Crystal structure and fluorescence lifetime of NdAl3(BO3)4, a promising laser material

The structure of NdAl₃(BO₃)₄, determined by single-crystal x-ray analysis, is rhombohedral with space group R32 and cell parameters $\text{a}\text{= 9.3416 (6)}\text{A}\text{?}$, $\text{c}\text{= 7.3066 (8)}\text{A}\text{?}$, Z = 3. A full-matrix, least-squares refinement gives R = 0.033 and R_w = 0.037. The Nd atoms, Al atoms and B atoms occupy trigonal prisms, octahedra, and triangles of oxygen, respectively. Edge-shared Al octahedra form helices along the c-axis. These helices are connected by isolated B triangles and isolated Nd trigonal prisms. The fluorescence lifetime of the ${}^4\text{F}{}_{\mathrm{<mtext>3</mtext><mtext>2</mtext>}}\text{→}{}^4\text{I}{}_{\mathrm{<mtext>11</mtext><mtext>2</mtext>}}$ transition of Nd⁺³ is reported for the system Nd_xGd_1?xAl₃(BO₃)₄. The lifetime of NdAl₃(BO₃)₄ is 19us, and concentration quenching is reduced in the series, as happens in NdNa₅(WO₄)₄ (85μs) and NdP₅O₁₄ (115μs). The shorter lifetime is attributed to noncentrosymmetry; the reduced concentration quenching to isolation of Nd polyhedra.     

Concentration quenching of Tb3+ luminescence in LaOBr and Gd2O2S phosphors

The concentration quenching of trivalent terbium ${}^5\text{D}{}_{\mathrm{3,4}}\text{→}{}^7\text{F}{}_{\mathrm{J}}$ emissions from UV-excited (La, Tb) OBr and (Gd, Tb)₂O₂S phosphors was studied. The activation concentration x was varied from 5·10^?5 to 0.2 for (La_1?xTb_x) OBr and from 10^?3 to 0.1 for (Gd_1?xTb_x)₂O₂S. ${}^5\text{D}{}_3\text{→}{}^7\text{F}{}_{\mathrm{J}}$ emissions (blue) were observed to quench first and the Tb³⁺ concentration giving rise to maximum intensity was 0.003 in (La, Tb) OBr and between 0.005 and 0.01 in (Gd, Tb)₂O₂S. The optimum concentration for ${}^5\text{D}{}_4\text{→}{}^7\text{F}{}_{\mathrm{J}}$ (green) emissions was 0.05 in (La, Tb) OBr and 0.03 in (Gd, Tb)₂O₂S. Dipole-dipole and dipole-quadrupole interactions are possible mechanisms for the quenching of emissions from the ⁵D₃ and ⁵D₄ levels.A method for determining the Tb³⁺ concentration in these phosphors, based on the intensity ratios of the ${}^5\text{D}{}_3\text{→}{}^7\text{F}{}_{\mathrm{J}}$ and ${}^5\text{D}{}_4\text{→}{}^7\text{F}{}_{\mathrm{J}}$ transitions, is also presented.     

n-PbTep+−Pb1−xSnxTe heterojunctions prepared by a modified hot wall technique

$\text{n-PbTe}\text{p}{}^{\mathrm{+}}\text{?}\text{Pb}{}_{\mathrm{1?x}}\text{Sn}{}_{\mathrm{x}}\text{Te}$ heterojunctions with a long wavelength spectral cutoff (λ_c ≈ 6 μm) were prepared using the double-channel hot wall technique. The electrical and photoelectrical properties of the heterojunctions at 77, 197 and 300 K were investigated. Detectors with R_oA equal to 170 Ω cm² and a quantum efficiency of 25–40% were obtained. Reasons for the shift of the long wavelength spectral cutoff of the heterojunctions towards shorter wavelengths are given.     

Stationary photoconductivity of mixed Tl1−xAgxInSe2 crystals

Tl_1?xAg_xInSe₂ (x = 0 to 0.03) single crystals of solid solution were grown by Bridgeman-Stockbarger techniques. Photoelectric measurements were taken at 300 and 77 K. With an increase in the value of x, the equilibrium concentration is increased 10 to 100 times. At 77 K a region of impurity photosensitivity has been detected which is bordered by the fundamental absorbtion edge. The photosensitivity ($\text{R}{}_{\mathrm{d}}\text{R}{}_{\mathrm{p}}$) of the solid solution crystals at 77 K increases from 8.2 (x = 0) to 55.2 (x = 0.03) the conclusion is made that when Tl is replaced by Ag then the sensitization of semiconductor.     

Copper doped zinc oxide Y2BaZnO5: ERS and optical investigation

In copper doped Y₂BaZnO₅ oxides, copper exhibits a distorted square pyramidal coordination which is consistant with the values of g and A tensors obtained from O band ERS spectrum for a sample containing about 1 % Cu. Three values for g and A are observed, g₁ = 2.049₅, g₂ = 2.051₅, g₃ = 2.275, $\text{¦}\text{A}{}_1\text{¦ = 13 10}{}^{\mathrm{?4}}\text{cm}{}^{\mathrm{?1}}$, $\text{¦}\text{A}{}_2\text{¦ = 10 10}{}^{\mathrm{?4}}\text{cm}{}^{\mathrm{?1}}$ and $\text{¦}\text{A}{}_3\text{¦ = 147.5 10}{}^{\mathrm{?4}}\text{cm}{}^{\mathrm{?1}}$. Since $\text{g}{}_1\text{?}\text{g}{}_2$ an approximate C_4v point symmetry can be assumed for copper. The electronic spectrum shows three bands at 11700, 14500 and 20500 cm^?1 which can be assigned to the transitions A₁ → B₁, B₂ → B₁ and E → B₁ respectively. The orbital reduction parameters are calculated and the bonding covalency is discussed.     

Crystal structure and fluorescence lifetime of a laser material NdNa5(WO4)4

The structure of NdNa₅(WO₄)₄, determined by single-crystal x-ray analysis, is tetragonal with space group I 4₁/a and cell parameters $\text{a}\text{= 11.559(2)}\text{A}\text{?}$, $\text{b}\text{= 11.453(2)}\text{A}\text{?}$, z = 4. A full-matrix, least-squares refinement gives R = 0.077. The W atoms and the Nd atoms occupy isolated tetrahedra and dodecahedra, respectively. These polyhedra are connected by the Na atoms, which are located at two different sites, tetrahedral and octahedral. The fluorescence lifetime of the ${}^4\text{F}{}_{\mathrm{<mtext>3</mtext><mtext>2</mtext>}}\text{→}{}^4\text{I}{}_{\mathrm{<mtext>11</mtext><mtext>2</mtext>}}$ transition of Nd⁺³ is reported for the system La_1?xNd_xNa₅(WO₄)₄. The lifetime of NdNa₅(WO₄)₄ is 85 ± 5 μsec, which is comparable to NdP₅O₁₄. Concentration quenching is considerably reduced in both host structures, which we conclude is due to the isolation of the rare-earth polyhedra.     

Rate law versus oxygen pressure in spinel oxidation to γ lacunar spinels

In the controlled oxidation of spinels (Fe²⁺Fe³⁺_2?xM³⁺_x)O^2?₄ (M³⁺=Al³⁺, Cr³⁺ ; 0 < x < 2) and (Fe²⁺Al³⁺_2?xCr³⁺_x)O^2?₄ to the metastable phases γ(Fe³⁺_1?yM³⁺_y)₂O^2?₃ and $\text{γ(}\text{Fe}{}^{\mathrm{3+}}{}_{\mathrm{<mtext>1</mtext><mtext>3</mtext>}}\text{Al}{}^{\mathrm{3+}}{}_{\mathrm{<mtext>2</mtext><mtext>3</mtext><mtext>?</mtext><mtext>y</mtext>}}\text{Cr}{}^{\mathrm{3+}}{}_{\mathrm{<mtext>y</mtext>}}\text{O}{}^{\mathrm{2?}}{}_{\mathrm{3?}}\text{(0 <}\text{y}\text{<}\text{2}\text{3}\text{)}$, over the temperature range 200–450°C, the rate law is usually v = k Pⁿ_(O2) with $\text{n}\text{=}\text{1}\text{2}$. This law is well interpreted if we consider a total association vacancy-positive charge. However, for low oxidation extents a (a < 0.3) the law written as is in better agreement with a partial association of defects. For a total dissociation of defects exponent n of the pressure law is always smaller.     

Fatigue crack propagation from a crack inclined to the cyclic tensile axis

Cyclic stresses with stress ratio R = 0.65 were applied to sheet specimens of aluminium which have an initial crack inclined to the tensile axis at angles of 30°, 45°, 72° or 90°. The threshold condition for the non-propagation of the initial crack was found to be given by a quadratic form of the ranges of the stress intensity factors of modes I and II. The direction of fatigue crack extension from the inclined crack was roughly perpendicular to the tensile axis at stress ranges just above the threshold value for non-propagation. On the other hand, at stress ranges 1.6 times higher than the threshold values the crack grew in the direction of the initial crack. The rate of crack growth in the initial crack direction was found to be expressed by the following function of stress intensity factor ranges of mode I, K₁, and mode II, K₂: $\text{dc}\text{dN}\text{= C(K}{}_{\mathrm{eff}}\text{)sum}$, where $\text{K}{}_{\mathrm{eff}}\text{= [K}{}_1{}^4\text{+ 8K}{}_2{}^4\text{]}{}^{\mathrm{<mtext>1</mtext><mtext>4</mtext>}}$. This law was derived on the basis of the fatigue crack propagation model proposed by Weertman.     

Oxidation-reduction reactions of CeMO4+x (M = Ta or Nb) phases

Phase equilibrium methods, single crystal and powder x-ray diffraction analyses, thermogravimetric analysis and magnetic susceptibility measurements were utilized to define subsolidus phase relations $\text{in air}$ for the systems cerium oxide - Ta₂O₅ and cerium oxide - Nb₂O₅. Stoichiometric CeTaO₄ is stable in air (P_O2 = 0.21 atm) only above 1265°C. At 1265°C, the reversible reaction, $\text{3}\text{CeTaO}{}_4\text{+}\text{1}\text{2}\text{?}$CeTa₃O₉ + 2CeO₂ is established. If CeTaO₄ is quenched to room temperature and $\text{reheated}$ below 1000°C, or, if the material is rapidly cooled from above 1265°C to below 1000°C it absorbs oxygen according to, . The x parameter is variable and temperature dependent. Using a thermal microbalance, three distinct complex reaction series involving a homogeneity range in x were established, (a) 0.50 ≥ × ≥ 0.48 (<350°–600°C), (b) 0.17 ≥ × ≥ 0.06 (600°–950°C), (c) 0.40 ≥ × ≥ 0.34 (950°-room temperature). CeNbO₄ (not isostructural with CeTaO₄) also absorbs oxygen below ≈700°C in air to yield CeNbO_4+x materials.     

Intercroissances des structures de type perovskite et SrO deficitaires en oxygene : Les oxydes Ln2−xSr1+xCu2O6−x/2 (Ln = Sm,Eu, Gd)

New oxides Ln_2?xSr_1+xO_6?x/2 (Ln = Sm, EU, GD), corresponding to oxygen deficient intergrowths of double perovskite and SrO layers have been isolated for 0.70 ≤ x ≤ 0.90. They are characterized by an orthorhombic cell, $\text{a}\text{?}\text{a}{}_{\mathrm{p}}\text{? 3.9}\text{A}\text{?}$, $\text{b}\text{?}\text{3a}{}_{\mathrm{p}}$, and $\text{c}\text{? 20}\text{A}\text{?}$. A structural model has been obtained, showing that this structure, although closely related to that of La_2?xSr_1+xCu₂O_6?x/2+δ exhibits a different distribution of the oxygen vacancies, involving for copper several coordinations. The semi-conductive properties of these compounds, very different from the semi-metallic behaviour of La_2?xSr_1+xCu₂O_6?x/2+δ is explained by the distribution of the oxygen vacancies in the structure.     

Viscous dissipation effects on mixed convection about a rotating sphere

The effect of viscous dissipation on mixed convection flow about a rotating sphere is investigated analytically. A method based on Merk's type of series expansions is used to obtain the heat transfer rate and the skin-friction coefficients. Numerical computations were carried out for Eckert number Ec ranging from 0 to 0.1, rotation parameter B = 0, 1, 4 and buoyancy parameter ranging from 0 to 1 at various angular positions. As viscous dissipation increases heat transfer rate decreases. It is found that for Ec > 0, a critical value of B (say B_cri) exist such that $\text{Nu Re}{}_{\mathrm{R}}{}^{\mathrm{<mtext>?</mtext><mtext>1</mtext><mtext>2</mtext>}}$ increases as B increases up to B = B_cri and then decreases. B_cri decreases with Ec when the angle is fixed or decreases with angle when Ec is fixed. When Ec > 0, possibly there exist a λ, say λ_cri, such that $\text{Nu Re}{}_{\mathrm{R}}{}^{\mathrm{<mtext>?</mtext><mtext>1</mtext><mtext>2</mtext>}}$ increases with λ up to λ = λ_cri and then decreases. Also the effect of viscous dissipation on skin friction is investigated.     

Nature de la fluorescence de l'europium divalent dans les fluorures

The levels of the ${}^6\text{P}{}_{\mathrm{<mtext>7</mtext><mtext>2</mtext>}}$ (4f⁷) and 4f⁶5d¹ states of europium (+II) have been determined from fluorescence spectra in a series of fluorides M_xB_yF_z (M = alkaline-earth element, B = Li, Be, Mg, Y, Si). As in BaY₂F₈, SrSiF₆ and BaSiF₆, the ${}^6\text{P}{}_{\mathrm{<mtext>7</mtext><mtext>2</mtext>}}$ level lies even at room temperature far below the 4f⁶5d¹ band, only the f → f emission is observed. The influence of the choice of the alkaline-earth and the B cations and of the coordination of europium on the relative positions of the energy levels is discussed.     

Mass spectrometry of a silane glow discharge during plasma deposition of a-Si: H films

We undertook a mass spectrometric investigation of the ionic and neutral species present during the deposition of a-Si: H using an r.f. glow discharge in silane (mixed with helium or hydrogen). A correlation between the neutral composition of the plasma and the nature of the IR vibrational modes in the deposited film is proposed. The ionic species extracted from the silane discharge are not characteristic of the direct ionization of SiH₄. The predominance of the SiH₃⁺ ion is attributed to the ion-molecule reaction $\text{SiH}{}_2{}^{\mathrm{+}}\text{+ SiH}{}_4\text{→ SiH}{}_3{}^{\mathrm{+}}\text{+ SiH}{}_3$ Secondary ions Si₂H_n⁺ (n = 1?7) are also observed. Mass spectrometry of the ionic species resulting from the interaction of a hydrogen plasma with the a-Si: film suggests that atomic hydrogen plays an active role during the growth of the film.     

Electronic and spin configurations of Co3+ and Ni3+ ions in oxides of K2NiF4 structure: A magnetic susceptibility study

In La₄LiCoO₈, Li⁺ and Co³⁺ ions are ordered in two dimensions and Co³⁺ ions undergo transitions from the low-spin to the intermediate as well as the high-spin states. Both Sr₄TaCoO₈ and Sr₄NbCoO₈ exhibit low to intermediate-spin state transitions of Co³⁺ ions. In the system LaSr_1?xBa_xNiO₄, the e_g electrons are essentially in extended states forming a band. With increase in x, the band width decreases accompanying an increase in unit cell volume; high-spin Ni³⁺ ions are formed to a small extent with increasing x, but there is no spin-state transition. In LaSrAl_1?xNi_xO₄, at small x, there is a small proportion of high-spin Ni³⁺; when x ≈ 0.6, there is an abrupt decrease in the $\text{c}$/$\text{a}$ ratio, signalling the formation of the band. In LnSrNiO₄, the $\text{c}$/$\text{a}$ ratio decreases sharply between Ln = La and Nd; this is likely to be accompanied by a broadening of the band.     

Fracture toughness characterization of several aluminum alloys in semi-brittle fracture

A method has recently been developed for determining a nonlinear fracture toughness parameter defined by the relation $\text{G}\text{?}{}_{\mathrm{c}}\text{=}\text{C}\text{?}\text{G}{}_{\mathrm{c}}$ where G_c is the critical elastic strain energy rate as defined by Irwin. The $\text{C}\text{?}$ term is a function of the nonlinearity of the load-displacement test record and has been evaluated using the three parameter Ramberg-Osgood approach, although other curve fitting techniques could be applied as well. The method is quite straightforward and is applicable to plane stress, plane strain and mixed mode testing although only plane stress conditions are considered in this paper. For the case of a linear load-displacement record $\text{C}\text{?}\text{→ 1}$ and $\text{G}\text{?}{}_{\mathrm{c}}$ reduces to the linear elastic result.The toughness parameter $\text{G}\text{?}{}_{\mathrm{c}}$ has been evaluated for a number of high strength aluminum alloys and compared with published G_c values for these materials. The tests were conducted on center-cracked sheets of 2014-T6, 2024-T81, 7075-T6 and 7475-T61 aluminum alloys under conditions of varying specimen geometry and displacement gage length. It was found that the values of $\text{G}\text{?}{}_{\mathrm{c}}$ obtained from displacement readings with a gage length of 2 in. generally agreed with published values of $\text{G}{}_{\mathrm{c}}\text{=}\text{K}{}_{\mathrm{c}}{}^2\text{E}$. The $\text{G}\text{?}{}_{\mathrm{c}}$ values were found to vary inversely with gage length and a/w ratios. The variation in values for $\text{G}\text{?}{}_{\mathrm{c}}$ is of the same order of magnitude as the scatter in published values for G_c. However, $\text{G}\text{?}{}_{\mathrm{c}}$ appears to be less sensitive than G_c to changes in a/w.     

Study of the oxidation kinetics of finely-divided magnetites IV. Influence of zinc substitution

The oxidation kinetics of zinc substituted magnetites (Fe²⁺_1?xZn²⁺_xFe³⁺₂)O^2?₄ (O < x < 1) into the γ defect phase of type x(Zn²⁺Fe³⁺₂O^2?₄), $\text{3}\text{2}\text{(1?}\text{x}\text{)}\text{Fe}{}^{\mathrm{3+}}{}_2\text{O}{}^{\mathrm{2?}}{}_3$ is found to be governed by the diffusion with a chemical diffusion coefficient depending on vacancy concentration. For compounds rich in zinc the diffusion coefficient is constant and the rate law written as v = k Pⁿ_(O2) with $\text{n}\text{=}\text{1}\text{4}$ is in agreement with a partial association of defects. For low substitution extents the diffusion coefficient varies with the transformation extent α and exponent n from the pressure law is equal to $\text{1}\text{2}$, which agrees with a total association of defects.     

A thin film electrochromic display based on the tungsten bronzes

The main features of a passive thin film display cell based on the electrochemically reversible formation of a tungsten bronze according to the reaction

$\text{(colourless) WO}{}_3\text{+ x}\text{M}{}^{\mathrm{+}}\text{+ x}\text{e}{}^{\mathrm{?}}\text{?}\text{M}{}_{\mathrm{x}}\text{WO}{}_3\text{(blue)}$

where 0 < x < 1 are considered. Chemical analysis of an electrochemically coloured WO₃ film has confirmed the presence of M. It is shown that a critical requirement of these cells is that D_τ(qC_m/Q)² ≈ 1, where the symbols are, in order, the M⁺ diffusion coefficient, the required device response time, the electronic charge, the maximum practical volume concentration of M in the WO₃ film and lastly the area colouring charge. Typical energy requirements might be about 10 mJ cm^?2 per complete cycle in a favourable case.Ionic injection overpotentials and ionic diffusion both appear to play a significant role in determining cell currents. Preliminary diffusion coefficient results for Li⁺ in r.f. sputtered WO₃ films are reported, and their predicted dependence of film structure is discussed. The optical absorption of coloured WO₃ films is presented, and it is interpreted as being predominantly due to free-electron intraband transitions.     

Beam preparation system and beam emittance control,prerequisites for high-resolution magnetic spectroscopy

Using first order calculations derived for an achromatic system ($\text{δx}{}_{\mathrm{<mtext>F</mtext>}}\text{δE}{}_{\mathrm{<mtext>i</mtext>}}\text{= 0}$) or an optimized system (x_F minima), it is shown that the final resolution measured in the focal plane (possibly kinematically displaced) of the spectrometer depends only on the emittance of the accelerator and on the efficient area of the analyser, exclusive of the properties of the spectrometer. The use of this result is of course limited by higher order terms which may be important or by considerations out of the scope of this article, like target effects, etc.     

Concentration quenching of Nd3+ fluorescence in ordered perovskite oxides and fluorides

New ordered perovskite-type fluorides, Rb₂KNdF₆ and Cs₂KNdF₆, have been synthesized and their luminescence properties investigated. Their neodymium emission shows weak self-quenching. This results both from the isolation of the neodymium in discrete NdF₆ octahedra and from the weak absorption associated with the ${}^4\text{I}{}_{\mathrm{<mtext>9</mtext><mtext>2</mtext>}}\text{→}{}^4\text{I}{}_{\mathrm{<mtext>15</mtext><mtext>2</mtext>}}$ transitions in the region of the ${}^4\text{F}{}_{\mathrm{<mtext>3</mtext><mtext>2</mtext>}}\text{→}{}^4\text{I}{}_{\mathrm{<mtext>15</mtext><mtext>2</mtext>}}$ emission, which restricts cross-relaxation via the intermediate ${}^4\text{I}{}_{\mathrm{<mtext>15</mtext><mtext>2</mtext>}}$ levels. In contrast the emission of neodymium, substituted for lanthanum in the homologous Ba₂LaNbO₆ oxide, shows a strong concentration self-quenching.     

Characterization of antimony-doped tin oxide films for solar cell applications

Transparent conducting undoped tin oxide (SnO₂) and antimony-doped tin oxide (ATO) films were deposited onto Pyrex glass and single-crystal silicon substrates using an inexpensive chemical vapour deposition system. SnCl₂ and SbCl₃ were used as the source reagents with oxygen and nitrogen respectively as the carrier gases. The deposition conditions were as follows: temperature, 350–500 °C; oxygen flow rate, 0.8–3.25 1 min^-1; nitrogen flow rate, 0–0.1 1 min^-1; deposition time, 5–20 min. The antimony concentration in the film and its physical properties were the same on both substrates. A figure of merit (Tr¹⁰/R_sh where Tr is the transmission at a particular wavelength and R_sh is the sheet resistance) was used to compare the performance of these films. The maximum figure of merit for SnO₂ films $\text{(1.43 × 10}{}^{-3}\text{Ω}{}^{-1}\text{(}\text{Tr}\text{= 95\% and R}{}_{\mathrm{<mtext>sh</mtext>}}\text{= 420 Ω/□))}$ was obtained when they were deposited at 500 °C with oxygen at a flow rate of 1 1 min^-1. The sheet resistance of antimony-doped films is a minimum at 3 mol.% Sb and the transmission decreases as the antimony concentration increases. The maximum figure of merit obtained for ATO films was $\text{6.78 × 10}{}^{-3}\text{Ω}{}^{-1}\text{(}\text{Tr}\text{= 90.6\% and R}{}_{\mathrm{<mtext>sh</mtext>}}\text{= 55 Ω/□)}$ for an antimony content of 3 mol.% and a nitrogen flow rate of 0.07 1 min^-1. These results are explained theoretically and are compared with those reported by other workers.