Fe-Cr-V-Ni-Si-C系多元合金的原子间互作用势的构建及应用

使用第一性原理赝势方法及量子化学从头算方法计算的物理量以及最小二乘法拟合的数据构建了多元合金Fe-Cr-V-Ni-Si-C系的原子间互作用势，并利用该原子间互作用势计算了实验合金N5(Fe9.07Cr7.56V0.8Ni0.49 Mo0.96Mn1.52Si3.3C)，N6(Fe9.65Cr7.72V1.17Ni0.50Mo0.91Mn1.42Si3.3C)，N7(Fe9.81Cr7.65V1.58Ni0.46Mo0.86Mn1.35Si3.3C)，N8(Fe10.05Cr7.59V2.24Ni0.40M     

Cr,Mo,Ni在$lt;i$gt;α$lt;/i$gt;-Fe（C）中占位、键合性质及合金化效应的第一性原理研究

基于密度泛函理论第一性原理方法,采用广义梯度近似下的PW91泛函形式,计算了合金元素Cr,Mo,Ni固溶于α-Fe（C）的电子结构,从晶格畸变、结合能、态密度、重叠布居及差分电荷密度等计算结果出发探讨了合金元素在α-Fe（C）中占位、键合性质及其合金化效应,结果表明：Cr优先占据铁素体晶胞顶角位置,而Mo,Ni 优先占据体心位置;Cr与晶胞的结合能最大,晶胞最稳定,Ni次之,Mo最低;Cr,Mo,Ni 在晶胞中都存在金属键、共价键和微弱离子键的共同作用,成键轨道主要是Cr3d与Fe3d,Mo4d与Fe3d,Ni3d与Fe3d,C2p的交互作用形成的;Cr与晶胞原子间的键合作用强,晶胞的稳定性好,对增强钢材的机械性能帮助较大,Ni的键合作用较弱,但还是能保持晶胞的稳定性,Mo虽然键合作用强,但反键作用也非常强,使晶胞的稳定性大大降低,对钢材的机械性能危害较大. 关键词： 第一性原理 α-Fe（C）')" href="#">α-Fe（C） 键合性质 合金化效应     

Cr,Mo,Ni在α-Fe(C)中占位、键合性质及合金化效应的第一性原理研究

基于密度泛函理论第一性原理方法,采用广义梯度近似下的PW91泛函形式,计算了合金元素Cr,Mo,Ni固溶于α-Fe(C)的电子结构,从晶格畸变、结合能、态密度、重叠布居及差分电荷密度等计算结果出发探讨了合金元素在α-Fe(C)中占位、键合性质及其合金化效应,结果表明:Cr优先占据铁素体晶胞顶角位置,而Mo,Ni优先占据体心位置;Cr与晶胞的结合能最大,晶胞最稳定,Ni次之,Mo最低;Cr,Mo,Ni在晶胞中都存在金属键、共价键和微弱离子键的共同作用,成键轨道主要是Cr3d与Fe3d,Mo4d与Fe3d,Ni3d与Fe3d,C2p的交互作用形成的;Cr与晶胞原子间的键合作用强,晶胞的稳定性好,对增强钢材的机械性能帮助较大,Ni的键合作用较弱,但还是能保持晶胞的稳定性,Mo虽然键合作用强,但反键作用也非常强,使晶胞的稳定性大大降低,对钢材的机械性能危害较大.     

Cr,Mo,Ni在γ-Fe(C)中的键合性质及对相结构稳定性的影响

基于密度泛函理论第一性原理方法,采用广义梯度近似下的PW91泛函形式,计算了合金元素Cr,Mo,Ni固溶于γ-Fe(C)的电子结构,从重叠聚居数、电荷布居数、态密度、差分电荷密度及结合能等计算结果分析探讨了合金元素在γ-Fe(C)中的键合性质及对奥氏体相稳定性的影响.结果表明:Cr,Mo在奥氏体晶胞中都存在金属键、共价键和微弱的离子键的共同作用,而Ni仅有金属键和共价键作用,几乎不受离子键作用,成键轨道主要是Cr,Mo,Ni的d轨道与Fe 3d,C 2p轨道的交互作用形成的.依据合金元素对γ-Fe(C)电子结构的影响,探讨了Cr,Mo,Ni固溶后对奥氏体相稳定性的影响.     

合金元素对钢中NbC异质形核影响的第一性原理研究

为了探索不同合金元素对Nb C异质形核的影响,本文利用第一性原理研究了合金元素X(X=Cr,Mn,Mo,W,Zr,V,Ti,Cu和Ni)对ferrite(100)/Nb C(100)界面性质的影响,并且分析了上述合金元素掺杂前后界面的黏附功、界面能和电子结构.研究结果表明,Cr,V和Ti掺杂的界面具有负的偏聚能,说明它们容易偏聚到ferrite/Nb C界面,但Mn,W,Mo,Zr,Cu和Ni却难以偏聚到此界面.当Mn,Zr,Cu和Ni取代界面处的Fe原子后,界面的黏附强度降低,即这些合金减弱铁素体在Nb C上的形核能力.然而Cr,W,Mo,V和Ti引入界面后,其黏附功比掺杂前的界面要大,且界面能均降低,即提高了界面的稳定性.因此,W,Mo,V和Ti,尤其是Cr,能够有效地促进铁素体形核和细化晶粒.电子结构分析表明,Zr和Cu引入界面后,界面处的Zr,Cu原子和C原子的相互作用变弱;然而Cr和W引入界面后,Cr,W和C原子之间形成了很强的非极性共价键,提高了ferrite/Nb C界面的结合强度.     

Cr掺杂以及Mo和Cr双掺Mn4Si7的第一性原理计算

采用基于密度泛函理论中第一性原理的赝势平面波法,分别对本征Mn4Si7、Cr掺杂Mn4Si7以及Cr和Mo双掺Mn4Si7的电子结构及光学性质进行了计算和分析。计算结果表明本征Mn4Si7禁带宽度为Eg=0.813 eV,Cr掺杂Mn4Si7禁带宽度为Eg=0.730 eV,Cr和Mo双掺Mn4Si7禁带宽度为Eg=0.620 eV,均为间接带隙半导体、p型掺杂。此外,在低能区掺杂体系的介电函数、折射率、消光系数、吸收系数以及光电导率均强于本征Mn4Si7,表明Cr掺杂Mn4Si7以及Cr和Mo双掺Mn4Si7有运用于红外光电子器件的巨大潜力。     

Y12TM（TM=Sc、Ti、V、Cr、Mn、Fe、Co、Ni、Cu、Zn）团簇的电子结构与磁性研究

基于第一性原理,在密度泛函理论框架下,用广义梯度近似(GGA)研究了二十面体Y12TM(TM=Sc、Ti、V、Cr、Mn、Fe、Co、Ni、Cu、Zn)团簇的电子结构和磁性,计算了它们的束缚能(BE)、中心原子到表面原子的间距、最高占据轨道(HOMO)、最低占据轨道(LUMO)及其能隙.研究表明:Y13、Y12Sc、Y12Ti、Y12V、Y12Cr团簇的主体原子和杂质原子呈现出铁磁性作用,而Y12Mn、Y12Fe、Y12Co、Y12Ni、Y12Cu、Y12Zn团簇的主体原子和杂质原子呈现出反铁磁作用.     

掺杂ZnTe对电子结构与磁性质的影响

为了研究Mn、Fe、Co、Ni掺杂ZnTe的电子结构和磁性的相关性质.本文基于第一性原理的数值基组的方法计算了Mn、Fe、Co、Ni掺杂ZnTe的能带结构、态密度,分析了掺杂结构的稳定性和磁性性质.结果发现Mn、Fe、Co、Ni掺杂ZnTe的杂质替换能分别为-1.14 e V,-1.23 e V,39.95 e V,-4.32 eV,表明Mn、Fe、Ni掺杂的ZnTe在实验上较容易实现.Mn、Co掺杂ZnTe导致体系产生的总磁矩分别为0.997μB,1.103μB,其中磁性的主要来源于Mn、Co原子在Zn位的取代而引起,产生局域磁性主要取决于Mn、Co的d轨道与Te的p轨道耦合作用.     

Mg12O12纳米线掺杂3过渡金属元素的第一性原理计算研究

基于密度泛函第一性原理计算,系统研究了Mg12O12笼状团簇组装一维纳米线及其掺杂3d族元素体系的几何结构与电子结构。结果表明：Mg12O12团簇组装一维纳米线为非磁性半导体,带隙值为3.16 eV;掺杂Sc和V后,体系由半导体转变为金属;掺杂Ti、Cr、Mn、Fe、Co、Ni、Cu后体系仍然保持半导体特性、但带隙值明显减小,而掺杂Zn时带隙值变化不大;掺杂V、Cr、Mn、Fe、Co、Ni、Cu后纳米线具有磁性。     

合金元素对α-Fe氢扩散行为影响的第一性原理研究

本文采用基于密度泛函理论的第一性原理方法,研究了H原子在α-Fe和α-Fe-Me(Me=Cr、Mo、Ni、Cu、Mn)晶胞中的扩散行为,建立了α-Fe和α-Fe-Me中氢扩散系数与温度间的关系表达式,探讨了合金元素Me对α-Fe中H扩散行为的影响作用.研究结果表明:合金原子Me与H原子间存在一定的键合作用,并且这种键合作用主要由Me价电子的d、s轨道与H的1s轨道所贡献;Cr、Ni、Cu、Mn元素将降低H原子扩散激活能,而Mo元素会提高氢扩散激活能,显著降低氢扩散系数,这说明添加适量Mo元素将有利于防止铁素体氢致开裂,这将对抗H₂S应力腐蚀新材料的设计提供一定理论依据.     

Heusler合金Mn50–xCrxNi42Sn8的相变、磁性与交换偏置效应

研究了Mn50–xCrxNi42Sn8 (x=0, 0.4, 0.6, 0.8)多晶样品的相变、磁性和交换偏置效应.结果表明,该系列合金在室温下都具有非调制的四方马氏体结构.马氏体逆相变温度随Cr含量增加而逐渐降低. 20 k Oe磁场下的M-T曲线表明,该系列合金的磁性比较弱.两相之间的磁性差最大为△M=7.61 emu/g.磁性的变化主要与Mn-Mn间距的变化以及Ni(A位)-Mn(D位)间杂化作用的强弱有关.在低温下,马氏体相的磁性随着Cr含量增加而增强.在500 Oe的外加磁场作用下,从室温冷却到5 K,在Mn50Ni42Sn8合金中观察到高达2624 Oe的交换偏置场.随着Cr含量的增加,交换偏置场逐渐减小.当Cr含量x=0.8时,随着冷却场的增加, 5 K时的交换偏置场先迅速增加然后逐渐减小.当冷却场为500 Oe时,交换偏置场最大.这主要归因于自旋玻璃态与反铁磁性区域的界面交换耦合作用的变化.     

Cu对Ni50Mn36In14相变和磁性的影响

文章研究了Cu替代部分Ni对铁磁性形状记忆合金Ni₅₀Mn₃₆In₁₄相变和磁性的影响规律. 研究表明,在Ni_50-xCu_xMn₃₆In₁₄中,随着Cu含量的增加,相变温度逐渐降低. Cu含量低于5%时,奥氏体的磁性强于马氏体的磁性, 母相和马氏体相的饱和磁化强度的差值ΔM随着Cu含量的增加而增大. 当Cu含量x=4.5时, ΔM迅速增加到80 emu/g, 并在该材料中观察到了磁场驱动的马氏体到奥氏体的转变,显示了该材料作为磁驱动磁电阻材料的潜在应用前景.当Cu含量高于5%时,奥氏体保持铁磁状态, 马氏体相由反铁磁状态变为铁磁状态,马氏体的磁性强于奥氏体的磁性, ΔM大大削弱,磁场驱动性质消失.     

Ginzburg-Landau theory and solitary waves in shape-memory alloys

A one-dimensional dynamic Ginzburg-Landau theory of the martensitic phase transition in shape-memory alloys is established. The nonlinear equations of motion yield solitary wave solutions of kink and of soliton type. The kink solutions which cannot move without external force represent single domain walls either between austenite and martensite or between two martensite variants. The soliton solutions correspond to a matrix of austenite or of martensite containing a moving sheet of the other phase. The velocity of the solitons depends on their amplitude. In the static case they reduce to the critical nucleus. The energy of each type of solitary waves is calculated.     

The effect of Si content on the martensitic transfor-mation temperature of Ni55.5e18Ga26.5-xSix alloys

This paper investigates the effects of substitution of Si for Ga on the martensitic transformation behaviours in Ni-Fe-Ga alloys by using optical metallographic microscope and differential scanning calorimetry (DSC) methods. The structure type of Ni_55.5Fe₁₈Ga_26.5-xSi_x alloys is determined by x-ray diffraction (XRD), and the XRD patterns show the microstructure of Ni-Fe-Ga-Si alloys transformed from body-centred tetragonal martensite (with Si content x = 0) to body-centred cubic austenite (with x = 2) at room temperature. The martensitic transformation temperatures of the Ni_55.5Fe₁₈Ga_26.5-xSi_x alloys decrease almost linearly with increasing Si content in the Si content range of x ≤ 3. Thermal treatment also plays an important role on martensitic transformation temperatures in the Ni-Fe-Ga-Si alloy. The valence electronic concentrations, size factor, L2₁ degree of order and strength of parent phase influence the martensitic transformation temperatures of the Ni-Fe-Ga-Si alloys. An understanding of the relationship between martensitic transformation temperatures and Si content will be significant for designing an appropriate Ni-Fe-Ga-Si alloy for a specific application at a given temperature.     

Ag-rich phase formation in the Cu-6 wt% Al alloy with Ag additions

Ag-rich phase formation in the Cu-6 wt% Al alloy with additions of 4, 6, 8, 10, and 12 wt% Ag was studied using microhardness changes with temperature and time, differential thermal analysis (DTA), scanning electron microscopy (SEM), energy-dispersive X-ray analysis (EDX), and X-ray diffractometry (XRD). The results indicated that the Ag-rich phase formation follows two different processes depending on Ag concentration. For alloys with 4 and 6 wt% Ag the precipitate formation occurs as a second-order mechanism while for alloys with 8, 10 and 12 wt% Ag a zero-order reaction was observed.     

In situ synchrotron X-ray microdiffraction analysis of thermomechanically induced phase transformations in Cu–Al–Ni shape-memory alloy

Phase transformations in a single-crystal Cu–Al–Ni shape-memory alloy induced by thermomechanical effects were investigated in situ by high-resolution synchrotron X-ray microdiffraction. Contrary to the common belief, austenite texture maps revealed that austenite-to-martensite transformation occurred during heating of the partially transformed material under fixed specimen elongation. Twinned and detwinned types of martensite coexisted during this austenite-to-martensite phase transformation. Twinning and detwinning structures evolved to accommodate changes in stress and strain generated in the temperature-varying environment. Small amounts of austenite exhibiting distorted crystallographic orientation were detected in regions of stress-induced martensite during heating of the partially transformed material. The results of this investigation provide insight into intriguing stress rate-dependent phenomena intrinsic of shape-memory alloys and elucidate complex phase transformations due to thermal and mechanical stress effects.     

Magnetic glass in shape memory alloy: Ni(45)Co(5)Mn(38)Sn(12)

The first order martensitic transition in the ferromagnetic shape memory alloy Ni(45)Co(5)Mn(38)Sn(12) is also a magnetic transition and has a large field induced effect. While cooling in the presence of a field this first order magnetic martensite transition is kinetically arrested. Depending on the cooling field, a fraction of the arrested ferromagnetic austenite phase persists down to the lowest temperature as a magnetic glassy state, similar to the one observed in various intermetallic alloys and in half doped manganites. A detailed investigation of this first order ferromagnetic austenite (FM-A) to low magnetization martensite (LM-M) state transition as a function of temperature and field has been carried out by magnetization measurements. Extensive cooling and heating in unequal field (CHUF) measurements and a novel field cooled protocol for isothermal MH measurements (FC-MH) are utilized to investigate the glass like arrested states and show a reverse martensite transition. Finally, we determine a field-temperature (HT) phase diagram of Ni(45)Co(5)Mn(38)Sn(12) from various magnetization measurements which brings out the regions where thermodynamic and metastable states coexist in the HT space, clearly depicting this system as a 'magnetic glass'.     

Ti-V系合金的结构、力学性质及电子结构的第一原理研究

采用基于密度泛函理论的第一原理方法,研究了Ti-V系合金Ti_3V, TiV和TiV_3的晶体结构,电子结构及力学性质.结果表明, TiV_3结构最稳定,其次是TiV,而Ti_3V稳定性最弱,但是, Ti_3V形成能力最强.三种合金的自间隙构型中,与Ti的自间隙构型相比,更容易形成V的自间隙构型;不管是Ti自间隙还是V自间隙, TiV_3的自间隙形成能均最大.力学性质的计算表明:三种合金均满足力学稳定性标准,且都为韧性材料;体模量及硬度计算表明, TiV_3的硬度最高,其次是TiV, Ti_3V的硬度最低,这与自间隙能的计算结果一致.电子结构计算表明:在费米能级处,三种合金均主要由Ti, V的p, d轨道电子提供态密度, TiV_3合金电子结构最稳定.差分电荷密度计算表明:在Ti_3V合金中,金属性强于共价性.在Ti_3V, TiV, TiV_3三种合金中,金属性逐渐减弱,共价性逐渐增强,合金变得稳定.     

Martensitic transformations and magnetic properties of nonstoichiometric alloys of the Ni-Mn-In system

Martensitic transformations and magnetic properties of Ni_89-x Mn _x In₁₁ (42 ≤ x ≤ 44) alloys have been investigated. Critical temperatures of magnetic and structural phase transitions in the studied alloy system have been determined. It has been shown that the martensitic transformation induced by the magnetic field is observed in all alloys. Temperature dependences of the spontaneous magnetization of austenite and martensite as well as the magnitude of the critical field, in which martensitic transformation occurs, have been determined.     

Mössbauer and XRD study of Al-Sn linished steel bimetal alloy

Aluminium alloy free CS1 type steel (0.06 wt% C, 0.45 wt% Mn) and samples of cold roll bonded steel bimetal alloys (MAS15 and MAS16) were fabricated and investigated by X-ray diffraction (XRD), ⁵⁷Fe conversion electron Mössbauer spectroscopy (CEMS) at room temperature. XRD has revealed only the existence of the alpha iron solid solution (steel) phase in the steel only sample, while identified steel and metallic Al and Sn constituent phases in the bimetallic alloys. ⁵⁷Fe Mössbauer spectroscopy revealed the presence of 4 % secondary iron-bearing phase attributed mainly to iron oxide/ oxyhydroxides (ferrihydrite) besides the steel matrix on the surface of the steel sample. A significant difference between the occurrences of the secondary phase of differently prepared bimetal alloys found in their ⁵⁷Fe CEM spectra allowed to identify the main phase of debris as different iron oxide/ oxyhydroxides.