimensional continuous or “birth and spread” growth on crystal face. The growth mechanism on the crystal face is affected by temperature and solvent.     

Ultrasound assisted crystallization of cephalexin monohydrate:Nucleation mechanism and crystal habit control

With the high-quality requirements for cephalexin monohydrate,developing a robust and practical crys-tallization process to produce cephalexin monohydrate with good crystal habit,appropriate aspect ratio and high bulk density as well as suitable flowability is urgently needed.This research has explored the influence of ultrasound on crystallization of cephalexin monohydrate in terms of nucleation mechanism and crystal habit control.The results of metastable zone width and induction time measurement showed the presence of ultrasound irradiation can narrow the metastable zone and shorten induction time.Cavitation phenomena generated by ultrasound were used to qualitatively explain the mechanism of ultrasound promoting nucleation of cephalexin monohydrate.Furthermore,on the basis of classical nucleation theory and induction time data,a series of nucleation-related parameters (such as crystal-liquid interfacial tension,radius of the critical nucleus and etc.) were calculated and showed a decreasing trend under ultrasound irradiation.The diffusion coefficient of the studied system was also determined to increase by 72.73％ under ultrasound.The changes in these parameters have quantitatively confirmed the mechanism of ultrasound influence on the nucleation process.In further,the calculated surface entropy factor has confirmed that the growth of cephalexin monohydrate follows continuous growth mechanism under the research conditions of this work.Through the exploration of crystallization conditions,it is found that suitable ultrasonic treatment,seeding,supersaturation control and removal of fine crystals are conducive to improving the quality of cephalexin monohydrate product.Optimizing the crystalliza-tion process coupled continuous ultrasound irradiation with fine-crystal dissolution policy has achieved the controllable production of monodisperse cephalexin monohydrate crystal with good performance.     

Primary nucleation of lithium carbonate

A set of laser apparatus was used to explore the induction period and the primary nucleation of lithium carbonate. Results show that the induction period increases with the decrease of supersaturation, temperature and stirring speed. Through the classical theory of primary nucleation, many important properties involved in primary nucleation under different conditions were obtained quantitatively, including the interfacial tension between solid and liquid, contact angle, critical nucleus size, critical nuleation free energy etc.     

Determination of metastable zone and induction time of analgin for cooling crystallization

The solubility, metastable zone width, and induction time of analgin for unseeded batch cooling crystallization in ethanol–aqueous system were experimentally determined. The solubility data could be well described by the van't Hoff equation model. The metastable zone width at various cooling rates was measured, and some parameters of nucleation kinetic were calculated using the Ny'vlt theory. Furthermore, the induction period of various temperatures and supersaturation ratios was also measured. According to classical nucleation theory, some nucleation parameters and interfacial energy was calculated through the induction time(t_(ind)) data. Homogeneous nucleation tended to occur when the supersaturation is high, whereas heterogeneous nucleation was more likely to occur when the supersaturation is low.     

C3S在纯水和化学外加剂溶液中水化液相的研究

本文研究了C_3S在纯水和化学外加剂溶液中水化时,液相成分的变化规律。发现C_3S在纯水中水化可分为4个阶段,其中第Ⅱ阶段相当于水化诱导期,此阶段中C_3S的溶解速度R_0为常数。化学外加剂的存在并不改变C_3S的水化本质,但能缩短水化诱导期。化学外加剂对C_3S水化速度的影响主要取决于组成该外加剂的阴、阳离子的本质。本研究还通过实验证明了硅酸盐离子对Ca(OH)_2核晶过程的“毒化”作用,为C_3S延迟核晶水化理论提供了直接证据。     

Unusual kinetic inhibitor effects on gas hydrate formation

Gas hydrate formation experiments were conducted with a methane-ethane mixture at 273.7 or 273.9 K and 5100 kPa and using water droplets or water contained in cylindrical glass columns. The effect of kinetic inhibitors and the water/solid interface on the induction time for hydrate crystallization and on the hydrate growth and decomposition characteristics was studied. It was found that inhibitors GHI 101 and Luvicap EG delayed the onset of hydrate nucleation. While this inhibition effects has been reported previously some unusual behaviour was observed and reported for the first time. In particular, the water droplet containing GHI 101 or Luvicap EG was found to collapse prior to nucleation and spread out on the Teflon surface. Subsequently, hydrate was formed as a layer on the surface. Catastrophic growth and spreading of the hydrate crystals was also observed during hydrate formation in the glass columns in the presence of the kinetic inhibitor. Finally, when polyethylene oxide (PEO) was added into the kinetic inhibitor solution the memory effect on the induction time decreased dramatically.     

The initial stage of hydrate formation in liquid volume on impurity particles upon contact of gas and water

A concept and appropriate theoretical construction have been proposed to describe initial stage of hydrate layer formation at the interface between water and hydrate-forming gas. The model presented indicates that this stage (or induction period) is accompanied by the dissolution of gas in water, as well as the formation and growth of hydrate in the bulk zone on impurity particles near the contact boundary. An analytical solution was obtained for the characteristic time during which the volume content of the hydrate phase at the contact boundary reaches one and, thus, nuclei form as a film prior to a hydrate layer at the gas–water boundary. This characteristic time is accepted as the induction time. According to the obtained formula, the induction period depends inversely on static pressure and in inverse two-thirds proportion on the number of impurity particles per unit volume of water. The problem of the formation and growth of hydrate at the interface between the hydrate layer and aqueous gas solution has been considered and solved. The temperature fields caused by heat generated during hydrate formation on the contact surface of hydrate massif and gas solution are analyzed.     

季戊四醇水溶液结晶介稳区性质的研究

用激光自动检测法测定了季戊四醇水溶液在不同降温速率、搅拌转速下的结晶介稳宽度以及不同过饱和度下的结晶成核诱导期。实验还采用折射率法测定了季戊四醇在水中的溶解度     

电磁场对碳酸钙成核诱导期影响的实验研究

基于电导率随滴定液容积变化特征与碳酸钙结晶过程的对比分析,研究了电磁场作用对碳酸钙结晶过程中成核诱导期的影响。在不同频率的电磁场作用下观察了碳酸钙溶液临界过饱和度及成核诱导期的变化,大量实验结果表明:电磁场作用能够降低碳酸钙溶液临界过饱和度,加速碳酸钙成核,缩短成核诱导期。通过机理分析,电磁场对碳酸钙成核过程的主要作用为:在洛伦兹力的影响下,溶液中的Ca2+及CO32-等带电离子运动方向要向相反方向偏离,增加了Ca2+和CO32-离子间的碰撞几率,加快新相晶核的生成。