Standard Gibbs' energies of formation of BaCuO2, Y2Cu2O5 and Y2BaCuO5

The Gibbs' energies of formation of BaCuO₂, Y₂Cu₂O₅ and Y₂BaCuO₅ from component oxides have been measured using solid state galvanic cells incorporating CaF₂ as the solid electrolyte under pure oxygen at a pressure of 1.01×10⁵ Pa BaO + CuO BaCuO₂ G _f,ox ^o (± 0.3) (kJ mol^–1)=–63.4–0.0525T(K) Y₂O₃ + 2CuO Y₂Cu₂O₂ G _f,ox ^o (± 0.3) (kJ mol^–1)=18.47–0.0219T(K) Y₂O₃ + BaO + CuO Y₂BaCuO₅ G _f,ox ^o (± 0.7) (kJ mol^–1)=–72.5–0.0793T(K) Because the superconducting compound YBa₂Cu₃O_7– coexists with any two of the phases CuO, BaCuO₂ and Y₂BaCuO₅, the data on BaCuO₂ and Y₂BaCuO₅ obtained in this study provide the basis for the evaluation of the Gibbs' energy of formation of the 1-2-3 compound at high temperatures.     

Microstructure and crystallographic texture of rolled polycrystalline Fe3Al

An imperfectly B₂ ordered Fe₃Al aggregate was cast, thermomechanically hot rolled and finally annealed at 870 K. Subsequently, the specimen was rolled at 800–830 K to a strain of 80%. The microstructure and the crystallographic texture of the rolled polycrystalline sample was investigated within the range =20–80%. The microstructure consisted of flat, elongated grains. In numerous grains straight slip lines were detected. Even after =80% recrystallization was not observed. The rolling texture of Fe₃Al considerably deviates from that of non-ordered body centered cubic (b.c.c.) alloys and pure b.c.c. metals. The {111}uvw texture fibre (7-fibre) was very pronounced, while the {hkl}110 fibre (-fibre) was very weak. The {112}110 orientation which represents the strongest texture component in non-ordered b.c.c. alloys did not occur at all. The textures are discussed in terms of the {110}111, {112}111, {112}111 and {123}111 slip systems. The contribution of crystallographic slip of the various types of potential slip systems was simulated by means of the Taylor theory.     

The mechanism of continuous dissolution of the lamellar structure in aged Al 22 at% Zn alloy

The mechanism of continuous dissolution was studied using transmission electron microscopy, X-ray diffraction and hardness measurements. The metastable phase was identified in the first stage of dissolution nucleating at the - boundaries. Interface dislocations at the - boundaries forming a perpendicular net in the 110 directions were identified as of screw character and of Burgers vector b=1/2a 110. During dissolution a change of shape of precipitates occurs leading to their fragmentation and to a change of the direction of boundaries into 110 directions.     

Anisotropy in the hardness and friction of calcium fluoride crystals

Anisotropy in the Knoop indentation hardness and the friction of diamond cones on calcium fluoride crystals has been investigated at experimental temperatures from 20 to 300° C. It is shown that the directions of minimum and maximum indentation hardness, on the (001) plane, are 110 and 100 respectively whilst the 1¯10 are harder than the 11¯2 directions on the (111) plane. Also, the sliding friction in the (001) plane is greatest in the 110 directions and least in the 100 and, on the (111) cleavage plane, [¯1¯12] sliding leads to higher friction than [11¯2]. The nature of anisotropy, for both hardness and friction measurements, does not change over the experimental temperature range covered in this work. Observations on the resultant deformation are made and these anisotropic properties are explained in terms of the effective resolved shear stresses developed on the {100} 011 primary slip systems at all experimental temperatures.     

Structural and magnetic characterization of nanocrystalline Ni-20%Fe permalloy films

Samples of nanocrystalline Ni-20%Fe permalloy, obtained by electrodeposition, were studied using an X-ray diffraction technique and magnetic force microscopy. After deposition, the alloy exhibited strong fiber texture with the major component being 1 0 0 and a lesser contribution from 1 1 1. An increase in deposition current density led to a reduction in the strength of the 1 0 0 texture. Despite the small magnitude of the magnetic interaction, images of magnetic domains were obtained using magnetic force microscopy. The images were, however, unstable and changed significantly with the scanning time. Annealing of the permalloy above 573 K caused rapid grain growth and a transformation of the 1 0 0 fiber to 1 1 1 fiber. Numerical analysis of the texture data was conducted to assess the atomic structure of grain boundaries in the as-deposited and annealed states.     

Photosensitive Centers in CdTe〈Ge〉, CdTe〈Sn〉, and CdTe〈Pb〉

The spectral and temperature dependences of photoconductivity in CdTePb crystals under band-gap and combined excitation were studied at photon energies in the range 0.53–1.7 eV and temperatures from 80 to 300 K. The high photosensitivity of the crystals and the observed IR and temperature quenching of photoconductivity indicate that, just as in CdTeGe and CdTeSn, the recombination processes in CdTePb are dominated by deep centers with drastically different capture cross sections for electrons and holes. Some parameters of the centers are determined. The results suggest that the likely defect species responsible for the high photosensitivity of CdTePb is an acceptor complex consisting of a Cd vacancy and a metal (Ge, Sn, Pb) ion on the Cd site: (V ^2– _CdM⁺)^–/0.     

Dislocations in extruded Co-49.3at% Al

Polycrystalline Co-49.3at% Al which had been extruded at 1505 K was examined using transmission electron microscopy. Diffraction contrast analysis showed that b = 100 as well as b = 111 dislocations contribute to elevated temperature deformation in CoAl. Therefore, it was concluded that sufficient slip systems exist in CoAl to allow for general plasticity in the absence of diffusional mechanisms. Since no examples of b = 110 dislocations were found, the importance of 110{1¯10} slip in CoAl at 1505 K is unclear. Dislocations of the type b = 001 were observed on both {110} and {100} planes while b = 111 dislocations were observed on {1¯10} planes.     

Atom positions in the R-phase unit cell in TiNi shape memory alloy

A crystallographic analysis of the atom positions in the unit cell of the R-phase of the TiNi shape memory alloy has been performed. In addition to a homogeneous shape change the atoms are found to shuffle in the [111]_B2 and –211_B2 directions during the B2 to R-phase transformation. The origin of these shuffles is found to be a complex interaction between 1101–10 transverse acoustic and 111 longitudinal acoustic soft phonon modes.     

Electron diffraction study of superlattices and orientation variants in Ca3SrAl6SO16

Samples having the nominal composition of Ca₃SrAl₆SO₁₆ were sintered at 1380 °C and analysed by electron diffraction. The frequent appearances of forbidden and satellite reflections in this compound imply the presence of a number of basal and nonbasal superlattices so that the microstructure of this cement clinker was characterized by various superstructures including one-, two- and even three-dimensional superstructures along the 0 0 1, 1 1 0, 1 1 2, 1 1 4 or 2 2 1, 0 1 3 and 1 2 3 directions with repeat periods of two or three times of that of basic one, respectively, and intergrowth of these. Various domain structures with 90°, 120° and 48.2°, etc., orientation relationships were also detected in these superstructures and the total number of these orientation variants related to the symmetry elements lost in the process of phase transformation, can be predicted according to the conclusions of Van Tendeloo and Amerlinckx, or they are equal to the number of those unique planes in the matrix.     

Etching of MgO crystals in acids: surface micromorphology

Several etchants based on simple acids are proposed for revealing dislocations on {100}, {110} and {111} faces of MgO single crystals. Some acids under different etching conditions are shown to produce etch pyramids at decorated dislocations, while etch hillocks, spherulites and dendrites are formed under different conditions. With increasing concentration of H₂SO₄, 110 pits, circular pits, 100 pits, 110 pyramids as well as 100 pits, dendrites and spherulites, and hillocks are formed in that order. Etching characteristics of other acids also showed a more or less identical trend. The observations are interpreted with the assumption that with increasing concentration of acid, an effective undersaturation and later supersaturation is developed very close to the dissolving crystal face. The chemistry of the dissolution process is also discussed.     

Dislocation structures in Zr3Al-based alloys

Transmission electron microscopy has been used to investigate dislocation structures in deformed binary and ternary Zr₃Al-based alloys. In the binary alloy deformed at temperatures between 293 and 673 K the dislocations in the Zr₃Al phase consisted of a/31 1 2-type partial dislocations bounding superlattice intrinsic stacking fault on {1 1 1} planes. The {111} a/31 1 ¯2 stacking fault energy was approximately 2mJ m^–2 at 673 K. In binary specimens deformed between 873 and 1073 K cube slip predominated. Dislocations consisted mainly of a/2 1 1 0 pairs separated by antiphase boundary. For this temperature range the {1 0 0} a/201 1 antiphase boundary energy was between 30 and 45 mJ m^–2. Alloying with niobium or titanium was found to increase the {111} a/31 1¯2 stacking fault energy and thus increase the propensity for antiphase boundary-type dissociation.     

Size-strength effects in sapphire and silicon nitride whiskers at 20° C

Tensile tests at 20° C have been carried out on seventy-three sapphire whiskers and on seventeen silicon nitride whiskers. The sapphire whiskers were of 0001, 1¯120, 10¯10, and 10¯11 orientations, while the silicon nitride whiskers were 0001, 11¯20, and 10¯13. Tensile strengths were in the range 45 to 1500 kg/mm², and deformation was found to be purely elastic. The tensile strength data have been analysed and fitted to empirical equations describing the effect of size on strength for different orientations. These empirical equations have been used to deduce possible fracture nucleation mechanisms. It is concluded that, in the case of 0001 sapphire whiskers, fracture nucleation may be due to dislocation pile-ups or interactions, while in the other cases a Griffith flaw mechanism is probably applicable.     

1 : 2 Long-range ordering and defect mechanism of WO3-doped perovskite Ba(Mg1/3Ta2/3)O3

The nature of the B-site cation ordering and the associated defect process necessary to stabilize the ordered domains were investigated using the WO₃-doped BaMg_1/3Ta_2/3O₃ BMT system as a typical example of BaB_1/3B_2/3O₃-type complex perovskites. It was shown that only the 1 : 2 long-range ordering of the B-site cation existed in both undoped and WO₃-doped BMT perovskites. The atomic defect mechanism associated with the stoichiometric 1 : 2 long-range ordering was systematically investigated. It is concluded that the substitution of W⁶⁺ for Ta⁵⁺ in the WO₃-doped BMT enhances the degree of the 1 : 2 long-range ordering and produces the positively charged W _Ta sites with a concomitant generation of tantalum vacancies V_Ta and mobile oxygen vacancies V _O for the ionic charge compensation.     

Deformation and recrystallization textures of copper single crystals and bicrystals

Recrystallization textures in rolled copper specimens have been investigated so as to elucidate the mechanisms of cube texture formation. The specimens are single crystals with the orientations corresponding to the main components of the rolled textures, such as {112}111,{110}112, etc. and bicrystals consisting of such oriented crystals. The cube texture was not observed in any single crystal specimens, but observed in only two bicrystal specimens with {112}/111{100}001 and {110}112/{100}001 orientations. The formation of cube texture seems to require the existence of a cube oriented region in the deformed state, and the favourable oriented matrix to allow the growth of such nuclei.     

Investigation of energy-gap anisotropy in superconducting aluminum,cadmium, and zinc

Measurements of the low-temperature specific heat of the pure metal and dilute nonmagnetic alloys of Al, Cd, and Zn are described. The washing out of the energy gap anisotropy with increasing impurity as predicted by Anderson was observed in aluminum-magnesium alloys, and the mean-squared anisotropy parameter a ² was measured to be a ²0.010. Values deduced from measurements on Zn and Cd and their corresponding alloys with 1₀ gave a ²0.02 for Zn and a ²0.05 for Cd. Values of the gaps determined by fitting to a two-gap model are given and compared to those deduced from previous work.     

On the mechanism of feathery crystallisation of aluminium

The growth of twinned crystals of aluminium on solidification is discussed with reference to the structure of the growing tip. It is shown that one must differentiate between two types of 112 growth directions in the twin boundary. Normally, all the tips grow in the same type of 112 growth direction and this particular type may give the tip a favourable shape, possibly by producing a sharp edge. If a tip is growing in a less favourable 112 direction, the favourable type can be established by the twins changing sides. This is observed to occur regularly in the continuous casting method according to Hunter. The re-entrant edge mechanism is not supported by the present results.     

Phase equilibria and thermodynamic properties in the system Ni-Mo-O

Coexisting phases in the Ni-Mo-O ternary system at 1373 K have been identified by X-ray diffraction, optical microscopy and scanning electron microscopy. The samples were equilibrated in evacuated quartz capsules. Only one ternary phase, NiMoO₄, was found to exist in the system. The reversible e.m.f. values of the following solid-state galvanic cells were measured in the temperature range 900 to 1500 K: (I) Pt, Ni + NiO/(CaO) ZrO₂/NiO + MoO₂ + NiMoO₄, Pt; (II) Pt, Mo + MoO₂/(CaO) ZrO₂/O₂, Pt; and (III) Pt, Mo + MoO₂/(CaO) ZrO₂/Ni-Mo + MoO₂, Pt. The Gibbs energies of formation of NiMoO₄ and MoO₂ and activities in Ni-Mo alloys were derived from the e.m.f. data. For the reaction NiO + MoO₂ + 2(02) NiMoO₄ we obtain G _r ⁰ = -201 195 + 69.70T (±400) J mol^–1; for Mo + (02) MoO₂ we obtain G _f ⁰ = –578880 + 168.5T (+500) J mol^–1. Based on the information from phase identification studies and thermodynamic stabilities, the isothermal section and oxygen potential diagram for the Ni-Mo-O system at 1373 K have been developed.     

Structure and Properties of LiGaO2Crystals

Structural evidence is presented that LiGaO₂crystals (sp. gr. Pna2₁, point gr. mm2) may have different polarities. X-ray structural analysis of nominally undoped and doped (Cr or V) LiGaO₂crystals grown by the Czochralski technique shows that LiGaO₂and LiGaO₂Cr crystals differ in polarity from LiGaO₂V. Defect LiGaO₂can be thought of as a twin constituted by individuals of different polarities. Polarimetry data indicate that both LiGaO₂and LiGaO₂V are optically active.     

Multi-length scale modeling of CVD of diamond Part II A combined atomic-scale/grain-scale analysis

Chemical vapor deposition of polycrystalline diamond films is studied by combining an atomic-scale kinetic Monte Carlo model with two one three-dimensional and one two-dimensional grain-scale models. The atomic-scale model is used to determine the growth rates of 111- and 100-oriented surface facets, the surface morphology of the facets and the extent of incorporation of the crystal defects. Using the atomic-scale modeling predicted growth rates for the 111- and 100-oriented facets, grain-scale modelling is carried out to determine the evolution of grain structure, surface morphology and crystallographic texture in the polycrystalline diamond films. It is found that depending on the relative growth rates of the 111- and 100-oriented facets, which can be controlled by selecting the CVD processing conditions, one can obtain either 110-textured films with a relatively smooth faceted surface or 100-textured films with a highly pronounced deep facets. In both cases, however, the film surface is composed entirely of the 111 facets. This findings are found to be fully consistent with the available experimental results.     

Texture study of two molybdenum shaped charge liners by neutron diffraction

The textures of two different conical shaped liners, fabricated by the same forging processes from arc-cast and powder-sintered ingots, were investigated by using neutron-diffraction measurements and three-dimensional orientation-distribution-function (ODF) analysis. The major textures of both liners could be described by the (1 1 1) uv w and (1 0 0) u v w type. The two liners had essentially identical texture at the 8 cm position (measured from the base of the cone) with strong sheet-type texture components, i.e. (1 1 1) ¯1 0 1, (1 1 1) ¯1 1 0 and (1 0 0) 0 1 1. However, the dominant textures at the 3 cm positions were 1 1 1 and 1 0 0 fibre textures with the fibre axes oriented parallel to the normal direction in both liners. A strong cube texture was observed at the 3 cm position of the arc-cast liner but it was not observed for the powder-sintered liner. The arc-cast liner had a generally higher degree of texture than the powder-sintered liner.