First-principles calculation of dehydrogenating properties of MgH_2-V systems

1 Introduction As potential energy storage materials, magnesium-based hydrogen storage alloys have been extensively researched due to their high hydrogen storage capacity, light weight and low cost[1―3]. However, a slow hydriding and dehydrogenating kinetics and high disso- ciation temperature limit its practical application for hydrogen storage. The mechanical alloying of MgH2 and transition metal elements has been experimentally confirmed to be an efficient method. For example, Ni, V, Ti,…     

Study on H atoms diffusion and adsorption properties of MgH<Subscript>2</Subscript>-V systems

Based on experimental results that VH_0.81/MgH₂ interface was found during the process of mechanically milling MgH₂+5at.%V nanocomposite, H atoms diffusion and adsorption properties of MgH₂-V systems have been investigated by using a first-principles plane-wave pseudopotential method based on the density functional theory. The results are as follows. When VH/MgH₂ interface is formed due to V alloying MgH₂ phase, the vacancy formed by H atoms near VH phase region is more stable than that without V alloying, while vacancy near MgH₂ phase region is less stable than that without V alloying. During the process of H atoms diffusion after V alloying, the max migration barrier energy of H atoms in MgH₂-V systems is reduced compared with that of MgH₂ phase, which means that H atoms diffuse easily. When H diffuses into VH from MgH₂ across VH/MgH₂ interface, among three substitutions such as the replacement of H for V vacancy, or interstitial site or V atoms, the replacement of H for V vacancy has the strongest diffusion ability, next interstitial site, and finally V atoms site. As far as H adsorbed on different surfaces of VH phase is concerned, physical adsorption is carried out more easily than chemical adsorption, and the behavior of H atoms adsorbed on the surface near VH phase region can be found more easily than that near MgH₂ phase region. Supported by the Ministry of Science and Technology of China (Grant No. 2006CB605104) and the National Natural Science Foundation of China (Grant No. 50771044)     

Statistical values of valence electron structure parameters applied to research on phase transition temperature and eutectoid reaction of titanium alloy

Based on the empirical electron theory of solids and molecules (EET), the statistical values of valence electron structure parameters Sn _A and SE _A which can characterize the properties of alloy phases are calculated, and influences of alloying elements (e.g., V, Nb, Mo, Hf, Zr, Fe, Mn, Co, Cr, Si, and so on) on the phase transition temperature and eutectoid reaction of titanium alloy are discussed with the statistical values of valence electron structure parameters. The research results agree well with real situations. Supported by the National Natural Science Foundation of China (Grant No. 50471022, 50741004) and National Key Basic Research Program of China (“973”) (Grant No. 2007CB613807)     

Theoretical calculation of the impact work in the alloying non-quenched and tempered steel

Liu et al.[1―5]1) have calculated the finishing rolling tensile strength σb, yield strength σs, elongation δ of the alloying non-quenched and tempered steel with the covalent elec-1) Liu Z L, Lin C, Guo Y C. Theoretical calculation of the finishing rolling elongation in alloying non-quenched and tempered steel. Progress in Natural Science, in presstron number nA of the strongest bond in alloying phases and the smallest electron density difference ?ρ of phase interfaces. It is calculat…     

Crystal structure and hydrogen storage behaviors of Mg/MoS<Subscript>2</Subscript> composites from ball milling

The Mg/MoS₂ composites were prepared by ball milling under argon atmosphere, and the effect of MoS₂ on the crystal structure and hydrogen storage properties of Mg was investigated. It is found that 10 wt% of MoS₂ is sufficient to prevent particle aggregation and cold welding during the milling process. The crystallite size of Mg will remain constant at slightly less than 38.8 nm with the milling process due to the size confinement effect of MoS₂. The dehydrogenation temperature of MgH₂ is reduced to 390.4-429.4 °C due to the crystallite size reduction. Through fitting by Johnson-Mehl-Avrami model, it is found that Mg crystal grows by three dimension controlled by interface transformation during the process of MgH₂ decomposition. MoS₂ has a weak catalyst effect on the decomposition of MgH₂ and activation energy of 148.9 kJ/mol is needed for the dehydrogenation process calculated by the Arrhenius equation.     

Structure and migration characteristic of heterointerfaces during the phase transformation from L1<Subscript>2</Subscript> to DO<Subscript>22</Subscript> phase

Based on the microscopic phase-field model, the structure and migration characteristic of ordered domain interfaces formed between DO₂₂ and L1₂ phase are investigated, and the atomistic mechanism of phase transformation from L1₂ (Ni₃Al) to DO₂₂ (Ni₃V) in Ni₇₅Al _x V_25−x alloys are explored, using the simulated microstructure evolution pictures and the occupation probability evolution of alloy elements at the interface. The results show that five kinds of heterointerfaces are formed between DO₂₂ and L1₂ phase and four of them can migrate during the phase transformation from L1₂ to DO₂₂ except the interface (002)_D//(001)_L. The structure of interface (100)_D//(200)_L and interface (100)_D//(200)_L·1/2[001] remain the same before and after migration, while the interface (002)_D//(002)_L is formed after the migration of interface (002)_D//(002)_L·1/2[100] and vice versa. These two kinds of interface appear alternatively. The jump and substitute of atoms selects the optimization way to induce the migration of interface during the phase transformation, and the number of atoms needing to jump during the migration is the least among all of the possible atom jump modes.     

Theoretical calculation of the finishing rolling impact work in non-quenched and tempered Si-Mn steel

Liu et al.[1―4] have given the calculation methods and general formulas of the finishing rolling tensile and yield strength of the non-quenched and tempered steel by using the electron structure parameters, and the calculated results agree well with the measured ones. In engineering technical standards, the σ b, σ s, δ and αk are always used simulta- neously. Therefore, the theoretical calculation neglecting δ and αk is not of integrity inboth learning and engineering. So the non-quench…     

A Novel Topological Index F^＊ and Its Correlation with Standard Formaton Enthalpies of ABn（g） Molecules

The topological index F^* is defined and obtained by the method of a non-dimensional unit calculation in which three matrices multiply with each other.These matrices represent the connectine cases of atoms in a molecule,the structural features of atoms on top and the bonded cases of the adjacent atoms respectively.The standard formation enthalpies of ABn(g) molecules were correlated with F^*(A=C,Al,Si,Ti,Zr,B=F,Cl,Br,I,H,n=1-4)and these correlation coefficients are all more than 0.96 .Some molecules(e.g CH4,SiH4,etc)can be preferably handled by F^* but can not be dealt with by other topological indices.By contrast to traditional hydrogen suppressed graph,the contribution of hydrogen atoms to structures and properties of molecules is considered.     

Structure and electrochemical properties of LiCoO2 synthesized by microwave heating

Microwave synthesis method was applied to the fast preparation of LiCoO₂. The structure of the synthesized oxides was analyzed by using X-ray diffraction. Only single-phase LiCoO₂ was obtained. Electrochemical behaviors of LiCoO₂ were investigated by charge-discharge cycling properties in the voltage range of 3.00 – 4.35 V (vs Li). The results show that the prepared LiCoO₂ powders calcinated at 900 °C for 120 min exhibit an initial charge and discharge capacity of 168 and 162 mA · h · g⁻¹ at 0.1C current rate, respectively, as compared to 159 and 154 mA · h · g⁻¹ of LiCoO₂ synthesized by conventional means. In addition, more than 95% of the capacity is retained even after 10 cycles. But with the increase of calcinating time, its electrochemical properties deteriorate. Compared with the conventional method, the microwave heating method is simple, fast, and with high energy efficiency.     

The electronic structure and grain boundary segregation by boron addition

The electronic structure and grain boundary segregation caused by boron addition to Ni₃Al have been studied by X-ray photoelectron spectroscopy and Auger electron spectroscopy, respectively. The obtained results show that the Ni2p_3/2 electron binding energy rises gradually in the sequence of pure Ni<Ni₇₆Al₂₄<Ni₇₄Al₂₆<Ni₇₅Al₂₅, while it reduces monotonously with an increase in boron addition to Ni₃Al. Besides, it is found that the grain boundary segregation of boron occurring in Ni₃Al is a combined equilibrium and non-equilibrium type in nature. Based on the concept of the bonding environmental inhomogeneity, measured by the shift in Ni2p_3/2 electron binding energy from the nickel atoms in the simple substance nickel to those in the intermetallic compound Ni₃Al (ΔE _B), being responsible for the brittle behavior of the alloy, a binding energy shifting criterion for the brittle-ductile fracture transition in Ni₃Al is presented; when ΔE _B>0, the brittle failure occurs in Ni₃Al; when δE _B<0, the ductile one appears. Combined with the above experimental rules, the criterion predicts that pure Ni₃Al is brittle, and there exist the stoichiometric effect and concentration effect in the ductilization process for Ni₃Al by boron addition. Hence the criterion can be taken as a theoretical guide to alloy design in developing ductile intermetallics. Project supported by the National Natural Science Foundation of China.     

Novel preparation and XPS analysis of V<Subscript>2</Subscript>O<Subscript>5</Subscript> xerogel

The V₂O₅ sol was fabricated by ultra-fast quenching. The vanadium with low valence (V⁴⁺) was found in V₂O₅ xerogel films by XPS analysis. The technology of oxygen top-blown was applied to analyze the XPS spectrum difference of V₂O₅ xerogel when the powder of V₂O₅ was melting in air or in oxygen atmosphere. The results show that the different melting atmosphere has certain influences on the chemical valence of V₂O₅ xerogel. ZHU Quan-yao: Born in 1968 Funded by the National Natural Science Foundation of China (No. 50172036, No. 59802009)     

Nanocomposite films of V<Subscript>2</Subscript>O<Subscript>5</Subscript>−MoO<Subscript>3</Subscript> xerogel with poly ethylene oxide intercalation

Poly ethylene oxide (PEO)_x−V₂O₅−V₂O₅−MoO₃ (x=0, 0.5, 1) films were prepared by the sol-gel method. The synthesis and structure of the films were investigated by XRD, TG-DTA, FTIR, etc. The results show that V₂O₅−MoO₃ xerogel has a layered structure and its interlayer space increased from 1.3181 nm at x=0 to 1. 7898 nm at x=1 after the nanocomposite films were dried, and PEO in the interlayer changes the interface structure by forming hydrogen bonds with V=0 bands. CV measurement indicates that the intercalation of PEO improves insertion/extration properties of Li⁺ ions in the interlayer. ZHENG Jin-xia: Born in 1976 Funded by the National Natural Science Foundation of China (No. 50172036) and Natural Science Foundation of Hubei Province(No. 2001ABB083)     

Viscoelastic properties of monodisperse spherical silica suspension

The viscoelastic properties of the suspension of monodisperse spherical silica produced by hydrolysis of tetraethoxysilane in alcohol solvent with ammonia as a catalyst in polyethylene glycol (PEG) were studied. The results show that the SiO2/PEG suspension possesses the reversible shear thinning and shear thickening behaviors. In the shear thinning region, the loss modulus (G″) almost remains unchanged, whereas the storage modulus (G′) decreases. In the shear thickening region, G″ and G′ increase for the formation of the "clusters". The larger G″ over G′ in all the stress studied shows that the system mainly possesses the viscous property, and that the energy dissipated(Ed) is larger than that stored. Ed of this suspension is proportional to the maximum strain (γmax) rising with the exponent of 1.92 under low shear stress; however, in the shear thickening region, Ed is proportional to γmax rising with the exponent of 5.00.     

First-principles calculations on the structure and electronic properties of boron doping zigzag single-walled carbon nanotubes

Calculations have been made for single-walled zigzag(n,0) carbon nanotubes containing substitutional boron impurity atoms using ab initio density functional theory.It is found that the formation energies of these nanotubes depend on the tube diameter,as do the electronic properties,and show periodic fea-ture that results from their different π bonding structures compared to those of perfect zigzag carbon nanotubes.When more boron atoms are incorporated into a single-walled zigzag carbon nanotube,the substit...     

Valence electron structure of the (ZrTi)B<Subscript>2</Subscript> solid solutions calculated by the three models

The Zr-rich (Zr_0.8Ti_0.2)B₂ and the Ti-rich (Ti_0.8Zr_0.2)B₂ solid solutions are formed when TiB₂ and ZrB₂ are hot-pressed. To forecast the properties of the two solid solutions, their valence electron structure was analyzed based on the empirical electron theory (EET) of solids and molecules. We used three different models, the average atom model, the average cell model and the real cell model, and compared with the calculation results from the three models. In the real cell model, the lattice constants of the solid solutions were supposed to be changed or unchanged. The results showed that different models could only result in slight change in the hybridization levels of the metal atoms in the two solid solutions and little difference between the calculation values. However, they can not change the variant trend of the valence electron structure nor the properties of the solid solutions. Thus, the three models and the methods are appropriate and the calculation results are reasonable and consistent. Supported by the National Natural Science Foundation of China (Grant No. 90505015)     

Preparation and microstructure of glass-ceramics and ceramic composite materials

The technology and microstructure of glass-ceramics and ceramic composite materials were studied. A suitable ceramic body was chosen on the basis of the sintering temperature of CaO-Al2O3-SiO2 system glass-ceramics. According to the expansion coefficient of the ceramic body, that of CaO-Al2O3-SiO2 system glass-ceramics was adjusted, fl-wollastonite was found present as the major crystalline phase in glass- ceramic. The CaO-Al2O3-SiO2 system glass-ceramic layer and ceramic body could be sintered together by adjusting the sintering period. The compositions of glass-ceramic layer and ceramic body diffuse mutually at 1 100 ℃, resulting in an interface between them. To achieve good sintered properties of glass-ceramics and the chosen ceramic body, at least a four-hour sintering time is used.     

Valence electron structure and properties of stabilized ZrO2

To reveal the properties of stabilizers in ZrO₂ on nanoscopic levels, the valence electron structures of four stable ZrO₂ phases and c-ZrO₂ were analyzed on the basis of the empirical electron theory of solids and molecules. The results showed that the hybridization levels of Zr atoms in c-ZrO₂ doped with Ca and Mg dropped from B17 to B13, the hybridization levels of Zr atoms in c-ZrO₂ doped with Y and Ce dropped from B17 to B15, and that the four stabilizing atoms all made the hybridization levels of O atoms drop from level 4 to level 2. The numbers of covalent electrons in the strongest covalent bond in the descending order are c-ZrO₂>Zr_0.82Ce_0.18O₂>Zr_0.82Y_0.18O_1.91>Zr_0.82Mg_0.18O_1.82>Zr_0.82Ca_0.18O_1.82. The bond energies of the strongest covalent bond and the melting points of the solid solutions in the descending order are Zr_0.82Ce_0.18O₂> c-ZrO₂>Zr_0.82Y_0.18O_1.91>Zr_0.82Mg_0.18O_1.82>Zr_0.82Ca_0.18O_1.82. The percentages of the total number of covalent electrons in the descending order are c-ZrO₂>Zr_0.82Y_0.18O_1.91> Zr_0.82Ce_0.18O₂>Zr_0.82Mg_0.18O_1.82> Zr_0.82Ca_0.18O_1.82. From the above analysis, it can be concluded that the stabilizing degrees of the four stabilizers in the descending order are CaO> MgO>Y₂O₃>CeO₂. Supported by the Major Project of the National Natural Science Foundation of China (Grant No. 90505015)     

Electrochemical behavior of diverse vanadium ions at modified graphite felt electrode in sulphuric solution

PAN-based graphite felt (PGF) treated in 98% sulphuric acid for 5 h and then kept at 450 ℃ for 2 h was evaluated for their electrochemical performance as electrodes of vanadium redox battery (VRB). Structure and characteristic of treated PAN-based graphite felt (TPGF) were determined by means of Fourier Transform Infrared Spectroscopy, Scanning Electron Microscopy, Brunauer-Emmett-Teller surface area analysis and VRB test system. The results show that the acid and heat synergistic effect increase the number of —COOH functional groups on the PGF surface, and the PGF is eroded by sulphuric acid oxidation, resulting in the surface area increases from 0.31 m2/g to 0.45 m2/g. The V(Ⅱ)/V(Ⅲ) redox reaction is electrochemically reversible on the TPGF electrode, while the V(Ⅳ)/V(Ⅴ) couple is a quasi reversible process. The diffusion coefficients of the oxidation for V(Ⅳ)/V(Ⅴ) obtained from the scope of peak current Ip vs scan rate v1/2 is 4.4×10-5 cm2/s. The improvement of electrochemical activity for the electrode is mainly ascribed to the increase of the number of —COOH groups on the TPGF, which behaves as active sites catalyzing the vanadium species reactions and accelerating electron transfer reaction and oxygen transfer.     

Devitrification behaviour of rapidly solidified Al87Ni7Cu3Nd3 amorphous alloy prepared by melt spinning method

Rapidly solidified Al87Ni7Cu3Nd3 amorphous alloy was prepared by using melt spinning. Its calorimetric behavior was characterized by using differential scanning calorimeter in a continuous or isothermal heating mode. phase transformation was investigated, with a special interest in primary crystallization, by using an in-situ examination of X-ray diffractometry （XRD） and high resolution transmission electron microscopy （HRTEM）. The results show that, the whole devitrification of rapidly solidified Al87NiyCu3Nd3 amorphous alloy involves two main processes of primary crystallization and secondary crystallization that consist mainly of two reactions. For primary crystallization, the apparent activation energies, EIso and EKis and growth activation energies Eg are about 153, 166 and 288 kJ/mol, respectively. The interdiffusion of Al atoms is a rate-controlled step of formation of the a（Al） particles, but slow diffusion of Ni and Nd atoms plays a significant role in retarding growth of the α （Al） particles. For secondary crystallization, EIso, EKis and Eg of the first reaction are about 291,208 and 290 kJ/mol, and those of the second reaction are about 367, 269 and 372 kJ/mol. The two reactions of secondary crystallization are controlled mainly in an interface-controlled three-dimensional mode, depending mainly on slow diffusion of Ni and Nd atoms.     

Phase structure and electrical properties of La<Subscript>2</Subscript>O<Subscript>3</Subscript>-doped BiInO<Subscript>3</Subscript>-PbTiO<Subscript>3</Subscript> ceramics with high curie temperature

The phase structure and electrical properties of pure and La2O3-doped Bi-InO3-PbTiO3 （BI-PT） ceramics were studied respectively. In （1 -x）BI-xPT （x=0.72-0.80） ceramics, the stability of tetragonal phase increased with increasing x, and pure perovskite structure was obtained for x=-0.80 ceramics. The phase transition temperature range was between 575 ℃ and 600 ℃ for x=0.72-0.80 ceramics, higher than that of PT （-490 ℃）. The c/a ratio almost linearly decreased with increasing La2O3 content in x-0.80 ceramics. It is believed that Pb^2＋ vacancies were formed by La^3＋ substituting Pb^2＋ in La2O3-doped BI-PT ceramics. Tc shifted to lower temperature by 30 ℃/mol% La2O3. The maximum dielectric constant 8557 around 559 ℃ was exhibited in 0.5mol%-doped BI-0.80PT ceramics. La2O3-doped ceramics could be poled resulting from decreasing of c/a ratio and improving of dielectric loss and resistivity. The maximum piezoelectric coefficient d33 was 12 pC/N for 2mol%-doped BI-0.80PT ceramics.