LaCl_3－SrCl_2－MgCl_2三元体系相图

本文借助于ＤＴＡ和Ｘ射线结构分析测定了ＬａＣｌ_３－ＳｒＣｌ_２－ＭｇＣｌ_２三元体系相图，发现它属简单低共熔型，体系内有对应于ＬａＣｌ_３、ＳｒＣｌ_２和ＭｇＣｌ_２的３个液相面、３条２次结晶线和１个三元低共熔点Ｅ（１５．０ｗｔ％ＬａＣｌ_３，４９．５ｗｔ％ＳｒＣｌ_２，３５．５ｗｔ％ＭｇＣｌ_２；５４５℃），并且在固相下有一个不稳定的化合物生成，在约５００℃时分解。     

ErCl_3－CaCl_2－LiCl三元体系相图的研究

利用ＤＴＡ研究了ＥｒＣｌ_３ＣａＣｌ_２ＬｉＣｌ三元体系相图。发现该相图有对应于ＥｒＣｌ_３、ＣａＣｌ_２、ＬｉＣｌ和Ｌｉ_３ＥｒＣｌ_６的４个液相面，５条二次结晶线，一个三元低共熔点Ｅ（５８．５％ＥｒＣｌ_３，２３．７％ＣａＣｌ_２，１７．８％ＬｉＣｌ，３９７℃），一个三元转熔点Ｐ（５２．５％ＥｒＣｌ_３，２７．２％ＣａＣｌ_２，２０．３％ＬｉＣｌ，４２８℃）。相应的４相平衡反应为：Ｌ＝ＥｒＣｌ_３＋Ｌｉ_３ＥｒＣｌ_６＋ＣａＣｌ_２；Ｌ＋ＬｉＣｌ＝Ｌｉ_３ＥｒＣｌ_６＋ＣａＣｌ_２．     

YbCl_3－CaCl_2－MgCl_2三元体系液相限的研究

借助于ＤＴＡ测定了ＹｂＣｌ３－ＣａＣｌ２－ＭｇＣｌ２三元体系液相限．发现本体系有对应于ＹｂＣｌ３、ＣａＣｌ２、ＭｇＣｌ２和不稳定化合物Ｘ的四个液相面，五条二次结晶线，一个三元低共熔点Ｅ（３８．０ｗｔ％ＹｂＣｌ３，３１．０ｗｔ％ＣａＣｌ２，３１．０ｗｔ％ＭｇＣｌ２；５５６℃）和三元转熔点Ｐ’（４５．５ｗｔ％ＹｂＣｌ３，２８．０ｗｔ％ＣａＣｌ２，２６．５ｗｔ％ＭｇＣｌ２；６００℃）．     

Subsolidus Phase Relations in the TiO_2-NiO-WO_3 System

The subsolidus phase relationships of the system TiO2-NiO-WO3 were investigated, aiming at exploring new potential visible-light active photocatalysis systems. After the solid-state chemistry reaction in air between 1000 and 1150 ℃, X-ray diffraction(XRD) data showed that two binary compounds and three ternary-phase regions were contained in this ternary system. No new ternary compound was discovered under our experiment conditions. None of these phases in this system revealed a remarkable homogeneity range.     

Thermochemische Untersuchungen zum System Bi/Se/O. I. Das Phasendreieck Bi2Se3/Bi2O2Se/Se

Thermochemical Investigation on the System Bi/Se/O. I The Phase Triangle Bi₂Se₃/Bi₂O₂Se/Se By total pressure measurements of compositions in the subsystem Bi₂Se₃/Bi₂O₂Se/Se was shown, that in thermodynamic equilibrium the three phases Bi₂Se₃/Bi₂O₂Se/Se coexist. The barogram of the triangle reduces to the barogram of the line Bi₂Se₃? Se, the compound Bi₂O₂Se is not from influence of the total pressure in the investigated temperature range.     

Phase equilibria in the Ag4SSe–As2Se3 system

The phase diagram of the system Ag₄SSe–As₂Se₃ is studied by means of X-ray diffraction, differential thermal analyses and measurements of the microhardness and the density of the materials. The unit-cell parameters of the intermediate phases 3Ag₄SSe·As₂Se₃ (phase A) and Ag₄SSe·2As₂Se₃ (phase B) are determined as follows for phase A: a=4.495 Å, b=3.990 Å, c=4.042 Å, α=89.05°, β=108.98°, γ=92.93°; for phase B: a=4.463 Å, b=4.136 Å, c=3.752 Å, α=118.60°, β=104.46°, γ=83.14°. The phase 3Ag₄SSe·As₂Se₃ and Ag₄SSe·2As₂Se₃ have a polymorphic transition α?β consequently at 105 and 120°C. The phase A melts incongruently at 390°C and phase B congruently at the same temperature.     

PrCl3-BaCl2-NaCl三元体系相图的研究

众所周知,希土氯化物熔盐体系相图对于熔盐电解制备希土金属具有重要意义。PrCl_3-NaCl与BaCl_2-NaCl体系均属简单低共熔体系;PrCl_3-BaCl_2体系属于有一化合物Ba_3PrCl_8分解的相图类型。而PrCl_3-BaCl_2-NaCl三元体系尚未见文献报道。本文在重新考察各相关二元体系相图的基础上测定了本体系相图,共测定五个多温截面,其分布见图1。     

Al-Zn-Sn Phase Diagram X-ray diffraction study at various temperatures

Further studies of the ternary phase diagram Al-Zn-Sn have been carried out by X-ray diffraction at various temperatures and by thermodilatometry in order to confirm our earlier experimental results which have been refuted by some recent work based on thermodynamic optimization. These new results, in particular the change with temperature of the crystallized fraction for Al-Zn-Sn mixtures containing up to 31.5 mass% of tin, confirm our previous results on the existence of a significant retrograde miscibility of tin in a solid solution α′ss (in the temperature range 286 to 335°C) which protrudes into the ternary system starting from the Al-Zn binary up to a tin concentration of about 50 mass%. This disagreement between theory and experiment highlights the difficulties of a thermodynamic optimization approach based on solid state solubilities in the binary systems and on ternary liquidus data which disregards the ternary interaction parameters in the solid state. Besides, this experimental study highlights the difficulties in understanding the phenomena which depend on phase stabilities. This revised version was published online in July 2006 with corrections to the Cover Date.     

Thermodynamic study of the SOLID-LIQUID equilibria in the MIPO3-Cu(PO3)2 systems

Thermodynamic exploration of solid-liquid equilibria of the M^IPO₃-Cu(PO₃)₂ (with MI=Li, Na, K, Rb, Cs, Ag, Tl) systems is carried out with a semi-empirical equation of the liquidus curves. The enthalpies of fusion of pure polyphosphates and some intermediate compounds were determined from DTA curves. The temperature, enthalpy and entropy of fusion are calculated for each solid phase with the exception of silver polyphosphate and the intermediate compound Cs₄Cu(PO₃)₆ which have very limited crystallization fields. The calculated values of the melting enthalpies are approximately equal to the measured ones. The melting enthalpy of Cu(PO₃)₂ calculated from different binary systems shows a wide variation in the obtained values, 35-54 kJ mol^-1. The experimental value is 33.65 kJ mol^-1. The calculated temperatures and compositions in most binary systems are in good agreement with experimental determinations. This revised version was published online in July 2006 with corrections to the Cover Date.     

In-situ Synthesis of the Thinnest In2Se3/In2S3/In2Se3 Sandwich-Like Heterojunction for Photoelectrocatalytic Water Splitting

The efficient utilization of solar energy for photoelectrocatalytic (PEC) water splitting is a feasible solution for developing clean energy and alleviating environmental issues. However, as the core of PEC technology, the existing photoanode catalysts have disadvantages such as poor photoelectrocatalytic conversion efficiency, low conductivity of photogenerated carriers, and instability. Here, we report the ultrathin two-dimensional sandwich-like (SW) heterojunction of In₂Se₃/In₂S₃/In₂Se₃ (SW In₂S₃@In₂Se₃) for the first time for PEC water splitting. Our findings identify the efficient separation of electrons and holes by constructing SW In₂S₃@In₂Se₃ heterojunction. The in situ synthesis of ultrathin nanosheet arrays by using surface substitution of Se atom to epitaxially grow cell In₂Se₃ maximizes the contact area of heterogeneous interface and accelerates the transmission of charge carrier. Benefitting from the unique structure and composition characteristic, SW In₂S₃@In₂Se₃ displays excellent performance in PEC water splitting. The photocurrent density of SW In₂S₃@In₂Se₃ reaches 8.43 mA cm⁻² at 1.23 V_RHE. Compared with In₂S₃, the SW In₂S₃@In₂Se₃ photoanode has nearly 12 times higher PEC performance, which represents the best performance among the In₂S₃-based photoanode heterojunction reported so far. The evolution rate of O₂ reaches 78.8 μmol cm⁻² h⁻¹, and the photocurrent has no apparent variety within 24 h.     

Systeme ternaire: H2O-Zn(NO3)2-NH4NO3

The solid-liquid equilibria of the ternary system H₂O-Zn(NO₃)₂-NH₄NO₃ were studied by using a synthetic method based on conductivity measurements. Two isotherms were established at -25 and -20°C, and the stable solid phases which appear are: Ice, NH₄NO₃ , Zn(NO₃)₂·6H₂O and Zn(NO₃)₂·8H₂O Neither double salts, nor mixed crystals are observed at these temperatures and composition range. This revised version was published online in August 2006 with corrections to the Cover Date.     

YbCl3-MCln体系相图的研究(M=Li、Mg、Ca、Pb; n=1,2)

借助于DTA与X射线衍射法研究了YbCl_3-MCl_n(M=Li、Mg、Ca、Pb; n=1或2)二元体系相图．发现YbCl_3-LiCl体系相图属固液异组成型，有化合物Li_3YbCl_6生成，它在481 ℃有一相转变. 其无变点分别为x_(YbCl_s)＝0.410；526 ℃和x_(YbCl_3)=0.340，547 ℃；YbCl_3-MgCl_2属类转熔型相图，在富YbCl_3相区666 ℃有一尚不知其性质的热效应，为x_(YbCl_3)＝0.380，628 ℃；YbCl_3-CaCl_2和YbCl_3-PbCl_2体系皆属简单低共熔型相图，其低共溶点分别为x_(YbCl_3)＝0.530, 615 ℃和x_(YbCl_3)＝0.340, 415 ℃. 后者在固相下有一不稳定化合物PbYbCl_5生成，在392 ℃分解，同时探讨了相图的某些规律．     

Subsolidus Phase Relations in the ZnO-BaO-V2O5 System

The subsolidus phase relations of the ZnO-BaO-V2O5 ternary systems were investigated by means of X-ray diffraction analysis. There are three ternary compounds, nine binary compounds and sixteen 3-phase regions found in this system. The crystal structure of the ternary compound Ba2ZnV2O8 was refined by Rietveld profile fitting method and the powder diffraction pattern is given. A new ternary compound Ba3.4Zn0.8V4O14.2 has been found by the powder diffraction pattern.     

Phase diagram investigation and thermodynamic study of Os-B system

The constitution of the Os-B system was investigated in this work. The phase regions were determined by metallographic investigations. The existence of the following borides was confirmed: OsB_1.1 (hex.), Os₂B₃ (hex.) and OsB₂ (orthorh.), while the new high temperature Os₂B₃ compound with a not yet identified structure was observed. OsB_1.1 melts congruently at 1820±15°C and OsB₂ at 1870±15°C, while the solid solubility of B in Os was found to be less than 0.5 at%B. Considering thermodynamic study of this system, the activities and activity coefficients for osmium and boron were determined in temperature interval 3300-3500 K, based on the known liquidus and solidus lines from phase diagram, according to calculation procedure given by Rao and Belton. This revised version was published online in July 2006 with corrections to the Cover Date.     

三元体系Cu(NO3)2-EBU-H2O 30℃时等温溶度及其新相研究

The isothermal solubility of the ternary system Cu(NO₃)₂-EBU-H₂O at 30℃ has been studied for the first time and the solubility diagram and refractive indices diagram have been given. New phase Cu(NO₃)₂·2EBU has been found in this system， which dissolves incongruently in water .The phase has been characterized by element anal-ysis， IR spectra and X-ray diffraction powder analysis.     

Mg-Sm体系相图及其Sm2Mg13金属间化合物的研究

本文借助于化学分析、X射线衍射、差热分析、金相和电子探针研究了Mg-Sm二元相图。发现并测定了金属间化合物,Sm_2Mg_(13)它属正交晶系,晶胞参数a=13.855(?)、b=9.357、c=7.457(?)。z=2,v=966.7(?)~3,dx=2.118克/厘米~3(Dobs=2.127克/厘米~3)。并得到一套衍射图谱。同时发现Mg-Sm二元体系有二个共晶反应,一个类共晶反应,三个化合物分解反应和三个多晶转变。     

Physicochemical study on selenites of the three-component system Yb2O3-SeO2-H2O

The solubility isotherm of the three-component system Yb₂O₃-SeO₂-H₂O at 100°C was studied. There are two fields of crystallization in the solubility diagram at this temperature - a small one of Yb₂(SeO₃)₃·4H₂O and a large one of YbH(SeO₃)₂·2H₂O. These compounds were identified by the Schreinemakers' method, and by chemical and X-ray analyses as well. Simultaneous TG and DTA curves of the two compounds obtained were made and the mechanism of the thermal decomposition was described. This revised version was published online in July 2006 with corrections to the Cover Date.     

Phase equilibria in the system NiO-V2O5-Fe2O3 in subsolidus area

Reactivity of FeVO₄ towards Ni₂V₂O₇ and Ni₃V₂O₈ in the solid state was investigated. On the base of XRD and DTA results, phase diagrams in subsolidus area of the FeVO₄-Ni₂V₂O₇ and FeVO₄-Ni₃V₂O₈ intersections of the ternary system NiO-V₂O₅-Fe₂O₃ have been worked out and the phase diagram of this ternary system in subsolidus area in the whole component concentration range has been verified. This revised version was published online in July 2006 with corrections to the Cover Date.