Phase evolution, Raman spectroscopy and microwave dielectric behavior of (Li1/4Nb3/4) doped ZrO2-TiO2 system

The phase evolution, Raman spectroscopy and microwave dielectric properties of (Li_1/4Nb_3/4) doped ZrO₂-TiO₂ system were investigated. The effects of the Zr/Ti ratio and the (Li_1/4Nb_3/4) substitution were addressed. X-ray diffraction and electron diffraction analysis showed that the crystalline phases of the (Li_1/4Nb_3/4) doped ZrO₂-TiO₂ ceramics depended greatly on the Zr/Ti ratio. The sample with Zr/Ti ratio of 7/9 crystallized as Zr₅Ti₇O₂₄ phase structure, a commensurate structure with a tripled a-axis superstructure and a Z^TTZ_TT sequence. Secondary phase of monoclinic ZrO₂ phase appeared when the Zr/Ti ratio was as high as 9/7. Raman analysis showed that the Raman peaks located at 651 and 624 cm⁻¹ were assigned to the vibration modes of Zr-O octahedron and Ti-O octahedron, respectively. The dielectric constant and quality factor (Qf value) of the (Li_1/4Nb_3/4) doped ZrO₂-TiO₂ ceramics decreased slightly as the Zr/Ti ratio changed from 6/10 to 9/7. The temperature coefficient of resonate frequency (TCF value) was sensitive to the Zr/Ti ratio and it showed a negative value when the Zr/Ti ratio was close to 5:7. Meanwhile, the TCF value of ZrO₂-TiO₂ ceramics could also be tailored by the (Li_1/4Nb_3/4) substitution.     

Electronic structure of ZrTiO4 and HfTiO4: Self-consistent cluster calculations and X-ray spectroscopy studies

Total and partial densities of states of the constituent atoms of ZrTiO₄ and HfTiO₄ titanates have been calculated using a self-consistent cluster method as incorporated in the FEFF8 code. The calculations reveal the similarity of the electronic structure of both titanates and indicate that the valence band of the compounds under consideration is dominated by contributions of O 2p states. These states contribute throughout the whole valence-band region; however their maximum contributions occur in the upper portion of the band. Other significant contributors in the valence-band region are Ti 3d and Zr 4d states in ZrTiO₄ and Ti 3d and Hf 5d states in HfTiO₄. All the above d-like states contribute throughout the whole valence-band region of the titanates; however maximum contributions of the Ti 3d states occur in the upper portion, whilst those of the Zr 4d (Hf 5d) states are in the central portions of the valence band. The FEFF8 calculations render that the bottom of the conduction band of ZrTiO₄ and HfTiO₄ is dominated by contributions of Ti 3d^? states, with also smaller contributions of Zr 4d^?/Hf 5d^? and O 2p^? states. To verify the above FEFF8 data, the X-ray emission bands, representing the energy distributions of mainly O 2p, Ti 3d and Zr 4d states, were measured and compared on a common energy scale. These experimental data are found to be in agreement with the theoretical FEFF8 results for the electronic structure of ZrTiO₄ and HfTiO₄ titanates. Additionally, X-ray photoelectron valence-band and core-level spectra were recorded for the constituent atoms of the titanates under study.     

Luminescence of orthovanadates M 3 + M3+(VO4)2 and M 2 + M4+ (VO4)2

The absorption, excitation, and luminescence spectra of vanadates of type M ₃ ⁺ M³⁺(VO₄)₂ and M ₂ ⁺ M⁴⁺(VO₄)₂ are studied, where M⁺ is Na, K, Rb, Cs; M³⁺ is Al, Sc; M⁴⁺ is Zr, Sn, Ti. The luminescence spectra maxima are located at 490–510 nm, while those of the excitation spectra are at 360–375 nm. Temperature characteristics of luminescence and thermostimulated luminescence are studied. The question of activation of complex vanadates by rare-earth ions is considered.Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 3, pp. 24–28, March, 1976.     

Micro‐Raman study of Zr‐substituted Bi4Ti3O12 ceramics

We have studied the lattice vibrational modes of Zr‐substituted Bi₄Ti₃O₁₂ ceramics using micro‐Raman spectroscopy. Replacement of Zr at the Ti site in the perovskite block is found from the increase in the lattice parameters as a function of Zr contents. Combined X‐ray diffraction patterns and Raman analysis suggested less than 40 mole% Zr solubility in Bi₄Ti₃O₁₂. At 40 mole% of Zr substitution or above, the unreacted monoclinic‐phase ZrO₂ is observed in the X‐ray diffraction patterns and the Raman spectra. The incorporation of Zr in Bi₄Ti₃O₁₂ reduces the soft mode wavenumber and the transition temperature. Moreover, temperature dependent studies confirmed the ferroelectric to paraelectric transition in Bi₄Ti₃O₁₂ at about 675 °C. On increasing the Zr content up to 40% on the Ti sites of Bi₄Ti₃O₁₂, a systematic decrease in the phase transition temperature from 675 to 630 °C was observed. Copyright © 2007 John Wiley & Sons, Ltd.     

Interlayer Exchange Coupling Across Quasi-Amorphous Ti-Co and Zr-Co Spacers

Co/Ti and Co/Zr multilayers with wedge-shaped and constant-thickness Ti and Zr sublayers were prepared using UHV DC/RF magnetron sputtering. Results showed that the Co sublayers are ferromagnetically coupled up to Ti and Zr spacer thickness of about 1.9 and 2.4 nm, respectively. Furthermore, a weak antiferromagnetic coupling of the Co sublayers was observed for a Ti (Zr) thickness range between 1.9 and 2.7 nm (2.4 and 3.2 nm). The Co sublayers are very weakly exchange coupled or decoupled for d _Ti 2.7 nm and d _Zr 3.2 nm. The rapid decrease of the interlayer exchange coupling could be explained by its strong damping due to formation of a non-magnetic quasi-amorphous Ti-Co and Zr-Co alloy layer at the interfaces.     

The first principle study of magnetic properties of Mn2WSn,Fe2YSn (Y=Ti,V), Co2YSn (Y=Ti,Zr, Hf,V, Mn) and Ni2YSn (Y=Ti,Zr, Hf,V, Mn) heusler alloys

The spin polarized electronic band structures, density of states (DOS) and magnetic properties of Mn₂WSn, Fe₂YSn (Y=Ti, V), Co₂YSn (Y=Ti, Zr, Hf, V, Mn) and Ni₂YSn (Y=Ti, Zr, Hf, V, Mn) huesler compounds are reported. The calculations are performed by using full-potential linearized augmented plane wave method (FP-LAPW) within density functional theory. The magnetic trend in these compounds is studied using values of magnetic moments, exchange interaction and calculated band gap. The results reveal that Mn₂WSn and Ni₂VSn show 100% spin polarization, Co₂YSn (Y=Ti, Zr, Hf, Mn), Fe₂YSn (Y=Ti, V), and Ni₂MnSn exhibit metallic nature and Ni₂YSn (Y=Ti, Zr, Hf) and Co₂VSn show semi-conducting behavior.     

Electrochemical and surface behavior of hydyroxyapatite/Ti film on nanotubular Ti-35Nb-xZr alloys

In this paper, we investigated the electrochemical and surface behavior of hydroxyapatite (HA)/Ti films on the nanotubular Ti-35Nb-xZr alloy. The Ti-35Nb-xZr ternary alloys with 3-10 wt.% Zr content were made by an arc melting method. The nanotubular oxide layers were developed on the Ti-35Nb-xZr alloys by an anodic oxidation method in 1 M H₃PO₄ electrolyte containing 0.8 wt% NaF at room temperature. The HA/Ti composite films on the nanotubular oxide surfaces were deposited by a magnetron sputtering method. Their surface characteristics were analyzed by field-emission scanning electron microscopy (FE-SEM), energy-dispersive X-ray spectroscopy (EDS) and an X-ray diffractometer (XRD). The corrosion behavior of the specimens was examined through potentiodynamic and AC impedance tests in 0.9% NaCl solution. From the results, the Ti-35Nb-xZr alloys showed a solely β phase microstructure that resulted from the addition of Zr. The nanotubular structure formed with a diameter of about 200 nm, and the HA/Ti thin film was deposited on the nanotubular structure. The HA/Ti thin film-coated nanotubular Ti-35Nb-xZr alloys showed good corrosion resistance in 0.9% NaCl solution.     

Ti-Zr-Ni单相准晶合金的室温力学性能研究

以Ti40₄₀Zr40₄₀Ni20₂₀合金为研究对象，用铜 模吸铸法制备出直径为3mm的致密单相准晶棒，通过维氏显微硬度测定和单向压缩实验方 法研究了该合金的室温力学性能 .结果表明：Ti40₄₀Zr40₄₀Ni20₂₀准晶具有良好 的弹性变形能力，室温弹性应 变可达125%.同时，它具有相对高的室温硬度（约55GPa），是普通Ti合金的15倍.T i40_{40 关键词： 准晶 Ti-Zr-Ni合金 解理断裂}     

Effect of Zr,Ti substitutions onT c in superconducting YBa2Cu3O7−δ system

Zr and Ti have been substituted in the system Y_1−x M _x Ba₂Cu₃O_7−δ(M=Zr, Ti,x=0.05,0.1). We find that theT _c value is unchanged, ∼90K for Zr substitutions up to 10% and in the case of Ti substitutions theT _c drops significantly. These changes may arise from their site preference.     

Electronic structure and glass forming ability in early and late transition metal alloys

A correlation between the change in magnetic susceptibility (Δχ_exp) upon crystallisation of Cu–Zr and Hf metallic glasses (MG) with their glass forming ability (GFA) observed recently, is found to apply to Cu–Ti and Zr–Ni alloys, too. In particular, small Δχ_exp, which reflects similar electronic structures, ES, of glassy and corresponding crystalline alloys, corresponds to high GFA. Here, we studied Δχ_exp for five Cu–Ti and four Cu–Zr and Ni–Zr MGs. The fully crystalline final state of all alloys was verified from X-ray diffraction patterns. The variation of GFA with composition in Cu–Ti, Cu–Zr and Cu–Hf MGs was established from the variation of the corresponding critical casting thickness, d_c. Due to the absence of data for d_c in Ni–Zr MGs their GFA was described using empirical criteria, such as the reduced glass transition temperature. A very good correlation between Δχ_exp and d_c (and/or other criteria for GFA) was observed for all alloys studied. The correlation between the ES and GFA showed up best for Cu–Zr and NiZr₂ alloys where direct data for the change in ES (ΔES) upon crystallisation are available. The applicability of the Δχ_exp (ΔES) criterion for high GFA (which provides a simple way to select the compositions with high GFA) to other metal-metal MGs (including ternary and multicomponent bulk MGs) is briefly discussed.     

Complete suppression of metastable phase and significant enhancement of magnetic properties of B-rich PrFeB nanocomposites prepared by devitrifying amorphous ribbons

The effect of refractory element addition on phase transformation, crystallization behavior and magnetic properties of Pr_8.5Fe_81.5B₁₀ (addition-free) and Pr_8.5Fe_81.5M₂B₁₀ (M=V, Cr, Nb, Zr, Ti) ribbons has been investigated. The annealed addition-free ribbon as well as the samples with V or Cr additions are mainly composed of the metastable Pr₂Fe₂₃B₃ phase, whereas annealed ribbons with Nb, Zr or Ti additions primarily consist of Pr₂Fe₁₄B and a minor amount of Fe₃B/boride. The complete suppression of the metastable Pr₂Fe₂₃B₃ phase due to Nb, Zr or Ti additions leads to a significant enhancement of the magnetic properties. For example, the remanence, the coercivity and the energy product are remarkably increased from 2.5 kG, 0.4 kOe and 0.2 MG Oe for the addition-free material to 9.2 kG, 4.7 kOe and 7.6 MG Oe for the specimens with Nb addition. The successful elimination of the metastable Pr₂Fe₂₃B₃ phase is believed to profit from two factors: (a) Nb, Zr or Ti atoms substitute the Pr site, comparatively increase the Pr content, and thus inhibit the nucleation of Pr-lean Pr₂Fe₂₃B₃ phases, and (b) the formation of Nb, Zr, or Ti borides consumes some part of B, which hinders the generation of the B-rich Pr₂Fe₂₃B₃ phase.     

On the properties of PZT solid solutions: A reply to a comment

Inside the two phase coexistence region of the Pb(Zr, Ti)O₃ solid solutions the properties of each phase can change with the ratio Zr/Ti only if there are metastable states. However, in the case of qeuilibrium states, the properties of each phase do not change, but only their relative amount. This conclusion is in agreement with our experimental results.     

Dependence of NiTi hydride stability by co-substitution by (Zr,Mg) onto Ti and (Cr,Cu) onto Ni: first-principles study

ABSTRACT

The thermodynamics of hydride formation is one of the most important properties of the metal-hydrogen system, and states its potential for further uptake. For this reason, much research is focused on the use of first principle calculations as a predictive tool in the study of hydride stability. In this paper, First-principles density functional calculations were performed to predict the effect of co-substitution in NiTiH, Ti by Mg and Zr (x?=?0.125, 0.25 and 0.375), as well as Ni by Cu and Cr (y?=?0.125). Structural, thermodynamic stability and electronic properties were investigated. The formation enthalpy when Ti is substituted either by Mg or Zr with respect to their content is calculated and compared to the host NiTiH; it is found that the hydride stability decreases as Mg content increases while it increases when Zr content increases. The substitution of Ni by Cu destabilises the hydride while the stability of the hydride is enhanced when Ni is substituted by Cr. The simultaneous substitution of Ti by Mg (x?=?0.375) and Ni by Cu (y?=?0.125), leads to considerable destabilisation and an increase in cell volume of the hydride. The corresponding Ni_0.875Cu_0.125Ti_0.625Mg_0.375 compound is identified with optimum characteristics among the considered compositions, thereby can be considered as potential material for hydrogen storage.     

X-ray absorption spectra: K-edges of 3d transition metals,L-edges of 3d and 4d metals,and M-edges of palladium

The X-ray absorption spectra of the 3d and 4d transition metals have been calculated within the single-particle approximation by a new linearized augmented plane wave method. The spectra, calculated with sharp atomic and band-structure single-particle levels, have been convoluted with a Lorentzian broadening function whose width is the sum of that of the core hole and the excited electrons. Plots are shown for (i) the K-edge fine structures up to at least 100 eV above the edge for Ca, Ti, Cr, Co, Cu, and Zn, (ii) the L_{2, 3} white lines for Ca, Ti, Cr, Co, and Cu, (iii) the L₃ white lines for Sr, Zr, Nb, Ru, Rh, and Pd, and (iv) the M_{2, 3} and M_4,5 spectrum of Pd. Systematic features which depend on the crystal structure and the placement of the Fermi level with conduction band are briefly discussed.     

Effect of Ti4+ ions on the magnetic and dielectric properties of Mg-ferrite

X-ray diffraction, the real part (ε′), the imaginary part (ε″) of dielectric constant, and the molar magnetic susceptibility (χ_M) for Mg_1+xTi_xFe_2−2xO₄ ferrite (0.1⩽x⩽0.9) were studied. The date of X-ray diffraction showed that the unit cell parameter increases with Ti concentration and ascribed to the predicted variation of the cation distribution, while Mg²⁺ ions are highly diffusible and very sensitive to heat. The effect of dilution by Ti ions is discussed in terms of increasing superparamagnetic and single domain (SP/SD) grains. The measurements of ε′ were performed at different temperatures as a function of frequency, while the magnetic susceptibility was studied at different magnetic field intensities. The variation of the dielectric properties depends mainly on the valence exchange between the different metal ions in the same site or in different sites. All parameters such as ε′, ε″, χ_M showed a decrease in value with increasing Ti and Mg concentration. The dispersion in ε′ with frequency disappeared gradually with increasing Ti concentration.     

Theoretical study of fusion reactions 32S + 94,96Zr and 40Ca + 94,96Zr and quadrupole deformation of 94Zr

The dynamic coupling effects on fusion cross sections for reactions~(32)S + ~(94,96)Zr and ~(40)Ca + ~(94,96)Zr are studied with the universal fusion function formalism and an empirical coupled channel(ECC) model. An examination of the reduced fusion functions shows that the total effect of couplings to inelastic excitations and neutron transfer channels on fusion in ~(32)S +~(94)Zr(~(40)Ca +~(94)Zr) is almost the same as that in ~(32)S +~(96)Zr(~(40)Ca +~(96)Zr). The enhancements of the fusion cross section at sub-barrier energies due to inelastic channel coupling and neutron transfer channel coupling are evaluated separately by using the ECC model. The results show that effect of couplings to inelastic excitations channels in the reactions with94 Zr as target should be similar as that in the reactions with ~(96) Zr as target. This implies that the quadrupole deformation parameters β_2of ~(94)Zr and~(96) Zr should be similar to each other.However, β_2 's predicted from the finite-range droplet model, which are used in the ECC model, are quite different. Experiments on~(48) Ca +~(94)Zr or~(36) S +~(94)Zr are suggested to solve the puzzling issue concerning β_2for~(94)Zr.     

Molecular dynamics study of radiation damage in lakargiite Ca(Zr,Ti,Sn)O3

The radiation stability of lakargiite Ca(Zr,Ti,Sn)O₃ was investigated by the molecular dynamics method using computer simulation. A nanofragment of the structure of a solid solution of the composition CaZr_0.8Sn_0.1Ti_0.1O₃ with sizes 310 × 290 × 315 Å, which contains 1.4 million atoms with a maximally disordered distribution of Zr, Ti, and Sn, was used for simulation. It has been established that the susceptibility of lakargiite to amorphization is considerably lower than that of other minerals such as zircon, monazite, and xenotime. The high radiation resistance of the studied solid solution makes it possible to suggest lakargiite as a possible matrix to utilize highly active radioactive wastes.     

掺杂对Ni51.5Mn25Ga23.5相变行为和磁性的影响

通过往母合金Ni_51.5Mn₂₅Ga_23.5掺入7种IVA, VA和VIA 过渡族元素得到系列掺杂合金Ni_51.5Mn₂₃M₂Ga_{23 .5}.M为掺杂元素.实验结果表明，掺杂效应一般引起马氏体相变温度的下降，其中，W 的掺杂是7种元素中唯一使相变温度升高的特例，且出现了中间马氏体相变.同时，在价电子 浓度不变的情况下，相变更敏感于原子的尺度效应.实验发现，Ti，Zr，Hf，V四种非磁性元 素的掺杂使Mn原子磁矩减小，而Nb，Ta，W三种非磁性元素的掺杂却可以明显地增大Mn原子 的磁矩.在考察掺杂效应时，不能忽略马氏体相变引起的晶格变化对材料磁性的影响. 关键词： NiMnGa 掺杂 马氏体相变 磁性     

Microprobe and TEM investigations into samarium-cobalt magnets of the 1–7 type

The preparation of magnets with energy products of up to 30 MGOe from Sm(Co, Cu, Fe, M)_z alloys with M=Ti or Zr and z=6.8 or 7.25, respectively, as well as their magnetic properties and microstructures have already been reported on. We describe, in addition, the distribution of the non-metallic impurities, O, N, and C, and the phases which they form with the metallic constiturents as found by electron beam micro analysis and transmission electron microscopy. Ti, Zr, and C combine in forming the very stable carbides TiC and ZrC. The possible role of these carbides in regard to the magnetic properties is discussed.     

Electronic properties of Pb(ZrTi)O3 solid solutions

The theoretical backgrounds and some experimental data on the electronic properties of polycrystalline Pb(Zr, Ti)O₃ solid solutions are summarized. These substances occur in the perovskite structure, and so their electronic band structure is presumed to be analogous to other perovskite compounds. Their forbidden gap energy has been determined to be about 3.30–3.56 eV on the basis of optical, photoacoustical, and photoelectrical measurements. Many local levels and traps exist in the forbidden gap because of the polycrystalline character and heterovalent doping. Their actual configurations and states strongly influence the optical, photoelectrical, piezoelectrical, and other physical properties of Pb(Zr, Ti)O₃ solid solutions.