四钼酸铵在过饱和溶液中的成核研究

本文根据经典均匀成核理论,分别研究了硝酸酸沉和盐酸酸沉制备的四钼酸铵过饱和溶液的成核过程,并讨论了过饱和比和温度对成核速率及成核机制的影响.研究结果表明,无论是硝酸酸沉还是盐酸酸沉,四钼酸铵过饱和溶液的成核速率均随过饱和比和温度的升高而增大;固液界面张力、临界半径及临界成核自由能均随温度的升高而减小.比较硝酸酸沉和盐酸酸沉四钼酸铵过饱和溶液的成核速率,发现后者的成核速率比前者大.     

马来酸氢十六酯(HHM)在过饱和溶液中的成核过程

本文研究了马来酸氢十六酯(HHM)在以甲苯为溶剂的过饱和溶液中的成核过程.测定了以诱导时间表示的成核速率.用经典的成核理论计算了固-液表面张力、成核自由能和临界成核半径.指出HHM晶体在甲苯为溶剂的过饱和溶液中的成核速率随着温度和过饱和比的提高而增大.溶剂的性质也将改变成核速率的大小.     

电光晶体硒酸氢铷过饱和溶液的成核研究

本文对硒酸氢铷(RbHSeO4,RHSe)晶体生长过饱和溶液的均匀成核过程进行了初步的研究.通过动态目视法测量RHSe过饱和溶液的诱导期,讨论过饱和比、温度对诱导期的影响,并根据经典均匀成核理论计算不同温度下的晶体表面张力、成核自由能和临界成核半径,为探讨RHSe单晶的水溶液生长的较佳条件提供依据.     

不同EDTA添加剂浓度下ZTS溶液诱导期及其成核特性研究

测定了25℃下,添加不同浓度的EDTA后,不同过饱和比下ZTS溶液的诱导期,研究了掺杂浓度及过饱和比对ZTS溶液成核的影响.研究显示,当溶液处于较高过饱和比时(S＞1.13),均匀成核占主导;而在较低过饱和比时(S＜ 1.11),则以非均匀成核为主.利用经典成核理论对实验所得数据进行分析,计算得到了界面张力、临界核形成功、临界核半径等成核特性,发现了溶液过饱和比及掺杂浓度对成核速度的影响,解释了添加EDTA能提高溶液稳定性的原因.利用界面张力的值计算得到了表面熵因子.     

对苯二甲酸十八酯(OTO)晶体在过饱和溶液中的成核过程

本文研究了对苯二甲酸十八酯在甲苯为溶剂的过饱和溶液中的成核过程。测定了以诱导时间表示的成核速率。通过经典成核理论计算了固－液表面张力,成核自由能和临界成核半径。指出ＯＴＯ晶体在甲苯为溶剂的过饱和溶液部的成核速率随着温度和过饱和度的提高而增大,溶剂的性质将改变成核速率的大小。     

过饱和温度和降温速率对BBO晶体浓度边界层厚度的影响

浓度边界层是晶体生长过程中分析界面输运现象的重要元素.我们从实验角度研究了扩散机制下的BaB2O4单晶生长中过饱和温度和降温速率对浓度边界层厚度的影响.过饱和温度和浓度边界层厚度之间为抛物线关系,降温速率和浓度边界层厚度变化率之间为线性关系.     

不同pH值下磷酸二氢铵(ADP)溶液成核过程研究

利用全程摄像的方法测定了不同情况下ADP过饱和溶液的诱导期,研究了不同pH值、不同温度的ADP过饱和溶液的成核过程,讨论了pH值、温度和过饱和度S等因素对诱导期的影响.结果表明:改变pH值后,在同一过饱和度下,溶液的稳定性在不同温度间差异较小,更利于晶体在较高的温度下稳定快速的生长;改变pH值后,溶液在整个过饱和度范围内更趋向于均匀成核.根据经典均匀成核理论,针对ADP溶液均匀成核的状况计算出了不同pH值和温度下的固-液界面张力、临界成核功等成核参数,并从上述参数的相互比较中得到了改变pH值后溶液稳定性变强的微观原因.最后通过对表面熵因子的计算,确定了ADP晶体的微观生长机制为连续生长模式.     

新型有机非线性光学材料L-酒石酸脲晶体生长研究

本文研究了有机非线性光学晶体L-酒石酸脲在过饱和溶液中的成核过程.测定了不同温度下L-酒石酸脲的溶解度和成核诱导期,计算了成核特征参数.讨论了不同温度、过饱和度对L-酒石酸脲成核诱导期的影响.研究表明L-酒石酸脲晶体的成核诱导期随着溶液温度和过饱和度的增大而减少.通过经典成核理论计算了L-酒石酸脲的固液表面张力、成核自由能和临界成核半径等系列成核参数.     

CVD金刚石薄膜表面的缺陷研究

用SEM方法观察分析了CVD金刚石薄膜表面的缺陷形貌和结构,直观的两种缺陷为孪晶和孔洞.孪晶反映了晶粒的不完整性,它的产生取决于气相中活性分子的浓度与生长表面活性位数目的比值,孪晶比率随碳源浓度升高和衬底温度的降低而增大;孔洞反映了膜的不致密性,其产生与膜生长速率和衬底表面初始成核密度切相关,孔洞密度随碳源浓度升高和衬底温度的升高而增大.     

动力学蒙特卡洛(KMC)模拟薄膜生长

本文以扩散理论为基础,利用KMC模拟方法,考察了温度对薄膜生长速率和表面形貌的影响以及生长表面的粗糙化相变过程.模拟表明,温度升高有利于提高薄膜生长速率,薄膜生长以“成核-岛数增长-岛的长大融合”的方式进行.模拟发现薄膜生长初期存在粗糙化相变过程,当温度低于相变温度时,薄膜分层生长,生长速率较慢;当温度高于相变温度时,薄膜表面粗糙度骤然升高,生长速率加快.     

Secondary Nucleation of Ammonium Alum in the Presence of Insoluble Additives in the Solution

Secondary nucleation of ammonium alum has been investigated in seeded batch crystallization from aqueous solutions. The presence of a time lag is established during which the nucleation rate increases up to a constant value. The duration of the time lag increases with increasing supersaturation. The effect of fine heteroparticles of alumina and silica on the rate of secondary nucleation is studied. The heteroparticles slightly increase the nucleation rate but cause the appearance of a considerable number of new nuclei when introduced some time after the process beginning. An assumption is made that the heteroparticles mainly affect the surviving of non-growing nuclei without changing the actual rate of secondary nucleation.     

Nucleation Studies in Supersaturated Triglycine Sulphate Solutions

Rates of nucleation of supersaturated aqueous solutions of Triglycine sulphate are measured by the induction period over the temperature range 30–50 °C. The effects of temperature and supersaturation on the induction period are reported. The interfacial tension, energy of formation and radius of the critical nuclei of the crystal are calculated in accordance with classical nucleation theory. Nucleation rate increases with increase in supersaturation and temperature, while interfacial tension decreases with increase in temperature.     

Investigation of metastable zone width of ammonium oxalate aqueous solutions

The metastable zone width of pure ammonium oxalate aqueous solutions, as represented by maximum supercooling ΔT_max, is investigated as functions of cooling rate R and saturation temperature T₀ by the polythermal method. The experimental results are discussed by using two recently advanced approaches: (1) self‐consistent Nývlt‐like approach based on a power‐law relationship between nucleation rate J and maximum supersaturation lnS_max, and (2) a novel approach based on the relationship between J and lnS_max described by the classical three‐dimensional nucleation theory. Analysis of the experimental data revealed that both approaches describe the experimental data on metastable zone width by the polythermal method reliably and provide useful information about the physical processes and parameters involved in nucleation kinetics. The values of various physical quantities predicted by both of these approaches are reasonable for a fairly‐soluble compound. A careful examination of the data on ΔT_max as a function of T₀ obtained by polythermal method and from density measurements showed that ΔT_max has a slight tendency to decrease with increasing saturation temperature T₀. The values of lnS_max at saturation temperature 303 K suggest that the metastable zone width of ammonium oxalate aqueous solutions is determined by primary nucleation in the polythermal method and by secondary nucleation during density measurements. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Influence of a polyacrylate antiscalant on gypsum nucleation and growth

Calcium sulphate dihydrate (gypsum) crystallization was studied under conditions, of supersaturation and temperature, simulating a brackish water desalination unit using solar energy. The effect of an commercial sodium salt of poly(acrylic acid), based compound known as RPI, on homogeneous nucleation and growth of gypsum was also examined. Gypsum was precipitated by mixing aqueous CaCl₂ and Na₂SO₄ solutions. It was found that, with increasing temperature or supersaturation, the induction time decreases and the growth rate increases. By using classical nucleation theory, the interfacial tension and the nucleation rate values were estimated. It was shown that the interfacial tension is temperature dependent. The addition of increasing quantities of RPI, in the same conditions of temperature and supersaturation, prolongs the induction time, decreases the nucleation rate and increases the interfacial tension. The addition mode of RPI (in calcium or in sulphate solution) was found as an important parameter in controlling the inhibition process of gypsum crystallization. XRD and SEM analysis showed that RPI antiscalant strongly affected the texture and the morphology of the deposit gypsum. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Effect of supersaturation on the crystallization of phenylbutazone polymorphs

The article describes the effect of degree of supersaturation, σ, on the crystallization of specific polymorphs of phenylbutazone from its methanolic solution at 20 °C. At low initial supersaturation, σ ≤ 2.0, the fraction of the metastable α polymorph in the crystallized product exceeds that of the δ polymorph, while at σ ≥ 5.0, the fraction of the stable δ polymorph increases in the crystallized product. The results are explained by the effect of supersaturation on the relative rates of nucleation and crystal growth of the polymorphs. Furthermore, the mechanism of nucleation and crystal growth also change with supersaturation. Supersaturated methanolic solutions of phenylbutazone exhibit a critical temperature at which the nucleation rates of the polymorphs decrease drastically. This effect is partly explained by the decreased mobility of phenylbutazone molecules at lower temperatures. Nucleation is most rapid when the crystallization temperature is close to the transition temperature, T_t(α ⟷ δ), between the polymorphs, α and δ. The nucleation rate decreases as the temperature difference between T_t(α ⟷ δ) and the crystallization temperature increases. (© 2005 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Investigation of nucleation kinetics and crystal defects of HMX

The nucleation kinetics of HMX (cyclotetramethylene tetranitramine, C₄H₈N₈O₈) in γ‐butyrolactone was studied in cooling process by induction time method. The laser scattering method was used to measure the solubility data and metastable region of HMX in γ‐butyrolactone. The induction time was measured over a range of supersaturation at different temperatures. Then, the nucleation mechanism of HMX in γ‐butyrolactone was investigated by analysis the relationships between induction time and supersaturation. The results indicated homogeneous nucleation dominated at high supersaturation of S >1.35, while the heterogeneous nucleation dominated at low supersaturation of S < 1.35. The values of interfacial tension at different final temperatures were calculated to indicate the ability of HMX to be crystallized. The growth mechanism of HMX was investigated by the data fitting applying different growth mechanism models and identified as two‐dimensional nucleation‐mediated (2D) growth. Finally, the effects of supersaturation and temperature on the crystal defects were analyzed based on the nucleation kinetics. When the temperature is below 303.15K, homogeneous nucleation dominated the nucleation process at higher supersaturation. Fine HMX crystals with more defects were produced. On the contrary, heterogeneous nucleation mechanism dominated at lower supersaturation. large regular HMX crystals with fewer defects were formed when the temperature is above 318.15K.     

Kinetics of protein crystal nucleation and growth in the batch method

We have applied the Johnson–Mehl–Avrami–Kolomogorov (JMAK) theory of crystal nucleation and growth to the problem of protein crystallization in the batch method. Without integrating the JMAK equation explicitly, we use dimensional analysis to derive a general formula for the half-life for decay of the protein supersaturation. This formula includes a dimensioned group and an arbitrary dimensionless function. We integrate the JMAK equation exactly for the special case where the growth rate is independent of the supersaturation and the nucleation rate is proportional to its square. This gives an equation for the time decay of the supersaturation and a formula for the half-life in which all arbitrary dimensionless functions are evaluated. The results are consistent not only with Von Weimarn's rule, which asserts that the average size of a crystal increases as the supersaturation decreases, but also with our experimental results for crystallization of lysozyme, in which the half-life at fixed pH decreases with increasing ionic strength and decreasing temperature.     

Batch Precipitation of Potash Alum Crystals by Mixing Aqueous Solutions of the Component Salts

The effects of temperature, supersaturation, excess of reacting component salts and method of precipitation on the batchwise precipitation of potash alum crystals, by mixing aqueous solutions of potassium sulphate and aluminium sulphate, have been investigated. From the primary characteristics of the process (crystal size, size distribution and yield) relative crystal growth rates and relative nucleation rates are calculated and interrelation of these rates with the corresponding supersaturation leads to a value of the nucleation order. It is concluded that secondary nucleation plays an important role in the batch precipitation of potash alum crystals.     

Evaluation of nucleation rate by in‐situ focused beam reflectance measurement in an unseeded batch cooling crystallization

Nucleation kinetics in the cooling crystallization of hexahydro‐1,3,5‐trinitro‐1,3,5‐triazine (RDX) from γ‐butyrolactone was studied by converting total counts/s measured by in situ focused beam reflectance measurement (FBRM) into number of crystals. The classical nucleation rate model, which is derived exclusively from the thermodynamic state for the nucleation and molecular collision frequency, was found to be inadequate to describe the experimentally measured nucleation rates. However, the nucleation rates predicted by the modified classical nucleation rate model, inclusive of an additional temperature term, were found to be in good agreement with those measured in the present work. Furthermore, the metastable zone widths are also found to be more accurately predicted by the modified classical nucleation rate model than the classical approach, which assumes that the mass‐based nucleation rate is an exponential function of supersaturation and is equal to the supersaturation rate.