X-ray diffraction and Ir-absorption characteristics of lanthanide orthophosphates obtained by crystallisation from phosphoric acid solution

Powders of LnPO₄ · H₂O (Ln = La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu and Y) prepared by crystallisation from boiling phosphoric acid (2 M H₃PO₄/1) solution were characterised by X-ray diffraction and FTIR-spectroscopy. Hexagonal LnPO₄ · H₂O (La Tb), tetragonal (Ho Lu and Y) and orthorombic DyPO₄ · H₂O crystalline modifications were identified. Ir-spectra of the hydrated hexagonal, anhydrous tetragonal LnPO₄ · H₂O (Dy, Ho, Er, Tm, Yb, Lu and Y) and anhydrous monoclinic (La Tb) are consistent with those reported in the literature. However, the hydrated tetragonal LnPO₄ · H₂O (Ho, Er, Tm, Yb, Lu and Y) display a surplus band (625 cm^–1) in the region of ₄, which was not reported in the literature. The band disappears after ignition at 950°C, while the tetragonal structure is still maintained, which may imply that it is attributed to hydrogen bonding of H₂O molecules to the phosphate oxygen in hydrated salts. Some of the phosphates, after ignition at 950°C, display additional P₂O₇ ^4– band at 1265–1267 cm^–1. That may be resulted from HPO₄ ^2– for PO₄ ^3– substitution in the phosphates crystallised in acidic (2 M H₃PO₄/1) solution.     

Optical absorption spectra studies for amorphous Cu2O-Bi2O3 glass system

Infrared absorption spectra were measured in the spectral range 4000–200 cm^–1 for the Cu₂O-Bi₂O₃ glass system. Strong bands were observed around 436–477, 600–632, 700–715, 810–875, 975–1000, 1550–1610 and 3225–3510 cm^–1 which are due to harmonics of the Bi-O-Bi stretching vibration, Cu-O stretching vibrations, O-Bi-O stretching vibrations, O-Bi-O bending vibrations, Bi-O stretching vibrations, free H₂O normal-mode bending vibrations and free H₂O molecules or OH^– ions, respectively. Quantitative justification of these absorption bands shows that the values of the experimental wave number for most recorded absorption bands agree well with the theoretical ones.The optical absorption spectra were recorded for the same glass system in the spectral range 300–700 Nm. These records show that the absorption edge has a tail extending towards lower energies. The edge shifts towards lower energies with increasing Cu₂O content. This shift is mostly related to the structural rearrangement and the relative concentrations of the glass basic units. By increasing the Cu₂O content, the optical energy gap decreases, while the width of the localized states increases.     

Raman microscopy study of basic aluminum sulfate Part II Raman microscopy at 77 K

The tridecameric aluminum polymer [AlO₄Al₁₂(OH)₂₄(H₂O)₁₂]⁷⁺ was prepared by forced hydrolysis of Al³⁺ up to an OH/Al molar ratio of 2.2. Upon addition of sulfate the tridecamer crystallised as the monoclinic basic aluminum sulfate Na_0.1[AlO₄Al₁₂(OH)₂₄(H₂O)₁₂](SO₄)_3.55. These crystals have been studied using Raman microscopy at 300 and 77 K and compared to Na₂SO₄·xH₂O and Al₂(SO₄)₃·xH₂O. The Raman spectrum of basic aluminum sulfate is dominated by two broad bands, which are assigned to the ₂ and ₄SO₄ ^2– triplets at 446, 459 and 496 cm^–1 and 572, 614 and 630 cm^–1. The ₁ is observed as a single band at 990 cm^–1, partly overlapped by the ₃ triplet at 979, 1009 and 1053 cm^–1 of the sulfate group in the Al₁₃ sulfate structure. Furthermore the band at 726 cm^–1 is assigned to an Al–O mode of the polymerised Al–O–Al bonds in the Al₁₃ Keggin structure. For the first time the OH-stretching region of the basic aluminum sulfate has been reported. The 77 K spectrum shows the presence of 3 crystal water bands at 3035, 3138 and 3256 cm^–1 accompanied by 3 Al–H₂O bands at 3354, 3418 and 3498 cm^–1 and 4 Al-OH bands at 3533, 3584, 3671 and 3697 cm^–1.     

Phase Relations in the LiOH–ZrO2–GeO2–H2O System at 500°C and 0.1 GPa

The phases crystallizing in the LiOH–ZrO₂–GeO₂–H₂O system at 500°C and 0.1 GPa are Zr^[8]Ge^[4]O₄, Li₂Ge^[6]Ge₂ ^[4]O₆(OH)₂, Li₃HGe₄ ^[6]Ge₃ ^[4]O₁₆ · 4H₂O, and Li₂Ge^[4]O₃. These phases differ in the oxygen coordination of Ge. At a ZrO₂ : GeO₂ molar ratio of 1 : 1, increasing the LiOH concentration leads to the crystallization of a ZrO₂ + Li₂GeO₃ mixture, instead of ZrGeO₄. At ZrO₂ : GeO₂ ratios in the range 1 : 2 to 1 : 6, Li₂Ge^[6]Ge₂ ^[4]O₆(OH)₂ crystallizes together with ZrGeO₄. The formation of the structures of ZrGeO₄ and Li₂Ge^[6]Ge₂ ^[4]O₆(OH)₂ is discussed in terms of the matrix assembly of crystal structures from cyclic subpolyhedral structural units.     

Infrared and Structural Properties of Y1?xNdxBa2Cu3O7?δ (0 ≤ x ≤ 1)

Infrared and structural properties of Y_1–x Nd _x Ba₂Cu₃O_7– (0 x 1) were investigated using infrared absorption spectroscopy and X-ray powder diffraction. The unit cell parameters of the samples were defined using X-ray diffraction data. The resistance measurements showed that the samples revealed superconductivity in the temperature range of 80–100 K. It was observed that by the substitution of Nd to Y in YBa₂Cu₃O_{7 –} IR band at 573 cm^–1 that is assigned as Cu–O axial antisymmetric stretching mode shifts to 533 cm^–1 while the band at 620 cm^–1 that is due to Cu–O symmetric stretching mode in YBa₂Cu₃O_7– shifts to 588 cm^–1.     

Raman microscopy study of basic aluminum sulfate

The tridecameric aluminum polymer [AlO₄Al₁₂(OH)₂₄(H₂O)₁₂]⁷⁺ was prepared by forced hydrolysis of Al³⁺ up to an OH/Al molar ratio of 2.2. Upon addition of sulfate the tridecamer crystallised as the monoclinic basic aluminum sulfate Na_0.1[AlO₄Al₁₂(OH)₁₂(H₂O)₁₂](SO₄)_3.55. These crystals have been studied using FT-Raman microscopy and compared to the basic aluminum nitrate, Na₂SO₄·xH₂O and Al₂(SO₄)₃·xH₂O. The Raman spectrum of basic aluminum sulfate is dominated by two broad bands which are assigned to the ₁ and ₃ bands at 981 and 1051 cm^{– 1} of the sulfate group in the Al₁₃ sulfate structure. Furthermore the band at 724 cm^{– 1} is assigned to an Al–O mode of the polymerised Al–O–Al bonds in the Al₁₃ Keggin structure. The sharp band at 1066 cm_{– 1} and the minor band at 1384 cm^{– 1} are interpreted to be due to a small amount of nitrate impurity on a different position in the structure than the nitrate present in the Al₁₃ nitrate crystal structure, based on the shift in band position of both the ₁ symmetric stretching and ₃ asymmetric stretching modes.     

Electron spin resonance spectra of Gd3+ ions in K2SO4-ZnSO4 glasses

Electron spin resonance (ESR) spectra of Gd³⁺ ions doped in K₂SO₄-ZnSO₄ glasses have been studied on an X-band ESR spectrometer at different temperatures (–120 to 150 C). The ESR spectrum at room temperature exhibits three prominent features with effectiveg-values of 5.6, 2.83 and 2.02. The spectra are similar to the U spectra familiar in many oxide and fluoride glasses, indicating very low and disordered site symmetries with a broad distribution of crystal fields. Remarkable changes have been observed in the spectrum with changes in the temperature, concentration and glass composition. The broadening of theg 2.02 line with increasing Gd³⁺ ion content indicates that the dipole-dipole interaction between the resonant centres increases with increase in Gd³⁺ ion content. A weak band at 36350cm^–1 is observed in the optical absorption spectrum of 0.5mol% Gd³⁺ in K₂SO₄-ZnSO₄ glass which has been assigned to the transition⁸S_7/2⁶P_7/2.     

Formation of oxide phases in the system Fe2O3-NiO

Mixed metal oxides in the system Fe₂O₃-NiO were prepared by coprecipitation of Fe(OH)₃/Ni(OH)₂ and the thermal treatment of hydroxide coprecipitates up to 800 or 1100°C. X-ray diffraction showed the presence of -Fe₂O₃, NiO and NiFe₂O₄ in samples prepared at 800°C. The oxide phases -Fe₂O₃, NiO, NiFe₂O₄ and a phase with structure similar to NiFe₂O₄ were found in samples prepared at 1100°C. Fourier transform-infrared spectra of oxide phases formed in the system Fe₂O₃-NiO are discussed. Two very strong infrared bands at 553 and 475 cm^–1, a weak intensity infrared band at 383 cm^–1 and two shoulders at 626 and 441 cm^–1 were observed for -Fe₂O₃ prepared at 1100°C. NiFe₂O₄, prepared at the same temperature, showed two broad and very strong infrared bands at 602 and 411 cm^–1, while NiO showed a broad infrared band at 466 cm^–1. Fourier transform infrared spectroscopic results were in agreement with X-ray diffraction.     

Photoinduced changes in Raman spectra of YBa2Cu3O6.4 films

The evolution of Raman spectra with illumination has been studied in YBa₂Cu₃O_6.4 films at temperatures between 5–300 K. Low laser power has always been used to avoid local overheating, which was controlled by measuring the local temperature by the Stokes/anti-Stokes ratio. Three important photoinduced effects have been found: (i) the enhancement of the intensity of the observed phonon modes: (Cu(2) at 141 cm^–1, O(2)-O(3) at 338 cm^–1, and O(4) at 488 cm^–1), which may be related to the ordering of oxygen vacancies, (ii) the increase of the electronic scattering background for low Raman frequencies, which is in agreement with the enhancement of the static conductivity(0) after illumination, and (iii) the suppression of the intensity of the two-magnon band, which may be caused by the increase of charge carriers due to photodoping.     

Oxygen self-diffusion in a potassium strontium silicate glass using proton activation analysis

Oxygen self-diffusion coefficients were measured in a 20K₂O-20SrO-60SiO₂ (wt%) glass above and below the glass transition temperature using the single spectrum proton activation analysis of oxygen-18 using the nuclear reaction ¹⁸O(p, )¹⁵N. The -particle spectrum recorded during proton irradiation is used to determine the ¹⁸O concentration profile. The self-diffusion coefficients, D, determined for the three diffusion times of about 22 h, 3 1/2 and 7 1/2 days were in good agreement within experimental error, except for the two lowest temperatures of the short-time run possibly because of the shallow depths of diffusion and surface exchange. In the temperature range 600 to 1000 K, D values with the relations, above the glass transition temperature D=7.6×10¹⁴ exp(–119 kcal/RT) cm²sec^–1, and below the glass transition temperature D=1×10^–12 exp(–10 kcal/RT) cm²sec^–1, were obtained.     

Effect of heat treatment on the infrared absorption spectra of Sr-Na borosilicate glass

Internal modes of vibrations are studied here at different temperatures (27–800°C) and in the frequency range 200–4000 cm^–1 through heat treatment. The baseline method was used. The strong bands of SiO₄ tetrahedra in this glass show an increase in absorbance at high temperature (600–800°C). The deformation of SiO₄ tetrahedra is investigated. This is found to depend on the ionic radius of the divalent metal oxide introduced, and the coordination number of the cation. Also from a study of the temperature dependence of the relative integrated intensity of the modes 600–800 and 850–1450 cm^–1, the relaxation time and rotational energy barrier of the glasses selected indicate that the glassy phases are transformed to crystalline phases at 500°C.     

Oxide impurity absorptions in Ge-Se-Te glass fibres

Oxide impurity absorptions in Ge-Se-Te glass fibres and the cause of the absorption loss around 943 cm^–1, the frequency of the CO² laser, have been investigated. The oxygen in the glass bounds preferentially to germanium and causes the absorptions due to Ge-O bond vibrations at 765 cm^–1 (band I) and 1230cm^–1 (band II). The excess absorptions due to these bands were determined as 0.228cm^–1/P.p.m. wt O₂ for band-I and 0.006cm^–1 /p.p.m. wt O₂ for band II. The loss of the fibre at 943cm^–1 increased with the oxygen content. It was, however, revealed from the deconvolution of the IR spectra into the independent absorption components that the absorption tails of band I and band II did not affect the loss at 943 cm^–1. The content of the impurities except oxygen analysed by a mass spectroscopy was too low to affect the loss at 943 cm^–1.     

Electrical conductivity in hot-pressed nitrogen ceramics

The a.c. and d.c. electrical conductivities of some hot-pressed polycrystalline nitrogen ceramics have been measured between 400 and 1000° C. The materials examined were Si₃N₄, 5.0% MgO/Si₃N₄ and two sialons, Si_(6–z) · Al _z · O _z · N_(8–z) having z 3.2 and z 4.0 respectively. The electrical behaviour of all the materials showed similar general features. The d.c. conductivities were about 10^{–10 –1} cm^–1 at 400° C and rose to between 10^–6 and 10^{–5 –1} cm^–1 at 1000° C. The a.c. Data, taken over the frequency range 15 Hz to 5 kHz showed that below about 500° C the a.c. conductivity ( _a.c.) varied with frequency as _a.c. ^s where 0.7 _d.c.) agreed well with the relation _d.c. = A exp(–B/T ^1/4). Above 700° C both the a.c. and d.c. conductivities followed log T ^–1. Hall effect and thermoelectric power measurements enabled the Hall mobility to be estimated as less than 10^–4 cm² V^–1 sec^–1 at 400° C and showed that the materials were all p-type below 900° C and n-type above 900° C. The electrical properties of all four materials are consistent with the presence of a glassy phase.     

Cu2+ ions in sodium fluoride-sodium borate glasses studied by EPR and optical absorption techniques

Electron paramagnetic resonance (EPR) and optical absorption spectra of Cu²⁺ ions in 80Na₂B₄O₇-(20 – x)NaF – xCuO (NFNB) glass system with 0 x 6 mol% have been studied. EPR spectra of all the glass samples exhibit resonance signals characteristic of Cu²⁺ ions. The values of spin-Hamiltonian parameters indicate that the Cu²⁺ ions in sodium fluoride-sodium borate (NFNB) glasses were present in octahedral sites with tetragonal distortion. The number of spins (N) participating in resonance was calculated as a function of temperature for NFNB glass sample containing 1 mol% of Cu²⁺ ions and the activation energy was calculated. From the EPR data, the paramagnetic susceptibility () was calculated at various temperatures and the Curie constant was calculated from the 1/ – T graph. The optical absorption spectra of these samples show a broad absorption band centered at 13280 cm^–1 which is assigned to the ² B _1g ² B _2g transition of Cu²⁺ ions in distorted octahedral sites. The optical band gap energy (E _opt) and Urbach energy (E) are calculated from their ultraviolet edges. It is observed that as the copper ion concentration increases, E _opt decreases while E increases. This has been explained as due to the creation of additional localized states by CuO, which overlap and extend in the mobility gap of the matrix. By correlating the EPR and optical data, the molecular orbital coefficients have been evaluated.     

A parametric study of the deposition of the TiN thin films by laser reactive ablation of titanium targets in nitrogen: the roles of the total gas pressure and the contaminations with oxides

The multipulse excimer laser-reactive ablation of a titanium target in nitrogen has been found to result in a total pressure of the ambient gas in the range 7–70 bar, in the deposition on to a silicon collector surface of high-purity f c c TiN thin films. These films were hard and adherent to substrate. The deposition rate was 0.03–0.05 nm per pulse for an incident laser fluence of 5 J cm^–2. For a lower gas pressure of a few microbars the deposits were amorphized with an excess of titanium. For a nitrogen pressure larger than 100 bar, the layers were contaminated with oxides. The oxides became more abundant with further increase in the gas pressure, and the deposited layer consisted of oxides only when the pressure reached several millibars.     

X-ray,electrical conductivity,and infrared studies of oxide spinels containing cobalt,titanium and manganese

X-ray, electrical conductivity and infrared studies of the system Co_2–x Ti_1–x Mn_2x O₄ were carried out with a view to investigate the cation distribution. Compounds 0 x 0.6 showed cubic symmetry, compounds 0.8 x 1 are tetragonal. X-ray intensity calculation indicated the presence Of Co²⁺ and Mn³⁺ at both octahedral and tetrahedral sites. A plot of activation energy against composition shows a break where crystal symmetry changes. The electrical conductivity-temperature behaviour obeys the Raschhinrichsen law. The mobility of holes calculated from infrared and conductivity data is of the order Of 10^–9 cm² V^–1 sec^–1. X-ray intensity calculations and conductivity measurements suggest the ionic configuration of the system to be Co _1–x ²⁺ Mn _x ³⁺ [Co _2–2x ²⁺ Mn _x ³⁺ Ti _x ⁴⁺ ]O ₄ ^2– .     

Analysis of electronic structure and charge density of the high-temperature superconductor YBa2Cu3O7

Self-consistent linearized augmented plane wave (LAPW) method calculations of the band structure, density of states, Fermi surface, Coulomb potential, charge density, core-level shifts, and electron-phonon interaction are presented for Y₁Ba₂Cu₃O₇. The calculated Sommerfield parameter is 4.35 mJ(mole Cu)^–1 K^–2, roughly about a factor of 2 smaller than experimentally deduced values of the enhanced value=(1 + )₀, suggesting that the Fermi surface mass enhancement is of the order of unity. The crystal charge density is best represented by overlapping spherical ionic densities when the Cu and O ions are assigned charges of +1.62 and –1.69, respectively, corresponding to about 0.3 holes per oxygen atom. Core-level energies for the inequivalent atoms differ by as much as 0.45 eV for Cu and 0.7 eV for O, amounts which may be detectable by core-level spectroscopies. These results provide important information on the character and magnitude of ionic contributions to bonding in these materials. Within the rigid muffin-tin approximation, calculated McMillan-Hopfield parameters yield estimates for the electron-phonon strength that appear to be too small to account for the observedT _c. We point out an unusual band of oxygen-derived chain states below, but within 0.1 eV of, the Fermi level.     

High-resolution measurements of the heat capacity of MnBr2·4H2O near its Néel temperature

The heat capacityC _P of the antiferromagnet MnBr₂ ·4H₂O has been measured for polycrystalline and single-crystal samples nearT _N(2.123 K) with temperature resolution of 1×10^–6 K. Similar rounding of the lambda anomaly is found in both cases. For |1 –T/T _N| 10^–1 all data can be well fitted by assuming the samples to consist of many independent subsystems obeying the same power laws but with a Gaussian distribution ofT _N's having a width of 1.1×10^–3 K. ForT>T _N, we findC _P ^–0.12, essentially as predicted for three-dimensional Ising models in the critical region. ForT<T _N and 10^–3 10^–1,C _P ln , which approximates Ising model behavior in this interval but is not expected to be valid for 10^–4. ForT>T _N and 2.5×10^–1, C_P agrees well with predictions for the classical Heisenberg model. This crossover at 10^–1 is consistent with the known anisotropy of the salt and with present theory. The data forT>T _N in the interval 10^–4 10^–3, while not in the range of obvious rounding, appear to be strongly influenced by the mechanism responsible for that rounding.Work supported by the National Science Foundation and the Office of Naval Research. Based on a thesis submitted by L.W.K. to Carnegie-Mellon University in partial fulfillment of the requirements for the Ph.D. degree. A preliminary account of this work was presented at the Atlantic City meeting of the American Physical Society, March 1972 [Bull. Am. Phys. Soc. 17, 299 (1972)].     

Preparation and electrical properties of ITO thin films by dip-coating process

Indium tin oxide (ITO) thin films were prepared on quartz glass substrates by a dip-coating process. The starting solution was prepared by mixing indium chloride dissolved in acetylacetone and tin chloride dissolved in ethanol. The ITO thin films containing 0 20 mol% SnO₂ were successfully prepared by heat-treatment at above 400 °C. Chemical stability of sol were investigated by using a FTIR spectrometer. The electrical resistivity of the thin films decreased with increasing heat-treatment temperature, that is carrier concentration increased, and mobility decreased with increasing SnO₂ content. The ITO thin films containing 12 mol% SnO₂ showed the minimum resistivity of =1.2 × 10^–3 ( cm). It also showed high carrier concentration of N=1.2 × 10²⁰(cm^–3) and mobility _H=7.0(cm² V^–1 s^–1).     

Phonon Modes in CMR Manganites at Elevated Temperatures

Phonon modes of the colossal magnetoresistance manganites La_0.7Ca_0.3MnO₃ and La_0.8Li_0.2MnO₃ have been investigated by far-infrared (100–700 cm^–1) reflectivity spectroscopy at elevated temperatures (300–800 K). The three principal optical phonons all move systematically to lower frequency as temperature increases, in accordance with a Grüneisen relationship. The La(Ca,Li)–(MnO₃) vibration (170 cm^–1) varies with cation mass as expected. The Mn–O stretching mode (580 cm^–1) has a higher frequency in the Li-doped compound than in the Ca-doped, whereas the O–Mn–O bending mode )340 cm^–1) occurs at the same frequency in each, demonstrating that the cation strongly influences the Mn–O– length but not the bond angle.