The high-pressure phase diagram of ammonia dihydrate

We have investigated the P–T phase diagram of ammonia dihydrate (ADH), ND3·2D₂O, using powder neutron diffraction methods over the range 0–9 GPa, 170–300 K. In addition to the ambient pressure phase, ADH I, we have identified three high-pressure phases, ADH II, III, and IV, each of which has been reproduced in at least three separate experiments. Another, apparently body-centred-cubic, phase of ADH has been observed on a single occasion above 6 GPa at 170 K. The existence of a dehydration boundary has been confirmed where, upon compression or warming, ADH IV decomposes to a high-pressure ice phase (ice VII or VIII) and a high-pressure phase of ammonia monohydrate (AMH V or VI).     

Recovery of low temperature electron irradiation-induced damage in n-type gaas

Undoped n-type GaAa was irradiated near 5 and 77 °K with electrons having incident energies between 0.46 and 1.30 MeV. The recovery of the electrical resistivity and the Hall coefficient upon annealing from 4 to 520 °K was monitored. Changes which occurred upon annealing below 200 °K could be reversed by ionizing radiation. A small amount of irreversible ionization-induced recovery was observed after irradiation near 5 °K. Major irreversible recovery stages were centered near 235 (stage I), 280 (stage II) and 520 °K (stage III). Recovery in stage I and II obeyed first order kinetics. The activation energies of stages I and II were determined as 0.72 and 0.83 eV, respectively. The carrier concentration changes per unit irradiation dose corresponding to the three recovery stages differed in their energy dependence indicating that the defects which are removed in stage III have the lowest threshold energy. The carrier concentration changes per unit irradiation dose corresponding to stages I and III were higher for irradiation near 5 °K than for irradiation near 77 °K.     

Structural instabilities and transverse effective charges in IV–VI compounds

Transverse effective charges for some IV–VI, III–V and II–VI compounds are investigated on the basis of the interband electron-phonon coupling with the use of the Penn model for electron energy bands. The results show that the large transverse effective charges of IV–VI compounds are related with strong electron-phonon interaction as well as with the softening of TO phonon in IV–VI compounds.     

Raman spectroscopic and optical absorption study of the high pressure behaviour and polymorphism in KO2

Abstract

Raman scattering, visible absorption, and optical observation studies have been made on polycrystalline potassium superoxide (KO₂) in a diamond anvil cell as a function of pressure and temperature. Three new phases are observed. With increasing pressure at 298 K, KO₂ transforms from the well known modified CaC₂ structure (Phase II), to two new phases (VII, and VIII). The transformation from III to VII occurs at about 3.2GPa. Phase VII transforms to phase VIII at about 4.4GPa. However, in some samples phase VII does not occur and phase II transforms directly into phase VIII at about 4.2 GPa. These structural transformations are indicated by marked changes in the Raman spectrum. The transitions out of phase II are also marked by a discontinuous red shift in the optical absorption edge. From optical observations we have also determined the pressure and temperature dependence of the transitions from phase II to the high temperature cubic (B1) phase I as well as from the high pressure phases VII and VIII to a new nonbirefringent phase IX. This new phase IX has the cubic B2 (CsCl) structure as is shown by our recent X-ray synchrotron experiments.     

Thermoluminescence and electron spin resonance after room-temperature X-ray irradiation of NaCl:Mn2+

A parallel investigation of thermoluminescence (TL) and electron spin resonance (ESR) spectra on room-temperature (RT) X-irradiated NaCl:Mn²⁺ has been performed. The TL spectra in the range 20–300°C consist of five glow peaks, numbered from I to V. Temperatures at maximum height are 41°, 68°, 118°, 152° and 216°C, respectively. Peaks I, II and IV obey first-order kinetics, whereas peaks III and V fit second-order behavior. The wavelength spectrum for all glow peaks consists of two bands centered at 595 and 400 nm. The 595 nm emission is attributed to hole capture by Mn⁺ and subsequent deexcitation of Mn²⁺. The 400 nm emission is produced as a consequence of hole-F center recombination.The correlation of TL glow peaks to various defects has been investigated. Peak II is clearly related to manganese-vacancy dipoles and peak I can be roughly associated to free cation vacancies. Peak IV appears to relate to large Mn-aggregates, whereas peak V is intrinsic and not related to impurities.On the other hand, ESR data indicate that each glow peak in the 595 nm emission is associated to the annihilation of a given Mn-center; Peak I to Mn⁰C, peak II to Mn⁰C and Mn⁺, peak III to Mn⁺ and peaks IV and V to Mn⁰-D.     

Line width transitions in the deuteron magnetic resonance of polycrystalline ND4Cl,ND4Br,and ND4I

The line width of the deuteron magnetic resonance in polycrystalline ND₄Cl, ND₄Br, and ND₄I has been measured from 300°K down to 115°K. Below 200, 172, and 140°K in ND₄Cl, ND₄Br, and ND₄I, respectively, the line rapidly broadens. In addition, the I ? II transition of ND₄I causes a change of line width. The observed line widths agree with those calculated by the present writers from theVan Vleck second moment formula assuming a Gaussian line shape. For this agreement, in the phases II and III of ND₄Cl and in the phase I of ND₄I the deuteron-halogen interactions should be taken into account, whereas in the phases II and III of ND₄Br and ND₄I they should be omitted.     

Ordering of hydrogen bonds in high-pressure low-temperature H2O

The near K-edge structure of oxygen in liquid water and ices III, II, and IX at 0.25 GPa and several low temperatures down to 4 K has been studied using inelastic x-ray scattering at 9884.7 eV with a total energy resolution of 305 and 175 meV. A marked decrease of the preedge intensity from the liquid phase and ice III to ices II and IX is attributed to ordering of the hydrogen bonds in the proton-ordered lattice of the latter phases. Density functional theory calculations including the influence of the Madelung potential of the ice IX crystal correctly account for the remaining preedge feature. Furthermore, we obtain spectroscopic evidence suggesting a possible new phase of ice at temperatures between 4 and 50 K.     

Ice XII in its second regime of metastability

We present neutron powder diffraction results which give unambiguous evidence for the formation of the recently identified new crystalline ice phase [2], labeled ice XII, in completely different conditions. Ice XII is produced here by compressing hexagonal ice I(h) at T = 77, 100, 140, and 160 K up to 1.8 GPa. It can be maintained at ambient pressure in the temperature range 1.5相似文献   

Thermal resistivity,heat capacity and phase diagram of CBr4 under pressure

We have measured simultaneously the thermal resistivity and the heat capacity per unit volume for phases I, II, III and IV of CBr₄. We have used the transient hot-wire method, and have made measurements over the ranges 170 K to 425 K, and up to 2 GPa. Our results, and other evidence, indicate that I and III are plastic crystal phases, and that there is a significant degree of structural disorder in phase II. Three-phonon interactions probably provide the dominant contribution to the thermal resistivity of phase IV. Using structural analogies with the phases of CCl₄, we find that the relative values of the thermal resistivities are roughly as predicted by simple theory.     

First stages of the deposition of bismuth on copper examined by LEED: II. The (111) substrate

Three ordered overlayer structures are observed after evaporation for different times onto the (111) substrate. They are interpreted as monolayers with different densities: I, adsorption in sites of high coordination; II, a dense pseudo-square arrangement of bismuth atoms; III, a compact hexagonal arrangement. Structure III is only observed at high coverage and above 245°C. A reversible transformation occurs between II and III for a limited range of coverage. When they exist alone both structures II and III show melting type transitions. A schematic surface phase diagram is established.     

The bulk effect of point defects on young's modulus in electron irradiated copper

Abstract

Pairs of copper samples—one for electrical resistivity, the other for Young's modulus measurements - were irradiated simultaneously at 120°K with 3 MeV electrons up to an integrated dose of 2 × 10²⁰ el/cm². The effect of dislocation pinning and the bulk effect of point defects on Young's modulus E could clearly be separated. The following relation between the bulk effect ΔE/E and the resistivity increase Δρ[Ωcm] was found: ΔE/E = ?25 × 10⁴ × Δρ. Besides strong annealing in stages II and III (180–300°K) and some annealing between 300–500°K, stage V annealing (500–600°K) also was found. In stage III the resistivity annealed more than Young's modulus. whereas the converse occurred in stage V. These measurements are discussed in connection with the electron microsopical observation of point defect clusters after electron irradiation at 120°K and heating to room temperature.

Probenpaare, bestehend aus einer Widerstandsprobe und einer Probe zur Messung des Elastizitätsmoduls, wurden gleichzeitig bei 120°K mit 3 MeV-Elektronen bis zu einer Dosis von 2 × 10²⁰ el/cm² bestrahlt. Die direkte Reein-flussung des E-Moduls durch die im Gitter verteilten Punktdefekte (Volumeneffekt) konnte getrennt von der Beeinflussung durch Versetzungsverankerung gemessen werden. Es ergab sich dabei folgende Beziehung zwischen relativer Modulanderung ΔE/E und strahlungsinduziertem Widerstand Δρ[Ωcm]: ΔE/E = ?25 × 10⁴ × Δρ. Neben starker Erholung in den Stufen II und III (180–300 °K) und schwacher Erholung zwischen 300–500°K wurde auβerdem Stufe V (500–600°K) beobachtet. In Stufe III erholte sich der Widerstand starker als der E-Modul, wahrend in Stufe V das umgekehrte der Fall war. Die Messungen werden diskutiert in Zusammenhang mit der elektronenmikroskopischen Beobachtung von Punktdefektclustern nach Elektronenbestrahlung bei 120°K und anschlieβender Erwärmung auf Raumtemperatur.     

Irradiation effects in II-VI compounds

Abstract

A summary of published results on electron energy threshold measurements in II–VI compounds, and their interpretation in terms of damage on the metal and chalcogenide sublattices, is given. EPR results in irradiated II–VI compounds are also reviewed. These include the F⁺ center in ZnS; ZnO, and BeO and new results on the zinc vacancy (V) in ZnSe. For the zinc vacancy, optical absorption bands at 4680Å and 8850Å are identified with V^? and a band at 5000Å is tentatively assigned to V^?. The activation energy for anneal of the vacancy is measured to be 1.26±.06 eV, and this is tentatively identified as the activation energy for vacancy motion. An EPR spectrum produced in a 20.4 °K irradiation is tentatively identified as a zinc vacancy-interstitial pair. Complete annealing occurs for this defect in the range 60–100 °K.     

Epitaxial crystal growth by sputter deposition: Applications to semiconductors. Part 2

Sections I through IV, presented in Part 1 of this review, included discussions on experimental techniques, the physics of ion/surface interactions, and ion bombardment effects on film nucleation and growth kinetics. In this section, the literature on the growth of epitaxial semiconductor films is reviewed in detail in this section. The discussion is divided into separate subsections on elemental semiconductors, III–V, II–VI, IV–VI, “other” semiconductors, and metastable semiconducting alloys. In each case, an attempt was made to provide a critical analysis of the present understanding and state of the art. Early work on sputter deposition is described in a series of general review articles by Francombe^223–225 as well as in more recent reviews by Greene²²⁶ and Greene and Eltokhy²²⁷ directed specifically towards semiconductors.     

Ionic conductivity of Li2NaK(SO4)2

A DSC study of Li₂NaK(SO₄)₂ in the range 300∽925 K has revealed that the compound undergoes phase transitions at 654, 682, 778 and 866 K, before melting congruently at 900 K. The five phase which are observed are designated I, II, III, IV and V with increasing order of temperature. A comparison of the enthalpy of melting with the transition enthalpies suggests that the phases IV and V are plastic phases. The ionic conductivity was measured in the range 584∽895 K by an ac impedance technique. The phase IV showed the smallest activation energy as determined from the temperature dependence of the conductivity (E_a=0.82 eV). The highest conductivity (1.0 Ω⁻¹ cm⁻¹) was observed in phase V at 895 K.     

Kinetic analysis of high temperature secondary thermoluminescence glow peaks in α-Al2O3:C

The kinetic analysis of secondary glow peaks in carbon-doped aluminium oxide is reported. A glow curve measured at 0.4 °C s⁻¹ after beta irradiation to 3 Gy revealed at least five peaks as a result of various techniques of glow curve resolution; the dominant peak at 156 °C (peak II) and two weaker-intensity secondary peaks one at 36 °C (peak I) and the other at 264 °C (peak III). Peaks IIA and IV at 170 and 422 °C respectively only became apparent after removal of preceding more prominent peaks. The secondary peaks are particularly weak in intensity and are as usual dominated by the main dosimetry peak. The analysis in this report focusses on peak III, usually seen adjacent to the main dosimetry peak but whose presence is masked by the extreme sensitivity of the latter. Complementary analyses of the weaker intensity peaks I, IIA and IV are included. Peaks I, IIA and III are subject to first-order kinetics while for peaks II and IV the issue is less conclusive. The activation energy increases from 0.72 eV for peak I to about 1.3 eV for peak IV with values for peak II and IIA similar at ∼1 eV. In general, the frequency factor corresponding to the lower temperature peaks (I, II, and IIA) have values (10¹⁰–10¹² s⁻¹) that are an order of magnitude or so greater than for peaks III and IV (10⁹–10¹¹ s⁻¹). Except for peak I, peak II and all other secondary peaks are affected by thermal quenching whose activation energy was determined as ΔE = 0.95 ± 0.04 eV using peak IIA and as ΔE = 1.48 ± 0.10 eV using peak III. The overall conclusion is that all peaks correspond to electron traps and are associated with the same recombination centre.     

Spectrophotometric Studies of the Reaction of Zinc(II) with Some Azo‐Triazol Compounds and Its Application to the Spectrophotometric Determination of Microamounts of Zinc(II)

Abstract

A new, simple, and sensitive quantitative spectrophotometric method for the rapid determination of zinc(II) using six azo compounds based on 3‐amino‐1,2,4‐triazole, namely {3‐(2,4‐dihydroxy‐1‐phenylazo)‐1,2,4‐triazole) (I), 3‐(2‐hydroxy‐5‐methyl‐1‐phenylazo)‐1,2,4‐triazole) (II), 3‐(2‐hydroxy‐5‐acetyl‐1‐phenylazo)‐1,2,4‐triazole) (III), 3‐(2‐hydroxy‐5‐ethylcarboxylate‐1‐phenylazo)‐1,2,4‐triazole) (IV), 3‐(2‐hydroxy‐5‐formyl‐1‐phenylazo)‐1,2,4‐triazole) (V), and 3‐(2‐hydroxy‐5‐bromo‐1‐phenylazo)‐1,2,4‐triazole) (VI), has been developed for use in aqueous media containing 40% (v/v) methanol. Linear calibration graphs are obtained up to 2.6, 5.9, 5.2, 5.2, 8.2 and 9.0 µg mL^?1 using ligands I, II, III, IV, V, and VI, respectively. Absorption maxima, molar absorptivities, and Sandell's sensitivities of 1:2 (M:L) complexes were found to be 490, 530, 505, 520, 550, and 510 nm, 4.86×10⁴, 2.10×10⁴, 1.26×10⁴, 0.10×10⁴, 0.19×10⁴, and 0.29×10⁴ L mol^?1 cm^?1, and 0.0014, 0.0031, 0.0052, 0.0662, 0.0348, and 0.0225 µg cm^?1 for ligands I, II, III, IV, V, and VI, respectively. Using the masking agents, the color reactions are free from interference by more than 30 ions investigated. The method has been applied to the spectrophotometric determination of trace amounts of zinc in pharmaceutical formulations and human hair samples. A study of some zinc solid complexes showed that chelation takes place through one nitrogen atom of the azo group and proton displacement from the hydroxyl group.     

Enthalpy of formation of Schottky defects in semiconductors

The enthalpy of formation of Schottky defects in crystals of II–VI, III–V, and IV–VI compounds has been calculated with the use of a method based on Mie-Lennard-Jones pair potentials, whose parameters have been determined from the experimental data on the Debye temperature, Grüneisen parameter, Poisson’s ratio, elastic constants, and bulk modulus. The found values of the enthalpy of formation agree with the known literature data and can be used to calculate the density of these defects in the crystals.     

双水相体系中Cu(Ⅱ),La(Ⅲ),U(Ⅵ),Ce(Ⅳ)光谱行为及萃取分离

利用聚乙二醇2000(PEG)-(NH)2SO4-萃取剂(铜试剂)双水相体系,采用液-液萃取的方法,研究了PEG相、单纯水相中金属离子络合物及萃取剂的光谱行为,探讨了金属离子络合物在PEG相中存在形态及萃取机理。同时实验了在不同酸度,不同盐用量,不同萃取剂用量,以及在不同表面活性剂的影响下,铜、镧、铀、铈的萃取率,通过控制一定条件,实现了Cu(Ⅱ)与La(Ⅲ),Cu(Ⅱ)与Ce(Ⅳ)之间的定量萃取分离。     

Break-Through Investigation on Uranium Isotope Separation in the System Uranyl Ion Solution Ti(III)-Cationic Resin

A break-through experiment on separation of uranium isotopes was carried out by use of a cation-exchange resin in Ti(III) form. By analyzing the experimental results the apparent equilibrium constants of the order K = 1·00021–1·00034 were determined.

The maximum value on the experimental curies of the isotopic ratio versus effluent volume was interpreted by considering two antagonistic isotope effects: one relatively large given by an exchange reaction between U(IV) in resin and U(VI) in solution and another smaller given by the reduction reaction of U(VI) with Ti(III). The difference of the equilibrium constants of the these two isotope effects as a function of temperature was used for the determination of the apparent thermodynamic values of the resultant process, determined experimentally: ΔH⁰ = 0.8542 cal mol^?1 and ΔS⁰ = 3.33×10^?3cal°K^?1.