Calculating the thermodynamic parameters of the surface layer of the binary sodium-potassium system

The composition and number of surface monoatomic potassium layers in Na-K alloys are calculated on the basis of theory of the thermodynamic stability of surface layers of metal alloys with respect to their thickness. The surface layer of Na-K alloys is shown to be thermodynamically stable at surface layer thickness of two monoatomic potassium layers in the range of compositions with K in Na content of ∼13–15 at %. Good agreement is obtained using the surface activities of the components in binary metal melts as criteria.     

Materials discovery by crystal growth: Lanthanide metal containing oxides of the platinum group metals (Ru, Os, Ir, Rh, Pd, Pt) from molten alkali metal hydroxides

This review addresses the process of materials discovery via crystal growth, specifically of lanthanide metal containing oxides of the platinum group metals (Ru, Os, Ir, Rh, Pd, Pt). It provides a detailed overview of the use of hydroxide fluxes for crystal growth. The melt chemistry of hydroxide fluxes, specifically, the extensive acid base chemistry, the metal cation solubility, and the ability of hydroxide melts to oxidize metals are described. Furthermore, a general methodology for the successful crystal growth of oxides is provided, including a discussion of experimental considerations, suitable reaction vessels, reaction profiles and temperature ranges. Finally, a compilation of complex platinum group metal oxides recently synthesized using hydroxide melts, focusing on their crystal growth and crystal structures, is included.     

The influence of the composition of CsCl-LiCl-YCl<Subscript>3</Subscript> melts on their acid properties at 973 K

The acid properties of CsCl-xLiCl and CsCl-LiCl + xYCl₃ melts were studied at 973 K by the potentiometric method with the use of a Pt(O₂)|ZrO₂(Y₂O₃) oxygen electrode. The acidity of these melts increased as x grew. The oxobasicity index values (pI _L) were estimated, they were 3.84 for 2CsCl-LiCl and 5.55 for 0.875(2CsCl + LiCl) + 0.125YCl₃ melts. The acid properties of mixed “alkali metal halide-rare-earth metal halide” melts were close to each other, and the presence of Li⁺ cations in such melts did not influence their pI _L values because of the leveling of their acid properties.     

Effect of metals on melt oxidation of polyethylene

Oxidation of polyethylene (PE) melts in contact with metals (Cu, Pb, Au, Al, Zn, Ag) has been studied by infrared spectroscopy and differential thermal analysis (DTA). These metals may be divided into two groups, depending on their activity for oxidizing PE: namely, high-activity metals (Cu, Pb, Ag, Zn) and low-activity metals (Al, Au). During the oxidation of PE in contact with high-activity metals dissolution of the surface layer of metal is observed with accumulation of metal-containing compounds (salts of carboxylic acids) in the bulk of the polymer. With low-activity metals these phenomena are not observed. The rate of oxidation of PE on low-activity metals approaches the oxidation rate of nonmetals (polytetrafluoroethylene and inorganic glass). With certain high-activity metals (Cu, Pb) the process of oxidation is accelerated only in the early stage of oxidation; then the oxidation rate slows down and the oxidation process ceases. PE films separated from metal after being oxidized on it possess chemical memory, i.e., their oxidation rate depends on the nature of the metal with which they had been in contact, and on the duration of the contact oxidation. The effect of salts of carboxylic acids (metal stearates) on the oxidation of PE melts was also studied. Based on the data obtained, it is concluded that the rate of oxidation of PE melts on high-activity metals is controlled by metal-containing compounds which are the products of contact reactions.     

On surface tension theory of salt melts

Density functional theory was developed to take into account the effect of charge density gradient on the surface tension of asymmetric ionic melts. The predicted values are compared with the experimental data on the surface tension of the majority of alkali metal halides.     

Formation of autocomplexes in halide melts of trivalent metals

Chemical equilibrium with respect to the dissociation of charged autocomplexes (MX₆)^3? in ionic melts of the MX₃ type is analyzed. The chemical equilibrium M³⁺ + 6X^? = (MX₆)^3? in salt melts of trivalent metal halides shifts strongly toward dissociation, due to the electrostatic interactions between charged particles in the melts.     

The relationship between thermodynamic properties and local atomic structure of Al-TM (TM = Mn,Fe, Co,Ni, Cu) melts

The relationship between structure and thermodynamic properties of Al- transition metal (TM) (TM = Mn, Fe, Co, Ni, Cu) melts had been studied by using the results of X-ray diffraction experiments, reverse Monte Carlo simulations and the model of ideal associated solution (MIAS). It was considered that local atomic structure of melts is determined by dense non-crystalline atomic packing and energy of interatomic interactions. This allowed to choose the types of associates for the MIAS. It is shown that the prominent role of the atomic packing factor in the Al-Mn, Al-Fe melts leads to correlation between the local atomic ordering of melts and the one of relevant polytetrahedral phases and defines a set of associates. Strengthening of heteroatomic interactions in the Al-Co, Al-Ni melts leads to an increase of the energy factor role in determining their structure and properties that reduces the number of associates from three for the Al-Mn melts to one for the Al-Ni.     

Effect of polymer surface morphology on adhesion and adhesive joint strength. II. FEP Teflon and nylon 6

Heterogeneous nucleation and crystallization of FEP Teflon and nylon 6 melts against high energy surfaces (i.e., gold) produce an interfacial region, in these polymers, of high mechanical strength. Dissolution of the metal substrate rather than removal by mechanical means results in a polymer surface which is amenable to conventional structural adhesive bonding. Nucleation and crystallization of the polymer melts in contact with phases of low surface energy (e.g., vapor) result in the generation of weak boundary layers.     

Effect of the size of the aliphatic chain on the NMR spectra and the electrical conductivity of melts of alkali metal alkanoates in alkanoic acids

The dependence of NMR spectra of ⁷Li, ²³Na, ¹³³Cs and of the conductivity of melts of lithium, sodium, and cesium alkanoates in melts of alkanoic acids on the length of the aliphatic chain of the anion has been studied. As the anion size increases, chemical shifts of ²³Na and ¹³³Cs nuclei toward weak fields and ⁷Li nuclei toward strong fields are observed. The nature of the chemical shifts of alkali metal nuclei and of the electricity transport characteristic in the studied systems is discussed in connection with the nature of cation-anion interactions and the size and degree of free rotation of the anion.Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 29, No. 1, pp. 81–87, January–February, 1993.     

Thermal stability of alkali metal borates and alkaline earth metal borates

The correlation between the enthalpies of formation of alkali metal and alkaline earth metal borates and the composition of the vapor in equilibrium with their melts is considered. The thermal stabilities of the studied borates have been estimated. A method is suggested for determination of the relative composition of the vapor over borate melts on the basis of their enthalpies of formation.

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Zusammenfassung Es wurde die Beziehung zwischen den Bildungsenthalpien von Alkali- (Erdalkali-)metallboraten und der Zusammensetzung der sich mit der Schmelze im Gleichgewicht befindlichen Gasphase betrachtet. Die thermische Stabilität der untersuchten Borate wurde geschätzt. Es wurde ein Verfahren entwickelt, die relative Zusammensetzung der Gasphase über Boratschmelzen auf Grund ihrer Bildungsenthalpien zu bestimmen.

     

Synthesis of alkaline-earth metal tungstates in melts of [NaNO3-M(NO3)2]eut-Na2WO4 (M = Ca, Sr, Ba) systems

Alkaline-earth metal tungstates are synthesized in NaNO₃-M(NO₃)₂ (M = Ca, Sr, Ba) eutectic melts. The synthesis is based on the exchange reaction of calcium, strontium, or barium nitrate with sodium tungstate.     

The properties of the surface of molten mixtures of the LiCl-KCl eutectic with praseodymium,samarium, erbium,and ytterbium chlorides

The temperature dependence of surface tension was studied and the excess Gibbs energy of the surface of a sphere with a molar volume of molten quasi-binary mixtures of the LiCl-KCl eutectics with LnCl₃ (Ln = Pr, Sm, Er, and Yb) was calculated. The influence of rare-earth and alkali metal cations on the surface properties of the systems studied was considered. Deviations from ideal surface tension isotherms and excess Gibbs energy of the surface of a sphere with a molar volume are explained by the complex structure of melts.     

金属铜升温熔化过程的分子动力学模拟

采用分子动力学方法模拟了金属铜的升温熔化过程.原子间作用势采用FS (Finnis-Sinclair)势，结构分析采用双体分布函数(PCF)、均方位移(MSD)等方法.计算结果表明,在连续升温过程中，金属铜在1444 K熔化，在该熔化点的扩散系数为4.31×10－9 m2•s－1.上述结论与实验值相当接近，并且比之采用EAM镶嵌原子势所作模拟得到的结果更佳，说明FS势可以用来处理象液铜这样较复杂的无序体系.本文指出了升温速率在金属熔化过程中所起的作用.     

Concentration fluctuations and the heat capacity of overcooled melts in the Fe-B system

Concentration fluctuations, excess configurational entropies, and excess configurational heat capacities of melts in the Fe-B system are calculated at different temperatures. It is shown that concentration fluctuations play an important role in the amorphization of melts and should be considered in an analysis of the propensity of melts for amorphization.     

In situ spectroscopy and spectroelectrochemistry of uranium in high-temperature alkali chloride molten salts

Soluble uranium chloride species, in the oxidation states of III+, IV+, V+, and VI+, have been chemically generated in high-temperature alkali chloride melts. These reactions were monitored by in situ electronic absorption spectroscopy. In situ X-ray absorption spectroscopy of uranium(VI) in a molten LiCl-KCl eutectic was used to determine the immediate coordination environment about the uranium. The dominant species in the melt was [UO 2Cl 4] (2-). Further analysis of the extended X-ray absorption fine structure data and Raman spectroscopy of the melts quenched back to room temperature indicated the possibility of ordering beyond the first coordination sphere of [UO 2Cl 4] (2-). The electrolytic generation of uranium(III) in a molten LiCl-KCl eutectic was also investigated. Anodic dissolution of uranium metal was found to be more efficient at producing uranium(III) in high-temperature melts than the cathodic reduction of uranium(IV). These high-temperature electrolytic processes were studied by in situ electronic absorption spectroelectrochemistry, and we have also developed in situ X-ray absorption spectroelectrochemistry techniques to probe both the uranium oxidation state and the uranium coordination environment in these melts.     

Basicity-acidity and solubility of metal fluorides and oxides in salt melts

The concept relating the basic-acidic properties of compounds (metal fluorides and oxides) to their solubility in salt melts is suggested. The method for estimation of solubility on the basis of thermodynamic calculations is developed. The calculated values agree satisfactorily with experimental data and results of prediction.     

Synthesis of nanosized group IV borides in ionic melts of anhydrous sodium tetraborate

The preparation of nanosized Group IV metal diborides by reacting powdery titanium, zirconium, and hafnium with fine-grained boron in Na₂B₄O₇ ionic melts in the temperature range 600–850°C has been studied. Nanosized titanium, zirconium, and hafnium diborides are formed at temperatures of at least 750°C.     

Synthesis of Lower Oxides of Transition Metals from Chloride Melts

Synthesis of transition metal oxides MO₂ (M^{I V} = Mo, W, or Nb) and V₆O_{1 3} in alkali chloride melts and their crystallographic characteristics are described. The advantages of the proposed technology are demonstrated. The thermodynamic parameters of the proposed reactions are calculated.     

Study on the preparation of Mg-Li-Ag Alloys by electrochemical deposition from LiCl-KCl-MgCl2-AgCl Melts

Electrochemical deposition of Mg, Li and Ag on molybdenum electrodes in LiCl-KCl-MgCl₂-AgCl melts at 943 K to form Mg-Li-Ag alloys was investigated. Cyclic voltammograms (CVs) showed that the potential of Li metal deposition, after the addition of MgCl₂ and AgCl, was more positive than that of Li metal deposition before the addition. ??, AgMg₄ + ??, and ?? + ?? + LiAg phases of Mg-Li-Ag alloys were obtained by galvanostatic electrolysis. The element Mg distributed homogeneously in the alloys while element Ag mainly located on the grain boundaries.