利用δ53Cr定量评价Cr(VI)还原程度的实验研究

地下水污染的原位修复是当今国际上净化地下水最具发展前景的新技术,但对铬污染地下水原位修复尚未有科学有效的评价方法。定量评价地下水中Cr(Ⅵ)的被还原程度成为保护与修复铬污染地下水的关键问题。通过室内Cr(Ⅵ)的还原实验,分析Cr(Ⅵ)在还原过程中铬稳定同位素变化规律,研究其分馏机理,探索利用铬同位素定量评价地下水中Cr(Ⅵ)还原程度的可行性。研究结果表明:Cr(Ⅵ)在被还原成Cr(Ⅲ)过程中,发生明显的同位素分馏,即反应物中53Cr逐渐富集,同时生成物中52Cr逐渐富集;分馏过程可用瑞利分馏模型描述,分馏系数α为常数0.99842。表明δ53Cr能够定量评价水体中Cr(Ⅵ)的还原程度,为评价地下水铬污染修复提供了新途径。     

溶胶凝胶法制备（Eu^2＋，Dy^3＋）SrAl2O4

采用无机盐溶胶-凝胶法制备了颗粒均匀的形态为针状的(Eu2+,Dy3+)SrAl2O4纳米粉体.通过TG-DTA分析和X射线衍射和扫描电镜分析方法,对样品进行了微观结构和表面形态的表征.研究了纳米(Eu2+,Dy3+)SrAl2O4粉体在不同烧结温度下固相反应过程和成相规律.实验结果表明,当样品的烧结温度为500 ℃时是单一的Sr(NO3)2晶相;750 ℃左右生成了Sr3Al2O6,并伴有少量SrAl2O4晶体;1 100 ℃是生成了结晶度良好的针状纳米(Eu2+,Dy3+)SrAl2O4粉体.通过计算,样品粉体晶粒平均为80～100 nm.该晶体粒度随烧结温度升高而逐渐变大.     

Production of high titania slag by Electro-Slag Crucible Melting (ESCM) process

In this research, ilmenite concentrate of Iran region successfully was smelted by Electro-Slag Crucible Melting (ESCM) process to produce TiO₂-rich slag as primary product and pig iron as by-product. Moreover, effects of reductant (carbon) amount and smelting time on TiO₂ and FeO content of slag and iron recovery were studied. It is found that addition of carbon excess to stoichiometric amount decreases the iron recovery and TiO₂ content in slag. If the smelting time keeps between 0 to 17 min, the TiO₂ content and iron recovery will be increased, whereas smelting time in excess of 17 min will cause products decline significantly. At optimum conditions, TiO₂ content in slag and the iron recovery are 70 wt.% and 84%, respectively. Kinetic studies proved that the reduction of equivalent FeO was first-order reaction. The studies made by X-ray diffraction analysis showed that formation of the titanium sub-oxides (Ti₃O₅ and Ti₂O₃) causes the decrease in iron recovery and TiO₂ content.     

Diffusion-controlled corona reaction and overstepping of equilibrium in a garnet granulite, Yenisey Ridge, Siberia

Diffusion modelling is applied to layered garnet–pyroxene–quartz coronas, formed by a pressure-induced reaction between plagioclase and primary pyroxene in a metabasic granulite. The reconstructed reaction involves some change in composition of reactant minerals. The distribution of minerals between layers is satisfactorily explained by diffusion-controlled reaction with local equilibrium, in which the diffusion coefficient for Al was smaller than those for Fe, Mg and Ca by a factor of approximately four. Diffusion of Mg towards plagioclase implies a chemical-potential gradient for MgO component in a direction opposite to the changing Mg content of garnet; this is explained by the influence of Al₂O₃ on the chemical potential of the pyrope end-member. Grain-boundary diffusion is suggested to have operated, possibly with composition gradients different from those in the bulk minerals. Chemical-potential differences across the corona are estimated from the variation in garnet composition, enabling affinity (the free energy change driving the reaction) to be estimated as 6.9±1.8  kJ per 24-oxygen mole of garnet produced. This implies that the pressure for equilibrium among the minerals was overstepped by 1.4±0.4  kbar. The probable P–T conditions of reaction were in the range 650–790  °C, 8–10  kbar. Assuming a timescale of reaction between 10⁶ and 10⁸ years, estimated diffusion coefficients for Fe, Mg and Ca are in the range 9×10⁻²³ to 5×10⁻²⁰ m² s⁻¹. These are consistent with experimental values in the literature for solid-state diffusion, including grain-boundary diffusion.     

纳米铁还原高浓度硝基苯的实验

采用液相还原法制备纳米铁粒子,粒径约为50 nm,主要成分为ɑ-Fe。实验研究了纳米铁还原高浓度硝基苯的效果及反应动力学。结果表明:自制的纳米铁具有很高的活性,短时间内能将高浓度硝基苯彻底还原,效果远优于普通铁粉。当摩尔比满足n纳米铁∶n硝基苯=4∶1时,纳米铁还原硝基苯属于一级反应动力学,反应速率常数和半衰期分别为0.159 3 h-1和4.351 2 h。整个实验过程中,ρ(DO)在0.5 mg/L以下,pH值约为9.0,体系呈弱碱性的厌氧环境,有利于厌氧微生物的生长。纳米铁反应后的产物为Fe6(OH)12CO3和MgFe3O4,且以Fe6(OH)12CO3为主。纳米铁反应后较以前比粒径变化不大,分散性较好,但表面被严重腐蚀。     

硅灰石与盐酸快速反应规律及应用研究

在反应体系pH≤1．5时，硅灰石与盐酸快速反应，经40－100min反应后，体系分为固液两相，固相为水合 二氧化硅沉淀及少量酸不溶性杂质矿物，液相为以溶胶形式存在的二氧化硅和大量CaCl2；当反应pH值在0．3－0．6时，液相中以硅溶胶形式存在的二氧化硅量最大，占总量46％以上。快速反应中仍存在少量具有慢速反应特征的柱状颗粒，该颗粒中心CaSiO3很难反应完全。快速反应产物经表面积较大，若在酸反应前添加有机助剂聚乙二醇（PEG）,反应pH值在0．3－0．6。反应时间40－100min，反应后用KOH溶液中和到pH＝4，可制备高比表面积多孔SiO2，比表面积＞430m^2／g，孔径1－2nm。     

花岗质岩浆能够结晶分离和演化吗？

学术界普遍认为花岗岩能够分离和演化,实际上这是不对的,理由是没有野外和镜下观察的证据。岩浆演化的理论是对的,该理论是从研究玄武质岩浆得来的,只适合玄武质岩浆而不适合花岗质岩浆。本文指出,鲍温反应原理不适用于花岗质岩浆。文中呼吁要重视区分幔源岩浆和壳源岩浆,幔源岩浆可以演化,但是,幔源岩浆不可能演化为壳源岩浆,壳源岩浆不可能演化。     

Magnetic hysteresis and refrigeration capacity of Ni—Mn—Ga alloys near Martensitic transformation

This paper studies the magnetic hysteresis and refrigeration capacity of Ni--Mn--Ga alloys in detail during heating and cooling isothermal magnetisation processes. The Ni--Mn--Ga alloys show larger magnetic hysteresis when they transform from austenite to martensite, but smaller magnetic hysteresis when they transform from martensite to austenite. This behaviour is independent of either the pure Ni--Mn--Ga alloys or the alloys doped with other elements. Because of the existence of the magnetic hysteresis, the relation between the magnetic entropy change and refrigeration capacity is not simply linear. For practical consideration, magnetocaloric effect of Ni--Mn--Ga alloys should be investigated both on cooling and heating processes.     

补偿式量热计在热化学中的应用

简要介绍了 Ｄ Ｄ Ｃ Ⅱ型补偿式数字精密量热系统及原理和对系统的标定。报道了用该量热计对无限稀的酸和碱反应过程的微反应热的自动测定,为热化学反应过程中微热效应的测定和该量热计的拓展提供了一条新途径。     

慢速扩张脊下的复杂熔-岩相互作用：来自大西洋北纬14°97′区段洋中脊含铬铁矿纯橄岩的记录

在大西洋洋中脊北纬14°97′附近贫岩浆型慢速扩张脊区段的洋底岩石调查中,拖网取样及洋底钻探均发现蛇纹石化地幔岩石中有脉状纯橄岩。纯橄岩中的铬铁矿粒度以毫米级为主,个别颗粒直径接近厘米级别,成分上显示中等程度的铬值与镁值(Cr^#=52.2～56.1;Mg^#=44.6～51.5)较高的TiO₂含量(0.60%～0.91%)。铬铁矿内部包裹体中大量出现韭闪石+金云母组合,并发现自形磷灰石包裹体。这些特征与“俯冲带型铬铁矿”的成分特征及矿物包裹体组合非常类似。本文的样品观察说明在洋中脊下方的熔体通道内,高度演化的熔体可以形成小体积的富水岩浆并参与铬铁矿的形成。拖网调查与钻探研究证实,研究区的纯橄岩、异剥橄榄岩、富橄榄石橄长岩、辉石岩、辉长岩及橄榄辉长岩等均以脉体形式产于难熔的大洋岩石圈橄榄岩质地幔中。这些脉状岩石共同记录了洋中脊玄武质熔体向上迁移过程中与围岩方辉橄榄岩间的熔-岩反应,属于“交代橄榄岩”的范畴,揭示了慢速扩张洋脊之下熔体迁移诱发的复杂熔-岩相互作用。