Strategy to design high performance TiB2-based materials: Strengthen grain boundaries by solid solute segregation

TiB₂ exhibits a unique combination of excellent properties that make it promising candidate for applications in extreme environments, where retention of strength at high temperatures is essential. Tailoring grain boundary properties by segregation is believed a prominent way to design high-temperature performance of ceramics. In this work, segregation tendencies of solute elements, including Sc, Y, Zr, Hf, V, Nb, Ta, Cr, Mo, and W, in TiB₂ grain boundaries and the strengthening/weakening effects induced by segregations are investigated by first-principles calculations. The results reveal that small atoms tend to segregate to grain boundary sites with local compression strains, while large atoms prefer grain boundary sites with local expansion strains. Deteriorated grain boundary strength is usually caused by additional expansion strain induced by segregation, while improved grain boundary strength results from either enhanced local bonding induced by segregation of small atoms or increased fracture strain due to segregation of large atoms. Cr and V, especially Cr, exhibit strong segregation tendency and improvement on grain boundary strength, which provides useful guidelines for the design of high performance TiB₂-based materials.     

TiC陶瓷中H原子扩散行为第一性原理计算研究

采用第一性原理计算方法研究了H原子在立方T iC晶格中的结构稳定性及扩散行为.结果表明:H原子在TiC晶格中的最稳定位点位于Ti/C六面体中靠近C原子的C-H(C-HS)位置,H被C原子捕获而形成C—H键,键长1.15? (1?=0.1 nm),零点修正(ZPE)后形成能为1.58 eV;其次是Ti/C六面体中心位置(...     

B掺杂C3N对SO2催化氧化的第一性原理研究

通过第一性原理计算,采用Dmol3模块考察了B原子分别掺杂C3N二维材料的C位(B/C-C3N)和N位(B/N-C3N)所形成的两种单原子催化剂的结构、电子性质以及催化性能。首先,分析了B掺杂C3N的两种结构的稳定性与电子性质,发现B的掺杂使两种结构的稳定性均显著增强,B/C-C3N的电子性质变化更大,由半导体变成了导体。然后,分析了C3N、B/C-C3N和B/N-C3N这3种催化剂对SO2氧化反应的催化性能,计算比较了对O2与SO2的吸附能、电荷转移量、稳定构型、态密度以及O2活化后的键长。结果显示3种催化剂对O2的吸附能均大于SO2,均服从E-R机理,其中B/C-C3N对O2的吸附能最大、O2与SO2之间吸附能之差最大,对O2的活化程度最高,表现出最利于SO2催化氧化反应的性能。态密度分析也表明,O2与B/C-C3N在费米能级附近的杂化作用最强,这更利于反应的发生。因此,B/C-C3N具有成为SO2氧化反应优良催化剂的潜力。     

Mg17Al12、Al2Y及Al2Ca相稳定性与弹性性能第一原理研究

采用基于密度泛函理论的Castep和Dmol程序软件包,计算了Mg17Al12、Al2Y及Al2Ca相的结构稳定性、弹性性能与电子结构。形成热和结合能计算结果表明:Al2Y具有最强的合金化形成能力和结构稳定性;热力学性质计算结果表明:在298~573 K温度范围内,Al2Y的Gibbs自由能始终最小,其结构热稳定性最好,Al2Ca次之,Mg17Al12最差,Y和Ca合金化Mg-Al系合金形成Al2Y及Al2Ca利于提高镁合金的高温抗蠕变性能;弹性常数的计算结果表明:3种金属间化合物均为脆性相,Mg17Al12的塑性最好;采用弹性常数计算结果预测的Al2Y熔点最高,其结构热稳定性最好。态密度和Mulliken电子占据数的计算结果表明:Al2Y结构最稳定的原因,主要源于体系在Fermi能级以下区域成键电子存在强烈的共价键作用。     

第一性原理研究合金元素对3C-SiC/Mg界面的影响

采用基于密度泛函理论的第一性原理方法,研究掺杂单个Al、Zn、Cu、Ni、Li、Zr原子对3C-SiC/Mg体系界面结合的影响,选取代表性的Zn原子和Zr原子进行Mulliken电荷、重叠布居数和态密度计算分析。结果表明,3C-SiC/Mg界面模型最稳定的堆垛结构是将5层的Mg（0001）堆垛在10层的 3C-SiC（111）面上,C封端的中心型模型在6种3C-SiC/Mg模型结构中分离功最大,界面间距最小,界面的润湿性最好;掺杂Zn原子后,3C-SiC/Mg-Zn体系的分离功减小,掺杂的Zn原子与Mg原子成反键,态密度中赝能隙变小使得3C-SiC/Mg-Zn体系的共价键性减弱,不利于3C-SiC/Mg-Zn界面结合; 掺杂Al、Cu、Ni、Li、Zr原子后,体系的分离功增大,Zr原子对界面润湿性的改善效果最好。掺杂Zr原子后,界面层Mg原子与Si原子的反键消失,与C原子在界面处形成Zr-C强共价键,态密度离域性增强,成键能力增强,导致3C-SiC/Mg-Zr体系的分离功增大最多。     

（Co，Ir）3（Al，W）析出相稳定性和弹性性质第一性原理的研究

采用基于密度函数理论的缀加平面波加局域轨道方法和超晶胞方法对L12结构和六方结构（Co，Ir）。（Al，W）析出相的能量和电子结构以及L12结构（Co，Ir）。（Al，W）析出相的弹性常数进行了理论计算．研究了（Co，Ir）。（Al，W）析出相的稳定性和弹性性质．通过Voigt—Reuss—Hill方法计算出（Co，Ir）。（Al，W）析出相的杨氏模量和切变模量．能量和电子结构的计算结果表明，（Co，Ir）3（Al．W）析出相能以立方L1。结构稳定存在．弹性性质的计算结果表明，L1。结构（Co，Ir）s（Al，W）析出相的弹性模量较Co—Ir合金高．且能对Co—Ir合金起到强化作用；（Co，Ir）。（Al．W）析出相是一种脆性化合物．     

First-principles energy and vibration spectrum simulations of Cr/V interacting with H in W-based alloy in a fusion reactor

We perform first-principles total energy and vibration spectrum calculations to study the effect of Cr/V on the H formation and diffusion at temperature range 300–2100 K in dilute W–Cr/W–V alloy. Temperature and H chemical potential are two important factors to affect the H formation energy and migrating energy. The H formation energy referring to the static/temperature-dependent H chemical potential decreases/increases with the temperature. At each given temperature, the presence of Cr in W reduces the H formation energy, while the existence of V in W has little effect on the H formation energy. The diffusion energy barrier and pre-exponential factor strongly depend on the temperature and increase with the temperature from 300 to 2100 K. Both Cr and V additions in W has a large consequences on H migrating energy. The energy barriers at any given temperature can be reduced by ～0.05 and 0.10 eV in W–Cr and W–V alloys, respectively. The current study reveals that vibration free energy plays a decisive role in the formation energy and migrating energy of H with the temperature, while the thermal expansion energy has little influence on the H formation energy and migrating energy with the temperature.     

First-principles calculations and experimental studies of Sn-Zn alloys as negative electrode materials for lithium-ion batteries

The physical characters and electrochemical properties of various phases in a Sn-Zn electrode,such as formation energy,plateau potential,specific capacity,as well as volume expansion,were calculated by the first-principles plane-wave pseudo-potential method based on the density functional theory.Sn-Zn films were also deposited on copper foils by an electroless plating technique.The actual composition and chemical characters were explored by scanning electron microscopy (SEM),X-ray diffraction (XRD),plasma atomic emission spectrometry (ICP),and constant current charge/discharge measurements (CC).The results show that separation phases with tin and zinc including a small quantity of Cu6Sn5 phase were obtained,the initial lithium insertion capacity of the Sn-Zn film was 661 mAh/g,and obvious potential plateaus of about 0.4 V and 0.7 V were displayed,which is in accordance with the results of theoretical calculations.The capacity of the Sn-Zn film decreased seriously with the increase of cycle number.     

First-principles study for surface tension and depolarizing effect on ferroelectric properties of BaTiO3 nanowires

The spontaneous polarization in ferroelectric (FE) nanowires (NWs) can be considerably enhanced due to the nanosize confinement by the first-principles calculations. The spontaneous polarization in a fully-relaxed BaTiO₃ NW with 2.0 nm in diameter is 1.18 times higher than that of bulk counterpart. The ferroelectric properties of the wire are found to generally depend on its dimensions through effects of the surface tension and near-surface depolarizing effect. The surface tension seems to be crucial for the giant enhancement of spontaneous polarization.