Crystalline structural phase boundaries in (K,Na,Li)NbO 3 ceramics

Lead-free (K_xNa_1−x)_1−yLi_yNbO₃ ceramics (with x=0.50, y=0–0.08 and x=0.30–0.70, y=0.06, respectively) were synthesized using the conventional solid-state reaction technique. Compositional influences of K, Na and Li constituents on microstructures, crystalline structures, dielectric and piezoelectric properties were investigated. It has been known that microstructures change largely with the alkali constituents and that there exist three orthorhombic-tetragonal phase boundaries at room temperature. One occurs in (K_0.50Na_0.50)_1−yLi_yNbO₃ ceramics at y=0.05–0.06, which corresponds to the previously reported morphotropic phase boundary (MPB). The other two appear in (K_xNa_1−x)_0.94Li_0.06NbO₃ ceramics near x=0.40 and x=0.60, respectively. (K_0.50Na_0.50)_0.935Li_0.065NbO₃ and (K_0.45Na_0.55)_0.94Li_0.06NbO₃ ceramics show high piezoelectric properties with the d₃₃ values over 200 pC/N and the k_p values around 45% at room temperature. It is thought that the observed high piezoelectric properties are largely affected by the temperature-driven orthorhombic-tetragonal phase transition.     

Mixed hyperfine interactions in Fe-Mg-O: magnetic behaviour

The complex Mössbauer spectra exhibited by Fe_xO (x0.91) and (Fe_1–y Mg _y )_xO (y=0.15–0.85) powder samples at liquid helium temperature have been analysed by a Hamiltonian treatment to allow for the significant electric field gradients present at the Fe²⁺ defect sites. The magnetic behaviour of the defect clusters are considered in terms of antiferromagnetic couplings, consistent with the spin glass-like behaviour reported recently for magnesiowüstite.     

Structure, ferroelectric and piezoelectric properties of (Bi1−x−yNa0.925−x−yLi0.075)0.5BaxSryTiO3 lead-free piezoelectric ceramics

Lead-free multi-component ceramics (Bi_1−x−yNa_{0.925−x−y}Li_0.075)_0.5Ba_xSr_yTiO₃ have been prepared by an ordinary sintering technique and their structure and electrical properties have been studied. All the ceramics can be well-sintered at 1100 °C. X-ray diffraction patterns shows that Li⁺, Ba²⁺ and Sr²⁺ diffuse into the Bi_0.5Na_0.5TiO₃ lattices to form a new solid solution with a pure perovskite structure, and a morphotropic phase boundary (MPB) is formed at 0.04 < x < 0.08. As compared to pure Bi_0.5Na_0.5TiO₃ ceramic, the coercive field E_C of the ceramics decreases greatly and the remanent polarization P_r of the ceramics increases significantly after the formation of the multi-component solid solution. Due to the MPB, lower E_C and higher P_r, the piezoelectricity of the ceramics is greatly improved. For the ceramics with the compositions near the MPB (x = 0.04–0.08 and y = 0.02–0.04), piezoelectric coefficient d₃₃ = 133–193 pC/N and planar electromechanical coupling factor k_P = 16.2–32.1%. The depolarization temperature T_d reaches a minimum value near the MPB. The temperature dependences of the ferroelectric and dielectric properties suggest that the ceramics may contain both the polar and non-polar regions at temperatures near/above T_d.     

Water incorporation into the Ba2(In1 − xMx)2O5‪ (M = Sc 0 ≤ x < 0.5 and M = Y 0 ≤ x < 0.35) system and protonic conduction

Ba₂(In_1 − xM_x)₂O_{5 − y / 2}(OH)_y‪□_{1 − y / 2} (y ≤ 2; M = Sc³⁺ 0 ≤ x < 0.5 and M = Y³⁺ 0 ≤ x < 0.35) compounds were prepared by reacting Ba₂(In_1 − xM_x)₂O₅‪ phases with water vapor. This reaction is reversible. Analyses of the hydration process by TG and XRD studies show that the thermal stability of hydrated phases increases when x increases and that the incorporation of water is not a single-phase reaction inducing either a crystal system or space group modification. Fully hydrated (y = 2) and dehydrated (y = 0) samples have been stabilized at room temperature and characterized for all compositions. In wet air, all phases show a proton contribution to the total conductivity at temperatures between 350 and 600 °C. At a given temperature, proton conductivity increases with the substitution ratio and reaches at 350 °C, 5.4 10^− 3 S cm^− 1 for Ba₂(In_0.65Sc_0.35)₂O_4.2□_0.2(OH)_1.6.     

Magnetic properties of U (Fe x Al1−x )2 and U(Fe y Ni1−y )2 compounds

The results of magnetic measurements and ferromagnetic resonance studies performed on U(Fe _x Al_1–x )₂ and U(Fe _y Ni_1–y )₂ compounds over a large temperature range are reported. The saturation magnetization decreases nearly linearly when substituting Fe by Al or Ni. In the composition range x<0.84 and y<0.81, the compounds are Pauli paramagnets, except in the region with y0.10. For UNi₂ two types of magnetic behaviours are shown. This compound can be both a ferromagnet withT _c =23.5 K and a Pauli paramagnet, depending on the crystal structure. Above the Curie temperatures, the reciprocal susceptibility for the compounds with x>0.84 and y>0.81 obeys a temperature dependence of the formX=X _o+C(T-) ^–1. The effective iron moments decrease when substituting iron by nickel or aluminium. The ferromagnetic resonance measurements show that theg values are not composition-dependent. A linear variation of the mean iron magnetization with the exchange field is observed. Finally, the magnetic behaviour of iron in these compounds is analysed.     

Elektronen-Spin-Resonanz an (La1??xGdyCex)Al2

In the EPR of (La_1––x Gd _y Ce _x )Al₂ a bottleneck in the relaxation of the conduction electrons to the lattice is present at sufficiently high Gd-concentrations. The bottleneck can be broken by decreasing the Gd-concentration or by adding Cerium as a spin-flip-scatterer.g-factor and line broadening are measured for (La_1–y Gd _y )Al₂ and (La_1––x Gd _y Ce _x )Al₂ as a function of temperature and Gd- and Ce-concentrations. The Cerium induced relaxationsrate _eL (Ce) increases linearly with Ce-concentration up tox0.025. This corresponds to the fact, well known by measurements of the Kondo anomalies, that Cerium impurities show no significant interaction up to rather high concentrations.     

Diffusion of Au in amorphous Zr x Ni100−x alloys studied by Rutherford Backscattering Spectrometry

The diffusion coefficients (D) of Au in three binary amorphous Zr _x Ni_100–x (x=61, 65, and 67) alloys were measured in the temperature range 549–623 K using the technique of the Rutherford Backscattering Spectrometry (RBS). The D values were found to lie in the range 1.0×10^–21–9.0×10^–20 m²s^–1 for different alloys. The activation energy (Q) was calculated in each case on the basis of an observed Arrhenius temperature dependence of D. The activation energy was found to scale with the crystallization temperature (T _x) of the alloy. Other published measurements for Au diffusion in amorphous Zr-Ni alloys also appear to follow the scaling relation between Q and T _x.     

Elektronen-Spin-Resonanz an (La1−−x Gd y Ce x )Al2

In the EPR of (La_1––x Gd _y Ce _x )Al₂ a bottleneck in the relaxation of the conduction electrons to the lattice is present at sufficiently high Gd-concentrations. The bottleneck can be broken by decreasing the Gd-concentration or by adding Cerium as a spin-flip-scatterer.g-factor and line broadening are measured for (La_1–y Gd _y )Al₂ and (La_1––x Gd _y Ce _x )Al₂ as a function of temperature and Gd- and Ce-concentrations. The Cerium induced relaxationsrate _eL (Ce) increases linearly with Ce-concentration up tox0.025. This corresponds to the fact, well known by measurements of the Kondo anomalies, that Cerium impurities show no significant interaction up to rather high concentrations.     

Lithium ion conductive glass–ceramics with Li3Fe2(PO4)3 and YAG laser-induced local crystallization in lithium iron phosphate glasses

The glasses with the composition of 37.5Li₂O–(25 − x)Fe₂O₃–xNb₂O₅–37.5P₂O₅ (mol%) (x = 5,10,15) are prepared, and it is found that the addition of Nb₂O₅ is effective for the glass formation in the lithium iron phosphate system. The glass–ceramics consisting of Nasicon-type Li₃Fe₂(PO₄)₃ crystals with an orthorhombic structure are developed through conventional crystallization in an electric furnace, showing electrical conductivities of 3 × 10^− 6 Scm^− 1 at room temperature and the activation energies of 0.48 eV (x = 5) and 0.51 eV (x = 10) for Li⁺ ion conduction in the temperature range of 30–200 °C. A continuous wave Nd:YAG laser (wavelength: 1064 nm) with powers of 0.14–0.30 W and a scanning speed of 10 μm/s is irradiated onto the surface of the glasses, and the formation of Li₃Fe₂(PO₄)₃ crystals is confirmed from XRD analyses and micro-Raman scattering spectra. The crystallization of the precursor glasses is considered as new route for the fabrication of Li₃Fe₂(PO₄)₃ crystals being candidates for use as electrolyte materials in lithium ion secondary batteries.     

Mössbauer Study of La1−x Ca x Mn1−y 57Fe y O3 with x=0,0.25; y=0.01

Temperature dependent Mössbauer measurements are done on the samples of La_1–x Ca _x Mn_1–y ⁵⁷Fe _y O₃ with x=0 and 0.25, and y=0.01. With decreasing temperature, the specimen with x=0.25 shows a paramagnetic to ferromagnetic transition around 175 K. In the specimen x=0.0, the temperature dependence of both the center shift () and the recoilless fraction (f) can be fitted very well with the Debye theory with a _D=320±50 K. But for the specimens with x=0.25, f and show distinct deviations from the Debye behavior in the temperature range in which the resistivity shows a sharp decrease. Dips observed in both the f and around the transition temperature suggest that the Jahn–Teller distortion observed in these systems is dynamic in nature.     

Photoelectric properties of Pb1−x−y Sn x Ge y Te:In epitaxial films

Pb_1–x–y Sn _x Ge _y Te:In epitaxial films are examined in a wide temperature interval and at various background fluxes. These films have high sensitivity to infrared radiation in the spectral range <20m. The lifetime depends exponentially on temperature and varies from several seconds at T=10 K to 10^–2 s at T=20 K. The two-electron model of Jahn-Teller centers is proposed to explain the results. Multielement photoresistors based on these films are fabricated and D*=1.7×10¹³ cm Hz^1/2 W^–1 at T=25 K is achieved. Noise of the photoresistors is independent of background flux when it varies from 10¹² cm^–2 s^–1 to 10¹⁸ cm^–2 s^–1. As compared with Si:Ga and Ge:Hg photoresistors, the responsitivity is several orders larger at the operating temperature 25–30 K.     

A tunable green alkaline-earth silicon-oxynitride solid solution (Ca1? x Sr x )Si2O2N2:Eu2+ and its application in LED

A series of (Ca_1−x−y Sr _x )Si₂O₂N₂:yEu²⁺ (x=0.0–0.97, y=0.03) phosphors were synthesized by high-temperature solid-state reaction. The XRD patterns confirm the formation of a solid solution of (Ca_1−x−y Sr _x )Si₂O₂N₂:yEu²⁺. An intense tunable green light is observed with the increasing ratio of Sr/Ca. With an increase in x, the excitation and emission spectra show a redshift and blueshift, respectively, due to large centroid shift and small Stokes shift. The temperature dependent luminescence is also investigated in the temperature range of 77–450 K. The Huang–Rhys factor and the thermal-quenching temperature are determined. Intense green LEDs were successfully fabricated based on the (Ca_1−x−y Sr _x )Si₂O₂N₂:yEu²⁺ phosphor and near-ultraviolet (∼395 nm) GaN/blue (460 nm) InGaN chips. All the results indicate that the solid solution (Ca_1−x−y Sr _x )Si₂O₂N₂:yEu²⁺ is a promising phosphor applicable to near-UV and blue LEDs for solid-state lighting.     

57Fe Mössbauer study of Eu1−x Sr x FeO3−y

The samples of Eu_1–x Sr _x FeO_3–y (x=0.0–1.0) were prepared by the solid state reaction method. Their X-ray diffraction patterns and⁵⁷Fe Mössbauer spectra at room temperature were measured. It is found that Sr ions incorporate in the lattice of EuFeO₃, the change of crystal structure is related to the dopant.⁵⁷Fe Mössbauer spectra consist of one magnetic, one doublet and one single paramagnetic components. The Fe ions in the cubic phase are in intermediate valence state between Fe(III) and Fe(IV) and may participate in electron hopping.     

Magnetic and magnetotransport properties of Co-doped manganites with perovskite structure

A systematic study of the doping of the Mn-sites by cobalt in three series of manganites — La_0.76Ba_0.24(Mn_1−xCo_x)O₃ single crystals, La_2/3Ba_1/3(Mn_1−xCo_x)O₃ and La(Mn_1−xCo_x)O₃ ceramics has been performed. It was found that La(Mn_1−xCo_x)O₃ annealed at 800°C in the range 0.4x0.9 is a mixture of ferromagnetic domains with ordered Mn and Co ions and ionically disordered spin-glass domains. In the quenched samples the fraction of spin-glass-type component increases strongly. The La_2/3Ba_1/3(Mn_1−xCo_x)O₃ solid solutions exhibit also an evidence for phase separation in the range 0.5x0.8. All the La(Mn_1−xCo_x)O₃ samples show an insulating behavior, however, magnetoresistance reduces strongly when the cobalt content rises to x=0.5. The La_0.76Ba_0.24(Mn_1−xCo_x)O₃ single crystals show first-order phase transition below their Curie points associated with a change of ground state of the Co²⁺ ions. The magnetic phase diagrams are depicted. The results are discussed in terms of positive Mn³⁺–O–Mn⁴⁺, Mn³⁺–O–Mn³⁺, Mn⁴⁺–O–Co²⁺ and negative Mn⁴⁺–O–Mn⁴⁺, Co²⁺–O–Co²⁺, Co²⁺–O–Mn³⁺ superexchange interactions as well as Co²⁺ and Mn⁴⁺ ionic ordering.     

Mössbauer study of substituted barium ferrite BaFe11−x−y Co0.5Ti0.5Ni x ZnyO19−r

Substituted barium ferrite BaFe_11–x–y Co_0.5Ti_0.5Ni _x Zn_yO_19–r powders were prepared using a coprecipitation method and investigated by X-ray diffraction (XRD) and⁵⁷Fe Mössbauer spectroscopy. The results show that the as-prepared magnetic powders possess the typical hexagonal structure and demonstrate both a good dispersibility and a narrow particle size distribution. The hyperfine fields for all sites decrease slightly asx (ory) increases. The Ni²⁺ ions prefer to occupy the 2a and 12k sites, and Zn²⁺ ions occupy the 4f_IV site.     

Correlation inequalities and the Kosterlitz-Thouless transition for anisotropic rotators

I give a proof of the Kosterlitz-Thouless transition for sufficiently anisotropic (J _zJ _x ^–1 =J _zJ _y ^–1 <2q ^–(JKT)^–J) two-dimensionalN-component rotators (N 3). The method is based on Wells' inequality and is related to mean field Gaussian inequalities.     

An X-ray diffraction and Mössbauer spectroscopic study on thec-axis texture YBa2(Cu1−x Fe x )3O7−y thick films

YBa₂(Cu_1–x Fe _x )₃O_7–y thick films (x=0, 0.01, 0.02, 0.03) on ceramic substrate were prepared. X-ray diffraction determinations show the formation of partialc-axis texture perpendicular to the surface of the ceramic substrate in the preparation process. The⁵⁷Fe Mössbauer spectra were measured at 300 K, where the angle between the incidence-ray beam and the surface of the film is 90° and 36°, respectively. The⁵⁷Fe Mössbauer spectra with=90° possess four sets of asymmetrical doublets.     

EPR and optical absorption studies on VO ions in zinc lactate trihydrate

EPR and optical absorption studies of VO²⁺-doped zinc lactate trihydrate single crystals are done at room temperature. The EPR spectra of VO²⁺ are characteristic of tetragonally compressed octahedral site. The angular variation of the EPR spectra shows single site occupying interstitial position in the lattice. The spin Hamiltonian parameters are evaluated as g_x=1.9771, g_y=2.0229, g_z=1.9236 and A_x=76, A_y=104, A_z=197 (×10⁻⁴) cm⁻¹. Using these parameters and optical absorption data various bonding parameters are determined and the nature of bonding in the complex is discussed.     

On the superconductivity of the tin-hydrogen system

Conductivity and superconductivity studies of amorphous [Sn_1–y Cu _y–]_1–x H _x samples in connection with¹¹⁹Sn Mössbauer effect experiments on¹¹⁹Sn_1–x H _x give strong evidence that the observed increase of the superconducting transition temperatureT _c in the Sn–H-system is caused by the stabilization of an amorphous structure. Thus the Sn–H-system is very similar to the Sn–Cu-system and no H-specific effect is needed to explain the increase ofT _c.     

Self-assembling of C and Sn in Ge

Self-assembling of isoelectronic C and Sn impurities in Ge is predicted. The formation of the 1C4Sn tetrahedral cells is thermodynamically profitable in Ge-rich C_xSn_yGe_1−x−y (4x<y) alloys in the ultra dilute C impurity limit with 1×10^-8x1×10^-3. The concentrations of Sn atoms when all C atoms are surrounded only by Sn atoms are estimated for the lower molecular beam epitaxy, intermediate annealing and higher bulk crystallization temperatures. The origin of this phenomenon is a considerable decrease of the strain energy after self-assembling. The same self-assembling in Si is thermodynamically non-profitable due to the large cohesive energy of Si–C chemical bonds.