Ultrasound-assisted crystallization (sonocrystallization)

The positive influence of ultrasound (US) on crystallization processes is shown by the dramatic reduction of the induction period, supersaturation conditions and metastable zone width. Manipulation of this influence can be achieved by changing US-related variables such as frequency, intensity, power and even geometrical characteristics of the ultrasonic device (e.g. horn type size). The volume of the sonicated solution and irradiation time are also variables to be optimized in a case-by-case basis as the mechanisms of US action on crystallization remain to be established. Nevertheless, the results obtained so far make foreseeable that crystal size distribution, and even crystal shape, can be ‘tailored’ by appropriate selection of the sonication conditions.     

Modelling of electrolyte mixtures with application to chemical equilibria in mixtures—prototypes of blood''s plasma and calcification of soft tissues

Modelling of the biologic solutions has a great importance for basic physicochemical backgrounds of the living processes, mechanism of the diseases and drugs action, etc. The modelling of the chemical equilibria in solution that served as a prototype of the blood plasma with application to calcification of the tissues is performed. The concentrations of molecular–ionic forms containing calcium and hydrogen cations and phosphate anions in the range of ionized-calcium and total phosphorus concentrations from 0.5 to 3.0 mM and at the solution pH of 7.1–7.8 were calculated. The activities of the ionized species were described in approach to Debye–Hückel's theory. The full set of the equilibria taking into consideration dissociation of the water, phosphoric acid, formation of both inert and ionic calcium phosphates was considered. The states of calcium hydrophosphate dihydrate CaHPO₄·2H₂O (CHPD), calcium phosphate Ca₃(PO₄)₂ (CP), calcium hydrophosphate-phosphate dihydrate Ca₄H(PO₄)₃·2H₂O (CHPPD) and hydroxyapatite Ca₃OH(PO₄)₃ (HA) with respect to the boundary of the region in which they crystallise were determined. A criterion has been introduced to characterize the degree of salt supersaturation with respect to crystallisation, which is based on the concentration distance between the states of a salt in solution and at the boundary of its crystallisation. This criterion is used to provide a quantitative characteristic of the supersaturation of the phosphates and their tendency to crystallise in blood's plasma. It was established that the most soluble of the phosphates, CaHPO₄·2H₂O, is undersaturated and the other phosphates are supersaturated with respect to crystallisation. Thus, this phosphate does not take part in the calcification, and this is the source for ionized calcium in a blood plasma from the soft tissues. The role of the other phosphates in calcification of the soft tissues is decreased in the series HA>CP>CHPPD. The dependencies of the supersaturation of the solution on the pH and on the concentrations of calcium and phosphorus in a mixture are discussed.     

不同草酸/钙摩尔比条件下草酸钙晶体的生长及对HK-2细胞的毒性

研究了不同草酸/钙(Ox/Ca)摩尔比对CaOx晶体在损伤前后的人肾近曲小管上皮细胞(HK-2)表面的生长差异及形成的晶体对细胞的毒性差异. 实验结果表明, CaOx过饱和溶液对正常细胞和损伤细胞均会产生进一步的损伤, 导致细胞活力、 溶酶体的完整性和线粒体膜电位降低, 而细胞内活性氧(ROS)、 细胞骨架的紊乱程度、 磷酯酰丝氨酸(PS)外翻比例和骨桥蛋白(OPN)表达量均增加; 且随着过饱和溶液中Ox/Ca摩尔比的增加而损伤加重. 正常细胞主要诱导二水草酸钙(COD)晶体形成, 且COD的含量与Ox/Ca摩尔比成正相关. 损伤细胞表面主要生成一水草酸钙(COM), 且晶体的数量和聚集程度与Ox/Ca摩尔比成正相关. 相比于正常细胞, 损伤细胞诱导的晶体棱角更加尖锐, 其对细胞的损伤大于棱角圆钝的晶体. 实验结果还表明, 降低CaOx的过饱和度、 减小Ox/Ca摩尔比和修复受损伤的肾上皮细胞均有利于抑制CaOx结石形成.     

碳化硅单晶材料的溶剂热合成与表征

采用SiCl4、CCl4和金属K体系 ,以溶剂热合成法在高压釜中制备了碳化硅 (SiC)单晶材料 .通过X射线粉末衍射 (XRD)、Raman光谱和透射电子显微镜 (TEM)对产物进行了表征 .其中XRD数据显示所得产物为碳化硅 .TEM结果表明 ,采用不同剂量的金属K ,所得产物分别为丝状和片状的SiC单晶 .SiC单晶丝直径为 10～2 0nm ,长度可达 1.5 μm ;SiC晶片的横向尺寸为 0 .1～ 3μm ,具有规则多面体外形 ,显示阶梯状生长侧面 .此外 ,对SiC单晶材料的生长机理进行了讨论 ,研究了过饱和度对SiC晶体生长和形貌的影响 .     

Sonochemical synthesis of supersaturated Ga–Al liquid-alloy fine particles and Al3+-doped γ-Ga2O3 nanoparticles by direct oxidation at near room temperature

In this study, we investigated the fabrication of supersaturated gallium (Ga)–aluminum (Al) liquid alloy and Al³⁺-doped γ-Ga₂O₃ nanoparticles (NPs) at near room temperature (60 °C) using sonochemical and sonophysical effects. Supersaturated Ga–Al liquid alloy microparticles (D_av = 1.72 µm) were formed and stabilized at 60 °C by the thermal nonequilibrium field provided by sonochemical hot spots. Compared with liquid Ga, supersaturated Ga–Al liquid alloy was rapidly oxidized to a uniform oxide without Al₂O₃ or Al deposition. Thus, ultrafine Al³⁺-doped γ-Ga₂O₃ NPs were obtained after only 1 h of ultrasonic irradiation at 60 °C. The oxidation of liquid Ga was remarkably accelerated by alloying with metallic Al and ultrasonic irradiation, and the time was shortened. The average diameter and surface area of the γ-Ga₂O₃-based NPs were 59 nm and 181 m²/g, respectively. Compared with γ-Ga₂O₃, the optical bandgap of the Al³⁺-doped γ-Ga₂O₃ NPs was broadened, and the thermal stability improved, indicating Al³⁺-doping into the γ-Ga₂O₃ lattice. However, the lattice constant of γ-Ga₂O₃ was almost unchanged with or without Al³⁺-doping. Al³⁺ was introduced into the defect sites of Ga³⁺, which were massively induced in the defective spinel structure during ultrasonic processing. Therefore, sonochemical processing, which provides nonequilibrium reaction fields, is suitable for the synthesis of supersaturated and metastable materials in metals and ceramics fields.     

Explosivity Conditions of Aqueous Solutions

This paper focuses on the conditions for explosive boiling and gas exsolution of aqueous solutions from a thermodynamic point of view. Indeed, the kinetic nature of these processes, hence their explosivity, can be assessed by considering their relation with the spinodal curve of these liquids. First, the concepts of mechanical and diffusion spinodals are briefly described, which allows us to introduce the notions of superspinodal (explosive) transformations and subspinodal (non-explosive) ones. Then, a quantitative study of spinodal curves is attempted for the binary systems H₂O–CO₂ and H₂O–NaCl using equations of state having a strong physical basis. It is shown that dissolved gaseous components and electrolytes have an antagonist effect: dissolved volatiles (like CO₂) tend to shift the superspinodal region towards lower temperatures, whereas electrolytes (like NaCl) tend to extend the metastable field towards higher temperatures.     

Single bubble growth during water electrolysis under microgravity

Single bubble evolution on a micro-electrode (Pt, φ = 0.2 mm) was observed in 0.36 M KOH solution under terrestrial (1-G) and microgravity (μ-G) environments. The bubble size during galvanostatic electrolysis (j = −2.6 × 10³ A m⁻²) was measured by CCD images, which allowed us to calculate the gas evolution efficiency, f_G, by comparison with the consumed charge. The efficiency under μ-G increased until 1 s after starting electrolysis and then reached constant value (f_G = 0.85), while, under 1-G, it showed a lower value and remarkably decreased 2 s after the beginning of the measurement. Such differences between μ-G and 1-G were explained by the mass transfer rate of the dissolved gas. Bubble-induced microconvection dominated the mass transfer under μ-G without any buoyancy force, on the other hand, the single-phase free convection (microscopic natural convection) influenced the bubble growth under 1-G.     

Some Turán type results on the hypercube

For graphs H,G a classical problem in extremal graph theory asks what proportion of the edges of H a subgraph may contain without containing a copy of G. We prove some new results in the case where H is a hypercube. We use a supersaturation technique of Erd?s and Simonivits to give a characterization of a set of graphs such that asymptotically the answer is the same when G is a member of this set and when G is a hypercube of some fixed dimension. We apply these results to a specific set of subgraphs of the hypercube called Fibonacci cubes. Additionally, we use a coloring argument to prove new asymptotic bounds on this problem for a different set of graphs. Finally we prove a new asymptotic bound for the case where G is the cube of dimension 3.     

Nucleation kinetics of selenium (+4) precipitation from an acidic copper sulphate solution

The removal of selenium from copper sulphate solution prior to the electrowinning of copper is desirable in order to minimise contamination of the copper cathodes by selenium and other impurities. The selenium removal is effected by a precipitation process that takes place under high supersaturation conditions, which favour nucleation over any other particle formation processes. There is currently no fundamental information on the nucleation kinetics of this important process. In this study, the nucleation kinetics of selenium (+4) precipitation from an acidic copper sulphate solution was determined using the classical nucleation theory (CNT). Experiments were carried out by varying the levels of supersaturation from 8.66×10¹⁵ to 4.33×10¹⁷ at a temperature of 95 °C under atmospheric pressure. The nucleation rates for four different levels of supersaturation, the nucleation work and the nucleus size were determined. The kinetic constant A was found to be 3.92×10²⁷ m⁻³ s⁻¹, which shows that the nucleation process takes place through a homogeneous mechanism. The associated thermodynamic parameter (B) was determined to be 8.98×10⁰⁴.