Creation of ferromagnetic properties of V–Fe and Zr–Fe alloys by hydrogen absorption

The results of investigations of V_1?y Fe _y H _x and Zr_1?y Fe _y H _x alloys by ⁵⁷Fe Mössbauer spectroscopy are presented and discussed in view of hydrogen ability to create ferromagnetic properties of the alloy. The results indicate two different possibilities of hydrogen influence on the hyperfine magnetic field. Hydrogen absorption causes the ferromagnetic behaviour of the alloys at significant lower iron concentration compared to the concentration of magnetic transition in binary alloys. The main reason for such behaviour is the anisotropic lattice expansion in hydrogenated V–Fe and Zr–Fe alloys as well as the decomposition of paramagnetic Zr-rich intermetallic compounds in the aftermath of the strong electron affinity of hydrogen for zirconium. These trends give rise to growth of magnetic clusters of Fe atoms so strong that they can participate in the overall magnetic properties of the system under investigation.     

Correlation between the atomic and electronic structure of metallic glasses

⁵⁷Fe Mössbauer and photoemission measurements were performed on meltquenched amorphous Fe(Zr, B) and (Fe, Ni)B alloys. The atomic and electronic structure of Fe₉₀Zr₁₀ and Fe₈₈B₁₂ glasses were found to be different. Half of the Zr content could be replaced by B in the Fe₉₀Zr₁₀ glass without changing its structure. Mossbauer investigation of the amorphous (Fe_1?xNi_x)_100?yB_y (0<=x<=0.80, 12<=y<=40) system indicates preferential arrangement of Fe and Ni atoms on the transition metal sites. According to the present XPS measurements there is a remarkable shift of 0.5 eV to higher binding energies of the B ls core level energy in the Ni rich glasses compared to Fe₈₈B₁₂ corresponding to a stronger binding between the Ni and the B atoms than that of Fe and B.     

Effects of additives on hydrogen absorption and desorption characteristics of Nd(Fe,Mo)12 alloys

Effects of such additives as Co, Zr, Nb or Ga on hydrogen absorption and desorption characteristics of Nd(Fe,Mo)₁₂ alloys are investigated. It is found that Zr or Nb addition increases the disproportionation temperature of Nd(Fe,Mo)₁₂ alloys, and Co or Ga addition decreases the recombined temperature of its disproportionated products. This shows that Zr or Nb addition retards the disproportionation, while Co or Ga addition is effective for improving the recombination, which is similar to the effects of the additives on the hydrogen absorption and desorption characteristics of Nd₂Fe₁₄B alloys. However, according to X-ray diffraction (XRD) investigations for the magnetic-oriented samples, the final hydrogenation disproportiontation desorption recombination (HDDR) NdFe_10.5−XM_XMo_1.5 (M=Co, Zr, Nb or Ga) products are isotropic. The effects of additives on hydrogen absorption and desorption characteristics of Nd₂Fe₁₄B and Nd(Fe,Mo)₁₂ alloys are very similar, but the magnetic anisotropy of the final two HDDR products are different. In order to investigate this, similarities and differences of the two alloy systems and their corresponding HDDR phenomena are further studied. The results show that the formation of anisotropic powders may be related to the disproportionated products and crystal growth direction of the Nd₂Fe₁₄B and Nd(Fe,Mo)₁₂ system.     

Analysis of electronic structures of 3d transition metal-doped TiO2 based on band calculations

The electronic structures of titanium dioxide (TiO₂) doped with 3d transition metals (V, Cr, Mn, Fe, Co and Ni) have been analyzed by ab initio band calculations based on the density functional theory with the full-potential linearized-augmented-plane-wave method. When TiO₂ is doped with V, Cr, Mn, Fe, or Co, an electron occupied level occurs and the electrons are localized around each dopant. As the atomic number of the dopant increases the localized level shifts to lower energy. The energy of the localized level due to Co is sufficiently low to lie at the top of the valence band while the other metals produce midgap states. In contrast, the electrons from the Ni dopant are somewhat delocalized, thus significantly contributing to the formation of the valence band with the O p and Ti 3d electrons. Based on a comparison with the absorption and photoconductivity data previously reported, we show that the t_2g state of the dopant plays a significant role in the photoresponse of TiO₂ under visible light irradiation.     

The multiple hydrogen location near a α-Fe vacancy

The interaction between 10 hydrogen atoms and a α-Fe structure having a vacancy (V) has been studied using a cluster model and a semi-empirical theoretical method. The energy of the system was calculated by the atom superposition and electron delocalization molecular orbital method. The electronic structure was studied using the concept of density of states and crystal orbital overlap population curves.For the study of a sequential absorption, the hydrogen atoms were positioned in their energy minima configurations, near to the tetrahedral sites neighboring the vacancy, except the last H atom that was located far from the vacancy. The energy difference for H agglomeration was also computed. The vacancy-H_n complexes become less stable than VH species for more than three hydrogen's.The changes in the electronic structure of Fe atoms near the vacancy were also analyzed. The interactions mainly involve Fe 3d and 4s atomic orbitals. The contribution of Fe p orbitals is much less important. The Fe-Fe bond weakened as new Fe-H and H-H pairs were formed. The effect of H atoms is limited to its first Fe neighbors. The detrimental effect of H atoms on the Fe-Fe bonds can be related to the mechanism for embrittlement in α-Fe.     

合金元素Zr韧化不同计量比Ni3Al合金的微观机制

利用正电子湮没技术（PAT）测量了不同化学计量比二元Ni3₃Al合金及不同Zr含 量Ni3₃Al合金的正电子寿命谱，并估算了合金基体和晶界缺陷处的自由电子密度.结果表明，二元Ni77₇₇Al23₂₃合金的基体和缺陷态的自由电子密度都比二元 Ni74₇₄Al26₂₆合金的高. Ni3₃Al合金晶界缺陷处开空间大于Ni空位或Al空位的开空间，晶界缺 陷处的自 关键词： 3Al合金')" href="#">Ni3₃Al合金 微观机制 自由电子密度 韧化     

Effect of low-valent atom substitution on electronic structure and magnetic properties of Fe1.5M0.5CoSi (M=V, Cr, Mn, Fe) Heusler alloys

Quaternary Heusler alloys Fe_1.5M_0.5CoSi with M=V, Cr, Mn and Fe have been investigated theoretically and experimentally. All of these samples crystallize in the ordered Heusler-type structure. The calculated electronic structure shows a pseudogap around E_F in the minority spin states of Fe₂CoSi. With the substitution of low-valent atoms for Fe, the majority antibonding peak is shifted to higher energy and a minority gap around the Fermi level is opened. High spin polarization ratio is obtained in Fe_1.5M_0.5CoSi (M=V, Cr, Mn) alloys. The calculated total spin moments decrease with decreasing number of valence electrons and follow the Slater-Pauling curve, which agree with the experimental results well. The Curie temperature decreases as M atom varies from Fe to V, but is always higher than 650 K, which is suitable for technical applications.     

A first principles calculation of site occupancy of the B2 phase in Ti2AlX (X=V,Cr, Fe,Mo, Ta,Nb, Zr,Hf and Re) intermetallics

The site occupancy of the B2 phase in Ti₂AlX (X=V, Cr, Fe, Mo, Ta, Nb, Zr, Hf and Re) intermetallics have been studied using first principles pseudo potential plane wave method.The Ti, Al and X atoms are arranged in five different ways, in the lattice sites corresponding to B2 structure of Ti₃Al. In Ti₃AlX, the X atoms are substituted at the Ti and / or Al sites. Further, the equilibrium lattice constants and the formation energy (E_for) of these intermetallics with different site occupancies in the B2 phase have been predicted. The formation energy values suggest that the B2 phase is stable in all alloys. Amongst the five cases in a particular alloy, stable configuration is identified with the minimum E_for and is further considered for the calculations of mechanical properties. All the alloys are mechanically stable in terms of Born stability criteria and show anisotropic behaviour. All the alloys display ductile behaviour in terms of G/B ratio.     

非晶态贮氢材料锆镍合金的结构研究

本文报道了非晶态贮氢合金在吸氢前、后两种情况下作X射线散射分析得到的结果。根据对实验得到的径向分布函数RDF(r),简约径向分布函数G(r)的分析,表明吸氢后氢原子主要进入单一由锆原子组成的四面体间隙中,少部分进入由一个镍原子、三个锆原子组成的四面体间隙中;非晶态Ni_0.243Zr_0.757合金的平均配位数为10.6,内部原子配位情况在吸氢前后没有改变;样品在约20?范围内具有短程有序结构。 关键词：     

成分和过渡金属对FeZr基非晶态合金晶化温度的影响

本文系统研究了Fe_100-xZr_x,(Fe_1-xZr_x)₈₄B₁₆和Fe_90-xM_xZr₁₀(M=V,Cr,Mn,Co,Ni,Si,B)非晶态合金的晶化温度与成分的关系。主要结果有:用Zr替代Fe使晶化温度明显提高;在FeMZr非晶态合金系列中,晶化温度依M=Mn,Cr,V元素的顺序和M含量x的增大而提高,而依 关键词：     

Low temperature specific heat and magnetic properties of V/FE and V/FE/H alloys

Low temperature specific heats of V_1?xFe_x (0?x?0.34) and V_1?xFe_xH_n (x = 0.02; 0.05; 0.1; 0.15 a 0 ? n ? 0.98) were investigated between 1.5 and 16 K.In V/Fe alloys temperature independent band paramagnetism was observed at iron concentrations below 20at%; at higher iron contents local magnetic moments occur and contribute magnetic terms to the low temperature specific heat. According to Schröder [14] these contributions can be explained by thermal agitation of superparamagnetic clusters of the Fe atoms with local moments. In the temperature range of the specific heat measurements the magnetic terms are dependent on temperature (contrary to Schröder) and can be described by Planck-Einstein functions. A separation of the magnetic contributions from the lattice and electronic term of heat capacity could be obtained in a satisfying way by least squares fitting with three Planck-Einstein functions.In “nonmagnetic” V/Fe alloys with less than 20at% Fe absorption of hydrogen generates local magnetic moments and superparamagnetic contributions. These are, therefore, connected primarily more with the band electron concentration n_e, than with the iron content X_Fe At the highest n_e, values, n_e >0, large negative deviations from the regular course of the heat capacity plot are observed; these can be related to mictomagnetic behavior (freezing temperature of spin-glass state above the range of measurements, T_F > 16 K).After correction for the superparamagnetic contributions there remains in the Fe containing alloys an appreciable enhancement of the electronic heat coefficient γ, up to a factor of about 2 when compared with the iron-free V/H samples. This effect is interpreted as resulting from mass enhancements of the itinerant electrons by electron-magnon (and-paramagnon) interactions.     

Features of hydrogen interaction in the Pd-based alloys with 3d transition metals

The effect of an alloying metal and its magnetic state on the hydrogen absorption energy has been investigated in the Pd-based alloys Pd₃Me with 3d transition metals (Me = Ti, V, Cr, Mn, Fe, Co, Ni, and Cu) using calculations from first principles. The full-potential and linearly augmented plane wave (FP LAPW) method has been used in the local density approximation (LDA) for the exchange-correlation potential in the framework of the density functional theory (DFT). It has been found that the hydrogen solubility in an alloy increases if the centers of mass of s and d metal bands and s hydrogen band shift strongly toward the Fermi level. The changes in properties of hydrogen absorption as a function of its position in a crystal lattice structure and magnetic state of an alloy have been analyzed.     

Magnetic and electrical transport properties of amorphous Zr-Fe alloys

Amorphous Zr_1?xFe_x samples were prepared in the composition range 0.2 ? x ? 0.9 either by means of vapour deposition or melt spinning. The electrical resistivity was determined in the range 4.2–300 K. Negative temperature coefficients were observed in the whole concentration range. The extended Ziman theory (diffraction model) was found to be able to explain these results only if the effective valence of the Fe atoms involves not only s electrons but also d electrons. The magnetic properties and the ⁵⁷Fe Mössbauer effect of the Zr_1?xFe_x alloys were studied in the range 4.2–300 K. The Fe-rich alloys are ferromagnetic. The Fe moment vanishes in alloys of an Fe concentration lower than about 50 at%. In most alloys (x ? 0.8) the Curie temperature is below room temperature and continuously decreases with Zr concentration. By means of Mössbauer spectroscopy and magnetic measurements it is shown that compositional short-range order (CSRO) is present to a higher degree in melt-spun alloys than in vapour-deposited alloys. The effect of sign and magnitude of the heat of solution on CSRO and the magnetic properties is discussed.     

Influence of hydrogen absorption on magnetic properties of Zr(Fe1−xVx)2 ternaries

Measurements of magnetization, susceptibility and Mössbauer effect were made on Zr(Fe_1?xV_x)₂ ternaries and their hydrides. Absorbed hydrogen leads to a large increase (20–30%) in volume without a change in the crystal structure. Ferromagnetism in the Fe-rich region is enhanced by hydrogen absorption, whereas hydrogenation leads to suppression of superconductivity in the V-rich range. The Fe moments in the Zr(Fe_1?xV_x)₂ hydrides are remarkably larger than those in the corresponding host compounds. The Fe moment in the β-ZrFe₂ hydride extrapolated reaches to 2.9μ_B, which exceeds the saturation value in bcc Fe. The hyperfine fields of ⁵⁷Fe in both Zr(Fe_0.8V_0.2)₂ and the hydride distribute widely, indicating that the Fe moments are very sensitive to the local environment arround the Fe atoms. Arguments are presented that it is possible to interprete the Fe moment increase by hydrogenation in terms of a decrease in occupancy of the 3d-band state due to electron transfers from Fe to hydrogen and/or vanadium.     

Quadrupole splitting on57Fe nuclei and local structure of the amorphous alloys Ni−Zr,Ni−Ta

Quadrupole splittings on⁵⁷Fe nuclei were studied by Mössbauer spectroscopy in amorphous and crystalline Ni-based alloys with 37 at .% Zr and 25–50 at .% Ta with 0.5 at .%⁵⁷Fe addition. Quadrupole splitting distributions and then the topological short range in Ni?Ta alloys were found to be similar to that of the Ni₃Ta intermetallic compound. The distribution of splittigs for Ni?Zr alloy is similar to that of its crystalline counterpart.     

Zr基大块非晶中添加元素对非晶形成能力及耐蚀性的影响

运用实空间递归方法研究了添加元素Nb,Ta,Y,La对Zr基非晶合金的非晶形成能力和耐腐蚀性能的影响.用计算机编程构造了Zr基非晶中初始晶化相Zr₂Ni的原子结构模型,用Zr₂Ni中的二十面体原子团簇模拟非晶中的二十面体团簇.计算了替代二十面体中心或顶角位置原子前后Ni,Zr及合金元素的局域态密度、团簇中心Ni与近邻Zr原子及Ni与替代元素Nb,Ta,Y,La间的键级积分,还计算了合金元素替代前后团簇的费米能级.局域态密度计算结果表明：合金元素Cu占据二十面体团 关键词： 电子结构 Zr基大块非晶 非晶形成能力 耐蚀性     

A DFT study on small M-doped titanium (M = V, Fe, Ni) clusters: structures, chemical bonds and magnetic properties

The equilibrium structures, electronic properties of bimetallic Ti_1-4M (M=V, Fe, Ni) clusters are investigated by using the density functional method within generalized gradient approximation in conjunction with the valence basis set. Considering the spin multiplicity effect, the geometries with different spins are optimized to find the ground states. For the ground states, the natural bonding orbital analysis (NBO) is performed and shows that the 4s electrons always transfer to the 3d orbital in the bonding atoms so that 4s and 3d orbitals hybridize with each other. The electron transfers from Ti atoms to the ‘impurity’ atoms (V, Fe, and Ni) are also found. The two kinds of electron transfer mechanisms are considered to be the contributor for the stabilities of the studied clusters. The Wiberg bond order and AIM (atoms in molecules) analyses indicate that the relative stabilities of chemical bonds are: $\text{Ti-V/Ti-Fe} > \text{Ti-Ti} > \text{Ti-Ni}$\text{Ti-V/Ti-Fe} > \text{Ti-Ti} > \text{Ti-Ni}. The spin magnetic moments are found to be mostly located at Ti atoms. Several clusters like Ti₂V, Ti₃V, Ti₃Ni and Ti₄Ni present the high moments.     

An isotope effect in electrolytic hydrogen absorption of some transition metals studied by ERDA and SIMS techniques

The depth profiles of protium and deuterium which were charged electrolytically, were measured by elastic recoil detection analysis (ERDA) and secondary ion mass spectrometry (SIMS) techniques in order to study the isotope effect in hydrogen absorption of Ti, Zr, Nb, Ni and Pd. The absolute loading ratios of H(D)/metal were calculated from the ERDA spectra and the depth profiles of SIMS were compared with the results of the ERDA. The isotope absorption ratios are estimated to be (D/H)_Ti=0.43, (D/H)_Zr=0.53, (D/H)_Nb=0.17 and (D/H)_Pd=0.10. The content in Ni is below the detection limit. The mass balance equations based on the transport–absorption model, were applied to analysis of the experimental results. This model reveals that the isotope absorption ratios for the Nb and Pd cases are governed mainly by the flux of hydrogen ions flowing to the surface of the metal electrode. However, the competition between the absorption–conversion process and the recombination process mainly determine the isotope ratio for the Ti and Zr cases.     

The changes in the electronic structure of B2 FeAl alloy with a Fe antisite and absorbed hydrogen

The electronic structure and bonding in a B2 FeAl alloy with and without hydrogen interaction with a Fe antisite were computed using a density functional theoretical method. The hydrogen absorption turns out to be a favorable process. The hydrogen was found close to an octahedral site where one of its Al capped is replaced by a Fe antisite. The Fe–H distance is of 1.45 Å same as the Al–H distance.The density of states (DOS) curves show several peaks below the d metal band which is made up mostly of hydrogen based states (>50% H_1s) while the metal contribution in this region includes mainly s and p orbitals.An electron transfer of nearby 0.21e⁻ comes from the metal to the H. The overlap population values reveal metal–metal bond breaking, the intermetallic bond being the most affected. The H bond mainly with the Al atom and the reported Fe–H overlap population is much lower than that corresponding to FePd alloys and BCC Fe. The changes in the overlap population show the Fe–Al bond is weakened nearly 41.5% after H absorption, while the Fe–Fe bond is only weakened 34.5%. H also develops a stronger bond with the Al atoms. The main bond is developed with Al being twice stronger than Fe–H.     

Onset of magnetism in concentrated ternary alloys I

The onset of magnetism and the magnetic propreties of concentrated substitutional ternary alloys A(Fe_1?xB_x)₂ (A = Y, Zr, U; B = Mn, Co, Ni and Al), Y₂(Ni_1?xCo_x)₇, Y(Ni_1?xCo_x)₃, Y₆(Fe_1?xMn_x)₂₃ and Ti(Fe_1?xCo_x) as well as the amorphous alloy system (Fe_1?xNi_x)₇₇Si₁₀B₁₃ are discussed in terms of homogeneous and heterogeneous models based on the Stoner-, Edwards- Wohlfa arth- and the Landau theory of phase transitions of second order. For a detailed comparison of the nine ternary systems A(Fe, B)₂ (A = Y, Zr, U; B = Mn, Co, Al) we refer to a following paper. From the results obtained on alloying UNi₂ with Fe, Co and Cu we propose that the magnetic moment of UNi₂—contrary to UFe₂—resides mainly on U rather than on the Ni site. The appearance of magnetism in YNi_x compounds by either changing the Y : Ni ratio or substituting Ni by Co in YNi₃ and Y₂Ni₇ is mainly attributed to band effects for which a schematic N(E) curve is proposed. The breakdown of long-range magnetic order in Y₆(Fe, Mn)₂₃ seems to be caused by a lack of delocalized electrons and a preferential site occupation of Mn and Fe. The magnetic properties of Ti(Fe_1?xCo_x) change from an itinerant to a localized moment behaviour above and below x = 0.5 due to the occurrence of Fe antistructure atoms which drive the onset of long-range magnetic order. The occurrence of magnetism in amorphous alloys compared with that of crystalline alloys with a high degree of disorder may be characterized in a similar way.