Determination of the eutectic solubility lines of the ternary system NaHCO3–Na2CO3–H2O

A crystallizer was built and a procedure developed to accurately measure the eutectic solubility lines where ice and salt coexist in equilibrium with the solution, for potential application of Eutectic Freeze Crystallization. The eutectic solubility lines of the ternary system NaHCO₃–Na₂CO₃–H₂O were determined experimentally and calculated with the extended UNIQUAC model. The extended UNIQUAC model describes the experimental data quite well. Anhydrous NaHCO₃ and Na₂CO₃·10H₂O were the only two types of crystals present in equilibrium with ice crystals in the ternary system. At the quadruple point NaHCO₃ and Na₂CO₃·10H₂O are in equilibrium with a solution of about 4.34 wt% of Na₂CO₃ and 4.77 wt% of NaHCO₃ at −3.32 °C. The anhydrous NaHCO₃ crystals were needle shaped with lengths between 5 and 10 μm, that were agglomerated into particles of about 100–300 μm, while the Na₂CO₃·10H₂O crystals were hexagonally shaped with sizes between 100 and 500 μm.     

Hydrogen-bond mediated and concentrate-dependent NaHCO3 crystal morphology in NaHCO3–Na2CO3 aqueous solution: Experiments and computer simulations

Adding Na₂CO₃ to the NaHCO3cooling crystallizer, using the common ion effect to promote crystallization and improve product morphology, is a new process recently proposed in the literature. However, the mechanism of the impact of Na₂CO₃ on the crystal morphology is still indeterminate. In this work, the crystallization of NaHCO₃ in water and Na₂CO₃ –NaHCO₃ aqueous solution was investigated by experiments and ...     

Eutectic crystallization in the UO2–Al2O3–HfO2 ceramic phase diagram

In the frame of the Generation IV Sodium Fast Reactor (SFR) safety studies, a core catcher with a sacrificial material could be placed at the bottom of the nuclear reactor. Its role is to dilute the (U, Pu)O₂ molten fuel in case of a hypothetical core meltdown accident. A Al₂O₃–HfO₂ ceramic is a candidate for the sacrificial material. To understand how the molten fuel would mix with this sacrificial material, the UO₂–Al₂O₃–HfO₂ system was investigated at CEA Cadarache PLINIUS corium platform. The eutectic position of the UO₂–Al₂O₃–HfO₂ was determined: the eutectic temperature is 1728±22 °C (2001±22 K) and the eutectic composition is 30 wt% UO₂–35 wt% Al₂O₃–35 wt% HfO₂. Then, the pseudo-binary UO₂–(50 wt% Al₂O₃–50 wt% HfO₂) phase diagram has been proposed.     

光照条件下Na2CO3/H2O2协同降解偶氮染料研究

本研究主要在光照条件下,利用Na₂CO₃/H₂O₂反应体系降解偶氮染料酸性橙8(AO 8),考察了光照条件对AO 8降解的影响,探究了不同活性基团对AO 8降解的贡献。结果表明,在光照条件下Na₂CO₃和H₂O₂可以产生协同效应,与单独加入Na₂CO₃或H₂O₂相比,能够有效促进偶氮染料AO 8的降解。在优化条件下,该体系中AO 8的降解率达到73.83%。同时研究分析了不同活性基团在AO 8降解过程中的作用,其中贡献率表现依次为CO₃·^->HO·>O₂·^->¹O₂。本研究结果可为偶氮染料废水的处理提供了一条新的途径。     

HCl滴定Na2CO3溶液pH计算

从解离平衡、水解效应、共轭酸碱的缓冲效应、质子条件式、物料、电荷守恒关系入手建立相应的数学表达式,选出科学、合理的数学关系式跟踪计算滴定过程溶液pH变化情况。利用典型数据化学计量点、滴定突跃的pH,优化滴定方案。     

铅纳米晶掺杂Na2O–B2O3–SiO2玻璃的三阶光学非线性

采用溶胶–凝胶法制备了铅纳米晶掺杂的Na2O–B2O3–SiO2玻璃。利用X射线衍射仪、透射电子显微镜、选区电子衍射结合X射线能谱对纳米晶的微结构、尺寸大小及组成进行分析。用紫外–可见–近红外分光光度法和Z-扫描技术分析了该玻璃的线性和非线性光学性质。结果表明:铅纳米晶在玻璃中呈球形,结晶性较好并表现出良好的分散性,属于立方晶系,颗粒尺寸大小基本分布在10~31nm范围内;在整个测试波长范围内没有明显的吸收峰,光学透过率高;Z-扫描测试结果表明,样品的非线性光学性能优良,其中三阶非线性性能参数为:γ=1.67×10–16m2/W,β=7.02×10–11m/W,χ(3)=2.61×10–17m2/W2。     

Effects of PbO and SrO contents on crystallization and dielectric properties of PbO–SrO–Na2O–Nb2O5–SiO2 glass–ceramics system

PbO–SrO–Na₂O–Nb₂O₅–SiO₂ glass–ceramics were prepared via roll-quenching followed by controlled crystallization from 700 °C to 900 °C. The effects of PbO and SrO contents on crystallization and dielectric properties were investigated. The results show that Pb₂Nb₂O₇, Sr₂Nb₂O₇ and their solid solutions crystallize at 700 °C, NaNbO₃ is the primary phase at 800 °C, Pb₂Nb₂O₇ disappears and PbNb₂O₆ forms at 900 °C. The dielectric properties of the glass–ceramics formed through controlled crystallization has a strong dependence on the phase compositions that were developed during heat treatment. The highest dielectric constants (∼600) are found in samples with 6.0 mol% SrO annealed at 900 °C for 3 h. The dielectric–temperature characteristics of the samples show stability over the range from −60 °C to 180 °C, except the sample without SrO heated at 900 °C.     

Efficient degradation of methylene blue dye by catalytic oxidation using the Na8Nb6O19·13H2O/H2O2 system

Na₈Nb₆O₁₉·13H₂O particles were synthesized by a simple hydrothermal method. The catalysts were characterized by X-ray diffraction (XRD), scanning electronic microscopy (SEM) and thermogravimetric and differential scanning (TG-DSC). The XRD and TG-DSC analyses indicated that Na₈Nb₆O₁₉·13H₂O was an intermediate hexaniobate during the preparation of NaNbO₃ powders. Methylene blue (MB) dye degradation using Na₈Nb₆O₁₉·13H₂O/H₂O₂, Nb₂O₅/H₂O₂ and NaNbO₃/H₂O₂ systems were investigated, respectively. Among the catalytic oxidation systems, Na₈Nb₆O₁₉· 13H₂O showed the highest activity for degradation of MB in the presence of H₂O₂. The results indicated that the dye degradation efficiency could be 93.5% at 30 °C after 60 min in the presence of the Na₈Nb₆O₁₉·13H₂O/H₂O₂ system. It was also found that the degradation of MB over the catalytic systems followed pseudo-first-order kinetics, and the degradation rate was 0.02376 min⁻¹ in the Na₈Nb₆O₁₉·13H₂O/H₂O₂ system, which was higher than that in the Nb₂O₅/H₂O₂ and NaNbO₃/H₂O₂ systems. A possible mechanism for MB catalytic oxidation degradation using the Na₈Nb₆O₁₉·13H₂O/H₂O₂ system was proposed.     

Na2CO3?10H2O-Na2HPO4.12H2O/SiO2复合定形相变材料的制备及应用研究

以十水合碳酸钠(SCD)、十二水合磷酸氢二钠(DHPD)为相变主体,制备了低过冷度,无相分离的共晶水合盐(EHS),以九水合硅酸钠为成核剂。进一步使用气相SiO₂为支撑材料,采用浸渍法制备了相变前后形状稳定的 EHS/SiO₂定形相变储能材料(SSPCM)。所得SSPCM的相变温度为 24.08 ℃,焓值为 146.6 J/g,过冷度为 0.55 ℃,热导率为 0.5454 W/m?K。同保温泡沫相比,其可将模拟房内部中心温度的升温时间延长 3.26 倍,降温时间延长 1.39 倍,具有优异的“热缓冲”性能,在建筑节能领域具有广阔的应用前景。     

Effect of different nucleation catalysts on the crystallization of Li2O–ZnO–MgO–Al2O3–SiO2 glasses

Based on local raw materials, a range of LiZnMg aluminosilicate glasses were prepared to investigate the influence of TiO₂, Cr₂O_3, and ZrO₂ on the crystallization behaviour and thermal expansion characteristics. Differential thermal analysis showed that the crystallization propensity increases in the order TiO₂ > Cr₂O₃ > ZrO₂. Virgilite, β-spodumene ss, gahnite, enstatite and cristobalite were formed in the prepared glass-ceramics. The microstructure of glass-ceramic samples showed growths of rounded and subrounded grains in the base sample, whereas, somewhat rod-like and accumulated growths appeared in samples containing ZrO₂. However, a rather homogeneous texture of accumulated growths was developed in glass-ceramics containing TiO₂ and Cr₂O₃. The coefficient of thermal expansion of parent glasses was sensitive to the type of nucleating agent added (Cr₂O₃ > TiO₂ > ZrO₂) varying from 24.8 × 10⁻⁷ to 65.1 × 10⁻⁷ °C⁻¹ being almost unchanged with the heat-treatment. The microhardness values of glass-ceramic samples were in the 763–779 kg/mm² range.     

Synthesis,characterization and bioactivity of bioglasses in the Na2O–CaO–P2O5–SiO2 system prepared via sol gel processing

Different kinds of bioactive materials are used as bone substitutes. In particular, bioglasses containing Si, Ca, Na and P, bind to host tissues with a stable chemical bond. The phenomenon of bioactivity is associated with the formation of a crystallized hydroxycarbonated apatite (HCA) layer on the bioglass surface, when soaked in a simulated physiological fluid. This layer is similar to the mineral phase of bone.     

Crystallization behavior and properties of K2O–CaO–Al2O3–SiO2 glass-ceramics

In order to obtain high-strength anorthite glass-ceramics, K₂O–CaO–Al₂O₃–SiO₂ quaternary glass and relevant glass-ceramics were prepared and investigated. The results show that anorthite along with kalsilite or leucite was precipitated from the parent glass. Kalsilite crystals were formed firstly and then converted into leucite through reacting with SiO₂ in the glass phase. The morphology of the crystals was dependent on the heat-treatment temperature. Column crystals were transformed into fine granular grains when the sintering temperature changed from 900 °C to 1100 °C. The activation energy (E_α) and avrami constant (n) were also calculated as 463.81 KJ/mol and 3.74 respectively, indicating that bulk nucleation and three-dimensional crystal growth were the dominating mechanisms in the temperature range 1000–1100 °C. The maximum value of the flexural strength for the glass-ceramics containing leucite was 248 MPa and the coefficient of thermal expansion (CTE) was in the range 5.69~11.94×10⁻⁶ K⁻¹. The leucite is the main reason for the high CTEs and high flexural strength of glass-ceramics.     

钙添加剂对Na2CO3催化高铝煤焦水蒸气气化反应性的影响

以孙家壕高铝煤为实验煤样,将煤样在800℃制成煤焦,采用热重分析仪(TGA)研究了钙添加剂对孙家壕煤焦Na₂CO₃催化水蒸气气化反应性的影响。结果表明：Ca(OH)₂对孙家壕煤焦水蒸气气化具有催化作用,在对孙家壕煤焦进行800℃Ca(OH)₂催化水蒸气气化时,Ca(OH)₂的负载量在15%(质量分数,下同)时达到饱和;通过比较Na₂CO₃和Ca(OH)₂对孙家壕煤焦800℃水蒸气气化的催化活性,发现Na₂CO₃的催化气化活性比Ca(OH)₂的催化气化活性大,负载5%Na₂CO₃和10%Ca(OH)₂的孙家壕焦的800℃水蒸气气化反应性相等;添加10%Ca(OH)₂添加剂可以使负载10%Na₂CO₃的孙家壕煤焦在700℃...     

Z型g-C3N4/WO3·H2O的制备及其光催化CO2还原性能

以石墨相氮化碳(g-C₃N₄)和二水合钨酸钠为原料,采用水热合成法制备了复合材料g-C₃N₄/WO₃·H₂O(CNW-1),通过XRD、XPS、SEM、TEM对其进行了表征,探究了298 K、0.1 MPa条件下其对CO₂的可见光催化还原性能,并提出了可能的反应机理。通过调控WO₃结晶水含量可以实现CO和CH₄的产率调节,在反应10 h后,CNW-1具有最高的CH₄产率(0.33μmol/g),而g-C₃N₄/WO₃(CNW)具有最高的CO产率(0.67μmol/g)。该研究为CO₂选择性还原为C1化合物提供了一种有效策略,同时突出了以g-C₃N₄作为半导体构建Z型光催化体系在催化领域的应用潜力。     

The influence of In2O3 on electrical characteristics of iron mixed Li2O–PbO–B2O3–SiO2–Bi2O3 multi-component glass system

Glasses of the composition 19Li₂O–20PbO–20B₂O₃–30SiO₂–(10−x) Bi₂O₃–1Fe₂O₃: xIn₂O₃ with six values of x (0 to 5.0) were synthesized. Dielectric properties viz., dielectric constant, ε′(ω), loss, tan δ, ac conductivity, σ_ac, electric modulus, M(ω) over wide ranges of frequency and temperature and also dielectric break down strength have been studied as a function of In₂O₃ concentration. The temperature dispersion of real part of dielectric constant, ε′(ω) has been analyzed using space charge polarization model. The dielectric loss (and also the electric moduli) variation with frequency and temperature exhibited relaxation effects and these effects were attributed to the divalent iron ion complexes. The ac conductivity exhibited maximal effect, whereas the activation energy for the conductivity demonstrated minimal magnitude at about 1.0 mol% of In₂O₃. The conductivity mechanism is understood due to the polaronic transfer between Fe²⁺ and Fe³⁺ ions. The low temperature ac conductivity mechanism is explained following the quantum mechanical tunneling model. Spectroscopic studies viz., optical absorption and ESR spectra have revealed that the redox ratio (Fe²⁺/Fe³⁺) is maximal when the concentration of In₂O₃ is ~1.0 mol%. The higher values of dielectric parameters observed at 1.0 mol% of In₂O₃ are attributed to the presence of iron ions largely in divalent state and act as modifiers. The analysis of these results together with spectroscopic studies has indicated that when In₂O₃ is present in the glass matrix in higher concentrations (more than 1.0 mol%) iron ions predominantly exist in trivalent state, occupy substitutional positions and make the glass more rigid. Such enhanced rigidity of the network is causing the decrease of dielectric parameters with the concentration of In₂O₃. Finally it is concluded that In₂O₃ mostly participate in the glass network in octahedral positions and make act as reducing agent (for iron ions) in the studied glass matrix when its concentration is ≤1.0 mol%.     

铁精粉还原炉用Si3N4（Sialon）/SiC材料在H2O—H2—N2气氛中热力学计算分析

根据热力学原理对Si—C—N—H—O五元系统进行了平衡状态下的相稳定性计算,绘制了在1 073 K和1 223 K下的SiC、Si₃N₄、Si₂N₂O和SiO₂4个稳定相的稳定性与N₂分压和H₂O分压的关系图,即优势区域图,分析了其凝聚相的稳定区域。同时结合SEM显微结构分析氢气还原炉中Si₃N₄/SiC和Sialon/SiC制品抗H₂O—H₂—N₂气氛的侵蚀性能。     

抗SO2和H2O中毒的低温NH3-SCR脱硝催化剂研究进展

低温NH3-SCR技术能在较低温度下实现NOx高效转化为N2,具有较好的经济效益,应用前景广阔。若反应气体中含有H2O和SO2时,会导致低温NH3-SCR催化剂中毒失活,限制了低温NH3-SCR技术的应用。本文对低温NH3-SCR催化剂H2O和SO2中毒机理进行了阐述,重点关注以V、Mn、Ce、Fe 4种过渡金属和以贵金属为活性组分的低温NH3-SCR催化剂的研究进展,分析了元素掺杂、载体性质、制备方法和反应机理等方面与催化剂抗SO2和H2O中毒性能的关系。针对当前存在的问题,指出了今后的研究重点是深入分析催化剂中毒时硫酸盐类的生成过程,并提出相应的控制对策。     

The reaction between the magnesia–chrome brick and the molten slag of MgO–Al2O3–SiO2–CaO–FetO and the resulting microstructure

The reaction and microstructure at the interface of MgO–Cr₂O₃ brick and the molten slag of MgO–Al₂O₃–SiO₂–CaO–Fe_tO after static slag corrosion at 1823–1923 K for various times and the resulting microstructure were investigated and characterized. After the static slag corrosion at 1923 K for 4 h, the XRD results show the major phases of periclase MgO, MgCr₂O₄ spinel, and CaMgSiO₄ as the minor phase. MgCr₂O₄ phase causes MgO to form a discontinuous phase in MgO–Cr₂O₄ brick. After static slag corrosion at 1923 K for 4 h, SEM micrographs show that brick interior cracks, MgO and dissolved MgO. MgO dissolved due to the molten plag penetrated into the brick interior and reaction with it, leading to a localized dissolution of brick slag. TEM micrographs and ED patterns demonstrate that the minor phase of (Mg, Fe)(Al, Cr)₂O₄ precipitates in the MgCr₂O₄ matrix.     

Porous SiO2–TiO2–ZrO2 Obtained from Polymeric Systems Prepared by the Sol–Gel Process

An experimental strategy was developed to obtain Si–Ti–Zr transparent sols via the sol-gel process. The chelating agents isoeugenol (2-methoxy-4-propenylphenol, isoH), salicylaldehyde (2-hydroxybenzaldehyde, salH), and itaconic anhydride (2-methylenesuccinic anhydride, anhH) were employed separately to stabilize monomeric Ti and Zr precursors, in order to control their chemical reactivity, avoiding precipitation. In all cases a prehydrolyzed tetraethyl orthosilicate (TEOS) sol was the Si source. The sols were polymerized at room temperature (293 K) to obtain gels and these were dried and calcined at 873 K in air. The radial distribution functions (RDF) of the gels were obtained at room temperature. The solids were studied by scanning electron microscopy (SEM). The porosity and surface area of solids were determined by N₂ adsorption. The surface area results obtained range between 83–198 m²/g. The average pore diameters are 1.44–1.61 nm.