CO还原CaO—SiO2—FetO三元渣系的研究

在1723K进行了CO还原CaO—SiO_2-Fe_(t)O三元渣系的研究根据CO_2红外分析仪测定的出口气体中的CO_2浓度变化,计算了炉渣的表观还原速度常数K_(a)结果表明,K_(a)随炉渣中Fe_1O量增加呈抛物线变化;当炉渣碱度R<1.0,Fe_(t)O为50％和R为1.5,Fe_(t)O为70％时,K_(a)分别出现最小值用炉渣规则溶液模型可计算1723K时的CaO-SiO_2-Fe_tO三元渣系的Fe_1O活度值a_(Fe_1O)。     

MgO-B2O3二元系熔渣质量作用浓度计算模型

依据化学中广泛应用的同系线性规律,拟合钙、镁复合化合物标准反应吉布斯自由能之间的线性关系式,然后由3CaO·B2O3和2CaO·B2O3的标准反应吉布斯自由能求得3MgO·B2O3和2MgO·B2O3的标准反应吉布斯自由能,进而基于炉渣结构的共存理论和相图,推导MgO-B2O3二元渣系的热力学计算模型.结果表明:1 460℃时,在浓度为0.45＜x(MgO)＜0.80的范围内,理论计算的MgO-B2O3渣系的作用浓度N(B2O3)的变化规律与实测活度α(B2O3)是相同的,且拟合较好.     

PbO-CaO-SiO_2-FeO-Fe_2O_3渣系氧化铅活度热力学模型（英文）

基于炉渣结构分子和离子共存理论,建立1273~1733 K下的PbO-CaO-SiO2-FeO-Fe2O3渣系氧化铅活度热力学模型,计算PbO活度并绘制等活度曲线,考察炉渣碱度Q、氧化铁比率R和温度T对活度NPbO和活度系数γPbO的影响。结果表明,活度系数γPbO的模型计算值与文献测定值吻合程度高,说明该模型能较好地反映该渣系结构本质;NPbO呈拉乌尔正偏差,且随渣中PbO含量的升高而增大,但受温度的影响不明显;γPbO随Q的升高而增大;对于Q0.3的碱性渣,γPbO随R的升高而出现极大值。该研究结果可用于现代炼铅工艺的热力学研究和操作优化。     

温度和气氛对 CaO-SiO2-Al2O3-MgO-FetO 渣系FetO活度的影响

采用Mo[Mo＋MoO｜ZrO2（MgO）｜Fe＋（Fe1O）＋Ag｜Fe固体电解质电池测定不同温度和气氛条件下定组成CaO-SiO2-Al2O3-MgO-FetO五元渣系的Fe。0活度。结果表明,当Ar作为保护气氛时,温度由1673K升高到1785K,炉渣的Fep活度变化不明显。当气氛中CO,C02和Ar组成固定时,炉渣的Fet0活度随温度的升高而增大。温度为1673K时,炉渣的Fet0活度随着气氛中C02／CO的增加而增大。温度和气氛对渣系FetO活度的影响均通过体系的02分压实现。     

高阶亚正规溶液模型及其在MnO-SiO_2-Al_2O_3-CaO炉渣中组元活度的计算

本文介绍了用于计算四元均相系中组元活度的SELF-SReM4高阶亚正规溶液模型.模型由一组参数表示，根据精选的“边界条件”.可由二元系、三元系、四元系逐渐展开拟合出该组参数.用该模型计算了Mno－SiO2－al2O3－CaO四元系，包括四个三元子系中各组元的活度.SiO2－al2O3－CaO三元系的SiO2活度计算值与实验值和其它计算结果较一致；MnO-SiO2－CaO三元系计算结果与渣-金属平衡试验结果较一致     

含Ce2O3渣系作用浓度的计算模型

为研究精炼渣中Ce2O3的加入对渣中Al2O3活度的影响,根据炉渣结构离子与分子共存理论和相关相图,建立1500℃下Ce2O3-Al2O3和CaO-Al2O3-Ce2O3渣系作用浓度的计算模型,考察Ce2O3对Al2O3作用浓度的影响。结果表明：对于Ce2O3-Al2O3渣系,当Ce2O3的摩尔分数在0.49左右时,Ce2O3·Al2O3的作用浓度达到最大值0.90,使得Al2O3和Ce2O3的作用浓度均达到较低水平;对于CaO-Al2O3-Ce2O3渣系,模型所计算的Al2O3作用浓度与实测Al2O3活度的变化趋势一致,即Ce2O3含量一定时,随着w(CaO)/w(Al2O3)的增加,Al2O3的作用浓度降低;保持w(CaO)/w(Al2O3)不变,随着Ce2O3含量的增加,Al2O3的作用浓度降低。同时,由计算结果绘出CaO和Ce2O3的等作用浓度线。总之,精炼渣中添加一定量的Ce2O3能够有效地降低Al2O3的作用浓度,这能提高精炼过程中高质量洁净钢中Al2O3的去除速率和精炼渣的精炼效率。     

液态CaO-SiO_2和CaO-Al_2O_3-SiO_2渣中CaO的活度

利用石灰的加碳还原反应,设计了一个新的研究方法,以直接测定液态高炉型渣中CaO的活度.这一方法的成功,依靠溶剂金属的正确选择以降低熔液中钙的化学位,而使金属钙量提高到可以用化学分析测定的水平.我们估计钙在锡稀溶液中的活度系数很小,可能符合于我们的要求,因此研究了下列反应:CaO+C(石墨)=Ca(锡)+CO(气).以测定液态CaO-SiO_2和CaO-Al_2O_3-SiO_2渣中CaO的活度,在上式中符号下波纹线表示溶于渣中的组分,直线表示溶子金属中的组分,下同.对于CaO-Si0_2系,应用Gibbs-Duhem关系从CaO活度值算出了SiO_2的活度值,并根据一个统计力学模型讨论了活度曲线的形状.从CaO-Al_2O_3-SiO_2系的研究结果,可知在所研究的整个碱度范围內,渣中存在10%Al_2O_3都使CaO的活度增加;当Al_2O_3为20%时,则对CaO活度的影响视碱度不同而异.对Al_2O_3的这种行为,根据炉渣的离子结构理论提出了解释.     

液态“渣-金属”化学平衡法求取渣系组元活度的探讨

简单介绍以液态“渣-金属”化学平衡法求取渣系组元活度的方法及步骤，并以此测定了CaO—SiO2-Al2O3,CaO-SiO2-MgO和CaO－B2O3等渣系中CaO的活度结果表明．正确选择金属溶剂，正确配料──包括炼制好金属料需要的有关合金和适合渣料需要的预备渣，以及正确选择测试温度和平衡所需时间，是实验成功的关键.     

基于最小Gibbs自由能原理的CaO-SiO2炉渣和Si-Ca金属两相体系平衡热力学模型

基于封闭平衡体系Gibbs自由能最小原理对精炼Si液中杂质Ca的炉渣金属体系建立热力学模型,由该热力学模型得到Si液中Ca的摩尔分数xCa与CaO-SiO2二元渣系CaO的摩尔分数xCaO的关系和文献报道的实验结果吻合良好,即0.3相似文献   

THERMODYNAMICS OF LIQUID BLAST-FURNACE-TYPE SLAGS Ⅰ.EVALUATION OF ACTIVITIES OF CaO AND SiO_2

在本文中,作者综合分析了关于CaO—SiO_2、CaO—SiO_2—Al_2O_3及CaO—MgO—SiO_2—Al_2O_3系统熔渣中α_(SiO_2)及α_(CaO)的测定结果,并加以比较。关于CaO—SiO_2二元系,作者综合了Fulton与Chipman,张禄经与Derge及坂上六郎的实验数据,导出了1600℃时液态渣在整个浓度范围内的α_(SiO_2)及α_(CaO),分别用β鳞石英及固态CaO为标准状态。根据这样算出的α_(SiO_2)及α_(CaO)以及坂上的CaO侧电动势数据,作者导出了一个经验公式,可以用来从已知的电动势数据与α_(SiO_2)计算α_(CaO)。将这个公式应用于CaO—SiO_2—Al_2O_3三元系,算出了三元系熔渣内当Al_2O_3=10、20%时的α_(CaO)。然后将二元系和三元系中的α_(CaO)加以比较,导出了一个新的碱度计算公式。在此式中A1_2O_3显示双性,当碱度较高时它属于酸性,因此可以分子比例与SiO_2相加;反之,当碱度较低时它属于碱性,因此须从SiO_2中扣去。如将MgO以重量百分率与CaO相加,这个碱度公式也可以适用于四元系。由于新的碱度公式所根据的实验数据并不充分,所以它的能否适用须视应用结果如何而定。 Taylor与Stobo由脱硫平衡数据计算了三个熔渣内的α_(CaO),与作者的计算结果不能符合。本文初步分析了造成这个差异的原因。因为这个差异的     

Fe-15Ce合金在H2-CO2、H2-H2S及H2-H2S-CO2气氛下的腐蚀

研究了600℃时Fe-15Ce合金在H2-CO2、H2-H2S及H2-H2S-CO2 3种气氛中的腐蚀行为，Fe-15Ce合金腐蚀后发生了Ce的内氧化或形成了复杂的腐蚀产物膜，而未出现Ce的选择性氧化或硫化，这主要是合金中存在着两相及Ce在Fe中极低的溶解度的结果。Fe-15Ce合金在本实验条件下的氧化-硫化腐蚀速度低于相同温度、压力下的纯硫化。     

用氢-氧取代氧-乙炔作焊接切割的必要性及可行性

阐述了用氢代乙炔的必要性．通过时HGQU2000／315火焰电孤焊割机的考察和试用证实了用氢代乙炔的可行性，比较了两种气体的性质并提出了使用特性差异和注意事项．提出了进一步探索的问题。     

Thermodynamics and phase diagrams in the binary systems Na2O-SiO2, Na2O-GeO2, Na2O-B2O3, Li2O-B2O3, CaO-B2O3, SrO-B2O3, and BaO-B2O3

We applied our model to the enthalpy of mixing data of the binary systems Na₂O-SiO₂, Na₂O-GeO₂, Na₂O-B₂O₃, Li₂O-B₂O₃, CaO-B₂O₃, SrO-B₂O₃, and BaO-B₂O₃. The most stable composition in the liquid, that is where the enthalpy of mixing is most negative, is with a metal-oxygen ratio of 4 to 3, for monovalent metals (Na and Li) and 3 to 4 for divalent metals (Ba and Ca) in liquid silicates or borates. The same applies to the CaO-SiO₂, CaO-Al₂O₃, PbO-B₂O₃, PbO-SiO₂, ZnO-B₂O₃, and ZnO-SiO₂ systems. The oxygen to metal ratio, its constant value in various types of systems, reflects and describes the structure of the liquid. Using the analyzed enthalpies of mixing data and the available phase diagrams, we calculated the enthalpies of formation of the various binary compounds. The results are in excellent agreement with data in the literature that were obtained from direct solid-solid calorimetry.     

IrO2-MnO2中间层Ti/RuO2-TiO2-SnO2电极制备及性能

通过热分解法制备了含IrO2-MnO2中间层Ti/RuO2-TiO2-SnO2电极,采用SEM、EDX、XRD、CV等检测方法对中间层进行表征,同时采用强化加速寿命试验对电极电化学稳定性进行表征。结果表明:450℃时前躯体完全氧化并形成固溶体,制备的中间层晶粒细小,表面结构致密,电化学孔隙率小。添加中间层使Ti/RuO2-TiO2-SnO2电极强化寿命由未加中间层的7.5h提高到995.8h,远高于国家标准20h。     

ACTIVITY OF La_2O_3 IN LIQUID La_2O_3-CaF_2 AND La_2O_3-CaF_2-CaO-SiO_2 SLAGS

用石墨为还原剂,将渣中La_2O_3还原入液态Sn,以测定1500℃下La_2O_3-CaF_2和La_2O_3-CaF_2-CaO-SiO_2渣中La_2O_3的活度.对La_2O_3-CaF_2系,并用Gibbs-Duhem积分法求得CaF_2的活度. 根据液态渣的离子结构模型,对上述二渣系中La_2O_3的活度数据进行了简单的讨论.     

Mechanoluminescence in BaSi2O2N2:Eu

Mechanoluminescence (ML), a general term for the phenomenon in which light emission occurs during any mechanical action on a solid, can be divided roughly into two classes: destructive ML and non-destructive ML. For practical use in high-end applications (e.g. pressure sensors), materials with non-destructive ML properties are preferred. This paper reports on the strong non-destructive ML in BaSi₂O₂N₂:Eu. When irradiated in advance with ultraviolet or blue light, this phosphor shows intense blue-green light emission upon mechanical stimulation such as friction or pressure. The ML has an emission band peaking at 498 nm, which is ～4 nm red-shifted compared to the steady-state photoluminescence. The origin of the ML is discussed and related to the persistent luminescence of BaSi₂O₂N₂:Eu. The same traps are responsible for both phenomena. Based on the occurrence of ML in this phosphor, we were able to show that the predominant crystallographic structure of BaSi₂O₂N₂:Eu belongs to space group Cmc2₁.     

氢分子在贮氢材料Li2MgN2H2表面的吸附与解离

采用第一性原理计算方法研究了Li-Mg-N-H体系贮氢材料的放氢产物Li2MgN2H2的吸氢反应过程中的过渡态、表面电子态密度和表面能。结果表明:氢分子在Li2MgN2H2低指数表面中最低能量(100)表面的Mg-Mg-Li穴位吸附位置能够形成最稳定的吸附结构并发生解离,氢分子吸附能为-0.1898eV,解离能约为0.84eV(81kJ/mol),表明该反应所需的反应活化能仍较高,吸氢反应速度缓慢。     

Thermodynamic evaluation of phase equilibria in the CaCl2-MgCl2-CaF2-MgF2 system

The phase diagram of the CaCl₂-CaF₂-MgCl₂-MgF₂ reciprocal ternary system was calculated thermodynamically from available data on the common-ion binary subsystems and from available data on the CaCl₂-MgF₂ join. This join is very nearly quasibinary and divides the system into two quasiternary systems: the CaCl₂-MgF₂-CaF₂ system with a ternary eutectic calculated at 724 +-5 °C and the CaC₂-MgF₂-MgCl₂ system with a ternary eutectic calculated at 561 +-5 °C.     

High temperature corrosion of Fe-Cr-Mn-alloys in H2-H2S and H2-H2O-H2S gas mixtures

The sulfidation of Fe-20% Cr-30% Mn, Fe-25%Cr-20%Mn and Fe-25% Cr was studied at 700°C in H₂-H₂S and the oxidation and sulfidation in H₂-H₂O-H₂S after preoxidation in H₂-H₂O. The sulfidation rate is strongly increased for the Mn-containing alloys, layers of (Mn,Cr)S and (Mn,Fe)Cr₂S₄ are formed. Also the oxidation rate is enhanced compared to Fe-25% Cr by formation of MnCr₂O₄ instead of Cr₂O₃. The sulfidation after preoxidation leads to internal and external sulfidation of the Mn-containing alloys. With increasing oxygen pressure p(O₂) = 10^?26…10^?22 atm. of the H₂-H₂O-H₂S mixtures the sulfidation is suppressed, for the higher oxygen pressure 10^?23 and 10^?22 atm. fast oxidation prevails under formation of MnCr₂O₄. Manganese cannot increase the sulfidation resistance of alloys, in spite of the stability and low degree of disorder of its sulfide, since the mixed sulfide (Mn,Cr)S is formed which has a high degree of disorder, high diffusivities and high growth rate according to the doping effect of trivalent Cr³⁺.     

PHASE DIAGRAM OF TERNARY SYSTEM PrCl_2-CaCl_2-MgCl_2

Three surfaces corresponding to the primary crystallization of PrCl_3,CaCl_2 andMgCl_2 respectively,3 univariant curves related to the secondary crystallization and a ternaryeutectic(44.8 wt-% PrCl_3,31.8 wt-% CaCl_2,546℃)were found in systemPrCl_3-CaCl_2-MgCl_2 by means of DTA.A reaction occurs in this system:L=PrCl_3+CaCl_2+MgCl_2.