Fe—Al系金属熔体作用浓度的计算模型

根据含化合物金属熔体的共存理论和Fe-Al系相图,用回归分析法确定了Fe-Al系金属熔体在1315℃和1600℃时的结构单元,进而推导了各组元的作用浓度模型。将计算的N_(Fe),N_(Al)和实测的活度值α_Fe,α_Al相比较,得到了比较满意的结果。     

三元合金及金属间化合物中各组分活度系数的计算

根据Kohler三元溶体模型和Miedema二元系统生成热模型，建立了计算三元合金及金属化合物中各组分活度系数的方程。计算了三元合金Ti-5Al-2.5Sn,Ti-6Al-4V及不同温度下金属间化合物TiAl,Ti3Al和Ti2AlNb中各组分的活度系数。并与有关实验值进行了对比.计算结果表明此公式的计算结果与实验值吻合较好，解决了固态二元、三元合金及金属间化合物中各组分的活度系数的计算问题，Ti与A1活度系数均小于1，对Raoultl定律产生负偏差。根据所计算的活度系数和活度值，预测了SiC/TiAl,SiC/Ti3Al和SiC/Ti2AlNb复合材料的界面反应，表明SiC/Ti3Al界面反应较为严重。     

Al-Ti-B_4C-TiH_2系燃烧合成反应制备泡沫铝合金的热力学研究

利用燃烧合成技术在制备多孔材料方面有其独特的优势,基于Al-Ti-B4C-TiH2系燃烧合成反应制备泡沫铝。通过燃烧过程中的反应放热量、燃烧温度、原料配比临界条件的理论计算及DSC曲线分析对Al-Ti-B4C-TiH2系燃烧合成反应进行热力学研究。实验结果表明:Al-Ti间、Ti-B4C间反应分别在800℃及1 300℃左右发生,首先Al-Ti间反应,随着反应放热量的增加TiB4C间反应被激活,大量剩余的Ti优先与B4C反应直至无B4C存在,剩余的Ti再与Al反应,AlTi间反应的最终产物应为TiAl3。原料中的TiH2受热分解释放出气体迫使预制体膨胀得到泡沫铝。原料配比的临界条件中Al的质量分数为76%,且生成物中Al相质量分数为68.8%。     

基于离子和分子共存理论的炉渣氧化能力表征

选用文献报道的14个渣系铁氧化物活度aFetO作为基础实验数据,验证了基于炉渣离子–分子共存理论(IMCT)所定义的铁氧化物综合质量作用浓度NFetO表征炉渣氧化性的可能性和精度.为了得到14个渣系的NFetO,建立了CaO-SiO2-MgO-FeO-Fe2O3-MnO-Al2O3-P2O5渣系的IMCT-Ni模型,其他13个渣系NFetO可由该渣系的IMCT-Ni模型经简化得到.结果表明,铁氧化物综合质量作用浓度NFetO不仅可像活度aFetO一样表征炉渣氧化性,而且比实测aFetO精度更高.     

关于含化合物金属熔体结构的共存理论

从含化合物金属熔体的原子本性和分子本性(活度的负偏差、混合△G和△H显示最小值、过剩稳定性的突然升高、电阻率显示最大值和相图等)出发,提出了反映本熔体实际的原子和分子共存理论。根据此理论制定了不同金属熔体作用浓度(即实测的活度)的计算模型。计算结果与实际符合的事实证明共存理论恰当地反映了含化合物金属熔体的结构本质。     

Al-Zr,Al-Y和Zr-Y二元合金熔体热力学性质的计算

基于Miedema模型,利用热力学基本原理及元素的基本性质,计算Al-Zr,Al-Y和Zr-Y二元系统的混合焓、过剩熵、过剩吉布斯自由能以及各组元的活度.基于Al-Zr和Al-Y二元合金相图的数据,计算Al3Zr和Al3Y相析出反应的吉布斯自由能.研究结果表明:Al-Zr和Al-Y二元合金熔体的混合焓、过剩熵和过剩吉布斯自由能都小于0J,各组元的活度相对于理想溶液发生了较大的负偏差,而Zr-Y二元合金熔体的混合焓、过剩熵和过剩吉布斯自由能大于0J,各组元的活度相对于理想溶液发生了较大的正偏差,说明Al与Zr和Y原子有较强的相互作用,而Zr和Y原子相互作用不大.2种相析出反应的吉布斯自由能都小于0J,且Al3Y相的吉布斯自由能更小,表明过渡族元素Zr和稀土元素Y同时加入到纯Al时,更容易生成Al3Y;计算结果和实验结果相吻合,证明Miedema模型的合理性.     

二元相图中稳定化合物活度的计算方法

基于二元相图中存在大量稳定的化合物的理论基础.据此,提出了一种由含稳定化合物的二元相图中化合物计算活度的新方法.根据已有的从二元相图提取活度的公式,先求出2个组元的活度,再由质量作用定律求出平衡常数K0,从而可由得到的2个纯组元的活度,计算得到稳定化合物的活度.用此方法计算了In-Sb二元系中稳定化合物的活度,经验证此方法是可行的,其计算结果与文献值吻合很好.     

Al-V系二元相图的计算、评估及其活度

利用最新版本的Pandat热力学计算软件,采用最新的Ti合金数据库和合理的热力学模型,计算出了Al-V系二元相图.研究发现：从相率和相图的特殊点对其进行了详细的热力学评估,最大误差为1.14%,说明计算相图与试验相图吻合较好;在Al-V二元相图的基础上,提取了Al和V在不同物质的成分和温度下的活度;拟合了恒温下其活度的计算公式,其线性相关度R趋近于1;作出了V的活度-成分-温度关系曲线,有效地解决了"试验测活度难"的问题.     

含铝钛合金电渣重熔中的渣系设计及脱氧热力学

以炉渣离子、分子共存理论为基础,1Cr21Ni5Ti钢为研究对象,Al为脱氧剂,根据熔渣-金属中各个组元的平衡反应和质量守恒,建立了脱氧热力学模型,并在脱氧基础上设计了渣系.在脱氧剂Al不同的加入量条件下对1Cr21Ni5Ti钢中的Si,Al,Mn的平衡质量分数和渣中Ti O2的需求量进行了计算,Ti O2的加入保证了钢中Ti的含量.结果表明:随脱氧剂Al的增加,Si,Al,Mn,Al2O3的平衡质量分数呈上升的趋势,Si O2,Fe O,Mn O以及渣系中Ti O2的设计量呈下降的趋势;当Al加入量达到0.2%后,渣中不稳定氧化物含量很低,大部分Al进入到钢液中,造成钢液增[Al].根据1Cr21Ni5Ti的Si,Al,Mn的成分要求,得到Al的最大加入量为0.15%/吨钢,此时渣系中Ti O2的设计量为4%,达到保钛的目的.     

TiO2电解制取Al-Ti合金

采用工业铝电解质体系,在Na3AlF6 Al2O3中加入TiO2,在熔融状态下电解,直接得到Al Ti合金·利用扫描电镜对产物的形貌和化学成分做了分析,结果表明实验可行,合金中Ti的质量分数可达到9%以上,超过已往文献报道·而且Ti与Al以化合物的形式存在·此类产品可作为母合金使用·对熔盐电解法制备Al Ti合金的机理作了初步探讨,认为与Al Si合金的形成具有相似的机理:Al还原了TiO2中的金属Ti,与预先放置的铝(阴极)构成Al Ti合金;Ti与Al同时在阴极析出,形成Al Ti合金·保持一定的条件,电解能够始终进行·     

大型板坯电渣重熔过程的脱氧热力学模型

以12Cr2Mo1R钢所用渣系为研究对象,选择Al作为脱氧剂,建立脱氧热力学模型.在不同的Al添加量条件下对12Cr2Mo1R钢熔渣-金属界面处各物质的平衡质量分数进行计算,分析各物质平衡质量分数随Al添加量的变化规律,为在给定Al添加量条件下进行终点成分预报,以及根据钢种成分要求选择Al添加量范围提供理论依据.结果表明,随Al添加量的增加,Si,Mn,Al,Al2O3的平衡质量分数呈上升趋势;SiO2,MnO,FeO的平衡质量分数呈下降趋势.若仅从Si,Mn,Al成分合格的角度考虑,Al的添加量占吨钢的百分比不能超过02%.     

A thermodynamic model of calculating mass action concentrations for structural units or ion couples in NaClO_4-H_2O and NaF-H_2O binary solutions and NaClO_4-NaF-H_2O ternary solution

A thermodynamic model of calculating mass action concentrations for structural units or ion couples in NaClO4-H2O and NaF-H2O binary solutions and NaClO4-NaF-H2O ternary strong electrolyte aqueous solutions was developed based on the ion and molecule coexistence theory (IMCT). A transformation coefficient was needed to compare the calculated mass action concentration and the reported activity, because they were usually obtained at different standard states and concentration units. The results show that transformation coefficients between the calculated mass action concentrations and the reported activities of the same components change in a very narrow range. The transformed mass action concentrations of structural units or ion couples in NaClO4-H2O and NaF-H2O binary solutions agree well with the reported activities. The transformed mass action concentrations of structural units or ion couples in NaClO4-NaF-H2O ternary solution are also in good agreement with the reported activities in a total ionic strength range from 0.1 to 0.9 mol/kg H2O by the 0.1 mol/kg step with different ionic strength fractions of 0, 0.2, 0.4, 0.5, 0.6, 0.8, and 1, respectively. The results indicate that the developed thermodynamic model can reveal the structural characteristics of binary and ternary strong electrolyte aqueous solutions, and the calculated mass action concentrations of structural units or ion couples also strictly follow the mass action law.     

KBr-H2O、NH4Br-H2O和ZnBr2-H2O作用浓度计算模型

建立了强电解质水溶液KBr-H2O、NH4Br-H2O和ZnBr2-H2O作用浓度的计算模型,计算了上述三个溴化物二元水溶液体系在温度为298.15K、质量摩尔浓度达到饱和前的作用浓度.热力学模型计算的组元作用浓度以纯物质为标准态和摩尔分数为浓度单位,与文献报道的组元活度以无限稀为标准态和质量摩尔浓度为浓度单位经过活度的标准态转换后可良好地吻合,且转换系数在计算的浓度范围内基本守恒.以上热力学模型计算的组元作用浓度能反映出强电解质水溶液的结构本质;在本模型的假设下电解质水溶液呈现理想溶液特征,组元的作用浓度在计算的浓度范围内严格遵守质量作用定律.     

A thermodynamic model of calculating mass action concentrations for structural units or ion couples in NaClO4-H2O and NaF-H2O binary solutions and NaClO4-NaF-H2O ternary solution

A thermodynamic model of calculating mass action concentrations for structural units or ion couples in NaClO₄-H₂O and NaF-H₂O binary solutions and NaClO₄-NaF-H₂O ternary strong electrolyte aqueous solutions was developed based on the ion and molecule coexistence theory (IMCT). A transformation coefficient was needed to compare the calculated mass action concentration and the reported activity, because they were usually obtained at different standard states and concentration units. The results show that transformation coefficients between the calculated mass action concentrations and the reported activities of the same components change in a very narrow range. The transformed mass action concentrations of structural units or ion couples in NaClO₄-H₂O and NaF-H₂O binary solutions agree well with the reported activities. The transformed mass action concentrations of structural units or ion couples in NaClO₄-NaF-H₂O ternary solution are also in good agreement with the reported activities in a total ionic strength range from 0.1 to 0.9 mol/kg H₂O by the 0.1 mol/kg step with different ionic strength fractions of 0, 0.2, 0.4, 0.5, 0.6, 0.8, and 1, respectively. The results indicate that the developed thermodynamic model can reveal the structural characteristics of binary and ternary strong electrolyte aqueous solutions, and the calculated mass action concentrations of structural units or ion couples also strictly follow the mass action law.     

Microstructure and mechanical properties of a hot-extruded Al-based composite reinforced with core-shell-structured Ti/Al3Ti

An Al-based composite reinforced with core-shell-structured Ti/Al3Ti was fabricated through a powder metallurgy route followed by hot extrusion and was found to exhibit promising mechanical properties. The ultimate tensile strength and elongation of the composite sintered at 620°C for 5 h and extruded at a mass ratio of 12.75:1 reached 304 MPa and 14%, respectively, and its compressive deformation reached 60%. The promising mechanical properties are due to the core-shell-structured reinforcement, which is mainly composed of Al3Ti and Ti and is bonded strongly with the Al matrix, and to the reduced crack sensitivity of Al3Ti. The refined grains after hot extrusion also contribute to the mechanical properties of this composite. The mechanical properties might be further improved through regulating the rela-tive thickness of Al-Ti intermetallics and Ti metal layers by adjusting the sintering time and the subsequent extrusion process.     

自蔓延高温合成钒基固溶体贮氢合金的理论研究

提出采用自蔓延高温合成法制备钒基固溶体贮氢合金的新工艺.计算知NH4VO3-TiO2-Cr2O3-Ni-Al反应体系的绝热温度(Tad)为1 889.27 K,单位质量反应热为-2.67 kJ/g;对NH4VO3-TiO2-Cr2O3-Ni-Al反应体系的相关反应进行了热力学分析,表明体系生成V+Ti+Cr+Al2O3的趋势最大,生成物最稳定.确定了采用自蔓延模式的可行性.     

Mechanism of Ag and Al on improving the glass forming ability of CuZr-based alloys

By a mean field theoretical computation,the equilibrium distributions of additional Ag and Al in the crystalline phase of CuZr-based alloys were determined to occupy the two sublattices of the B2 structure randomly.With the molecular dynamics technique,the effects of Ag and Al on the enthalpy difference(ΔH) between the supercooled melt and the crystalline phase were evaluated.The improved glass forming ability of Cu45Zr45Al10 and Cu45Zr45Ag10 can be attributed to their remarkably smaller ΔH than that of CuZr.The calculated diffusion coefficients are more sensitive to the atomic weight of the component atoms than to their interaction strength.As the component atom with the largest mass,the additional Ag increases the viscosity of the supercooled melt significantly and the experimentally stronger glass formation ability of Cu45Zr45Ag10 than Cu45Zr45Al10 can be well understood.