First principles calculations of thermal equations of state and thermodynamical properties of MgH2 at finite temperatures

We present the first principles calculations of the thermodynamical properties of magnesium hydride (MgH₂) over a temperature range of 0–1000 K. The phonon dispersions are determined within the density functional framework and are used to calculate the free energy of MgH₂ within the quasiharmonic approximation (QHA) at each cell volume and temperature T. Using the free energies the thermal equation of state (EOS) is derived at several temperatures. From the thermal EOS structural parameters such as the equilibrium cell volume (V₀) and elastic properties, namely, bulk modulus (K₀) and its pressure derivative are computed. The free energies are also used to calculate various thermodynamical properties within QHA. These include internal energy E, entropy S, specific heat capacity at constant pressure C_P, thermal pressure P_thermal(V, T) and volume thermal expansion ΔV/V (%). The good agreement of calculated values of S and C_P with experimental data exhibits that QHA can be used as a tool for calculating the thermodynamical properties of MgH₂ over a wide temperature range. P_thermal(V,T) increases strongly with T at all the volumes but it is a slowly varying function of volume for T = 298–500 K. According to Karki [B.B. Karki, Am. Miner. 85 (2000) 1447] such volume based variations can be neglected and so it is possible to estimate the thermal EOS only with the knowledge of the measured P_thermal(V, T) versus temperature at ambient pressure and isothermal compression data at ambient temperature. Temperature dependence of ΔV/V(%) shows that V₀ increased with increase in temperature. However, the percentage decrease in K₀ superseded this percentage increase in V₀ even at temperatures moderately higher than 298 K. Therefore, we suggest application of temperature (T > 298 K) as an approach to enhance the hydrogen storage capacity of MgH₂ because of its better compressibility at these temperatures.     

Intrinsic microcrystalline silicon prepared by hot-wire chemical vapour deposition for thin film solar cells

Microcrystalline silicon (μc-Si:H) prepared by hot-wire chemical vapour deposition (HWCVD) at low substrate temperature T_S and low deposition pressure exhibits excellent material quality and performance in solar cells. Prepared at T_S below 250 °C, μc-Si:H has very low spin densities, low optical absorption below the band gap, high photosensitivities, high hydrogen content and a compact structure, as evidenced by the low oxygen content and the weak 2100 cm⁻¹ IR absorption mode. Similar to PECVD material, solar cells prepared with HWCVD i-layers show increasing open circuit voltages V_oc with increasing silane concentration. The best performance is achieved near the transition to amorphous growth, and such solar cells exhibit very high V_oc up to 600 mV. The structural analysis by Raman spectroscopy, X-ray diffraction (XRD) and transmission electron microscopy (TEM) shows considerable amorphous volume fractions in the cells with high V_oc. Raman spectra show a continuously increasing amorphous peak with increasing V_oc. Crystalline fractions X_C ranging from 50% for the highest V_oc to 95% for the lowest V_oc were obtained by XRD. XRD-measurements with different incident beam angles, TEM images and electron diffraction patterns indicate a homogeneous distribution of the amorphous material across the i-layer. Nearly no light induced degradation was observed in the cell with the highest X_C, but solar cells with high amorphous volume fractions exhibit up to 10% degradation of the cell efficiency.     

Pyroelectric properties of BST/PLT composite thick films with addition of xPbO–(1 − x)B2O3 glass

The Ba_xSr_1−xTiO₃ (BST)/Pb_1−xLa_xTiO₃ (PLT) composite thick films (20 μm) with 12 mol% amount of xPbO–(1 − x)B₂O₃ glass additives (x = 0.2, 0.35, 0.5, 0.65 and 0.8) have been prepared by screen-printing the paste onto the alumina substrates with silver bottom electrode. X-ray diffraction (XRD), scanning electron microscope (SEM) and an impedance analyzer and an electrometer were used to analyze the phase structures, morphologies and dielectric and pyroelectric properties of the composite thick films, respectively. The wetting and infiltration of the liquid phase on the particles results in the densification of the composite thick films sintered at 750 °C. Nice porous structure formed in the composite thick films with xPbO–(1 − x)B₂O₃ glass as the PbO content (x) is 0.5 ≥ x ≥ 0.35, while dense structure formed in these thick films as the PbO content (x) is 0.8 ≥ x ≥ 0.65. The volatilization of the PbO in PLT and the interdiffusion between the PLT and the glass lead to the reduction of the c-axis of the PLT phase. The operating temperature range of our composite thick films is 0–200 °C. At room temperature (20 °C), the BST/PLT composite thick films with 0.35PbO–0.65B₂O₃ glass additives provided low heat capacity and good pyroelectric figure-of-merit because of their porous structure. The pyroelectric coefficient and figure-of-merit F_D are 364 μC/(m² K) and 14.3 μPa^−1/2, respectively. These good pyroelectric properties as well as being able to produce low-cost devices make this kind of thick films a promising candidate for high-performance pyroelectric applications.     

Effect of GeF4 addition on the growth of hydrogenated microcrystalline silicon film by plasma-enhanced chemical vapor deposition

The effects of the addition of germanium tetrafluoride, GeF₄, are demonstrated on the growth of films of hydrogenated microcrystalline silicon, μc-Si:H, from SiH₄ and H₂ by r.f. plasma-enhanced chemical vapor deposition (r.f. PECVD). The structural and optoelectrical properties of the μc-Si(Ge):H(F) film are examined as a function of the flow rates of GeF₄ and H₂. The addition of GeF₄ enhances the deposition rate and the crystallinity of the Si network, when the flow rate ratio, r=Fr(GeF₄)/Fr(SiH₄) is below 10%. On the other hand, under conditions, r>0.1, the formation of a SiGe_x crystalline phase is promoted. The combination of the flow rates of GeF₄ and H₂ greatly affects the enhancement of crystallinity along with an increase in surface roughness.     

Temperature-independent electron tunneling injection in tris (8-hydroxyquinoline) aluminum thin film from high-work-function gold electrode

We fabricated electron-only tris (8-hydroxyquinoline) aluminum (Alq₃) single-layer devices with a device structure of glass substrate/MgAg anode (100 nm)/Alq₃ layer (100 nm)/metal cathode (100 nm), and systematically varied the work functions (WF) of the metal cathodes from WF = − 1.9 (Cs) to − 2.9 (Ca), − 3.8 (Mg), − 4.4 (Al), − 4.6 (Ag), and − 5.2 eV (Au) to investigate how electron injection barriers at the cathode/Alq₃ interfaces influence their current density–voltage (J–V) characteristics. We found that current densities at a certain driving voltage decrease and the temperature dependence of J–V characteristics of the devices gradually becomes weaker as the work functions of the metal cathodes are decreased. The device with the highest-work-function Au cathode exhibited virtually temperature-independent J–V characteristics, suggesting that a current flow mechanism of this device is mainly controlled by electron tunneling injection at the Au/Alq₃ interface.     

Effect of hydrogen radical on growth of μc-Si in hetero-structured SiCx alloy films

The changes of the crystallinity of μc-Si phase are studied in samples deposited with hydrogen dilution ratio, H₂/SiH₄, from 9.0 to 19.0 by hot-wire CVD (Cat-CVD). In the samples deposited at filament temperature, T_f, of 1850 °C, the crystalline fraction and the crystallite size of μc-Si phase increased with increasing the H₂/SiH₄. The carbon content, C/(Si+C), was almost constant. In the XRD patterns, the intensity of Si(1 1 1) peak decreased and that of Si(2 2 0) peak increased with increasing the H₂/SiH₄. In the samples deposited at T_f of 2100 °C with H₂/SiH₄ over 11.4, the μc-Si phase was not formed and the C/(Si+C) increased. The growth mechanism of μc-Si in hetero-structured SiC_x alloy films is discussed.     

Electro-optic properties of c-axis oriented LiNbO3 films grown on Si(1 0 0) substrate

We developed a spectroscopic–ellipsometric approach to evaluate the electro-optic coefficient of highly c-axis oriented LiNbO₃ films on an Si(1 0 0) substrate grown by electron cyclotron resonance plasma sputtering. Applying an electric field between the TiN transparent top electrode and Si substrate, the interference fringe appearing in the tan Ψ spectrum was slightly modulated by phase retardation in the wavelength domain. The change in effective wavelength was converted to refractive index change, yielding dispersion in the Pockels coefficient (r₃₃) between 0.3 and 0.8 μm. At 633 nm, we obtained an r₃₃ that was 57% of the bulk LN crystal value.     

Bias sputtered Ta modified diffusion barrier in Cu/Ta(Vb)/Si(111) structures

In this investigation, we have fabricated Ta(V_b)/Si(111) and Cu/Ta(V_b)/Si(111) systems using a DC bias sputtering technique at high Ar pressure (100 mTorr). For Ta/Si(111) system, tantalum layer was formed under various bias voltages ranging from 0 to −150 V. The films were characterized by Rutherford backscattering spectrometry (RBS), scanning electron microscopy (SEM) and four-point probe sheet resistance measurements (R_s). From electrical resistivity and SEM data, a minimum resistivity (99 μΩ cm) and well surface morphology at an optimum bias voltage (V_b=−50 V) was obtained for the Ta(V_b)/Si(111) system. The Ta films deposited under these conditions with 50 nm thickness are then used as a diffusion barrier in the Cu/Ta(V_b)/Si(111) multilayer structure. According to our RBS, SEM and R_s analysis, the Ta barrier layer formed under the controlled bias sputtering at high Ar pressure has demonstrated an improved Ta structure with excellent thermal stability up to 650°C for the Cu/Ta(V_b)/Si(111) system annealed in N₂ environment for 30 min. Formation of TaSi₂ was observed at 700°C after the barrier failure using RBS spectra.     

Dynamic crack growth in particulate bimaterials having discrete and diffuse interfaces: Role of microstructure

Role of microstructure on interfacial crack growth in particulate bimaterials made of glass particle reinforced epoxy is examined experimentally. Two types of bimaterials, one with a discrete jump in mean filler particle size across the interface and the other with two intermixed particle sizes in the interfacial region, are studied. The choice of particle sizes used in bimaterials is based on a set of experiments in which particle size effects on fracture behavior of monolithic specimens with single particle size are established using optical interferometry and high-speed photography. A non-monotonic steady state stress intensity factor (K_Iss) variation with mean particle size is observed in the size range of 7–203 μm for 10% volume fraction. Among the selected particles sizes, 35 μm mean diameter is found to produce the highest K_Iss. Increasing or decreasing particle size results in measurable reduction in K_Iss of the composite. Based on this result, discrete and diffuse bimaterials made of 35 μm and 203 μm diameter filler particles are studied. The K_Iss of the diffuse interface with intermixed particle sizes is bounded by the ones for monolithic configurations with single size particles. Further, K_Iss appears to vary linearly with the volume fraction of particle size having lower K_Iss in monolithic configurations. On the contrary, in case of a microstructurally discrete interface, the measured K_Iss is same as the one for the weaker half of the bimaterial.     

Templated grain growth of SrBi2Ta2O9 ceramics: Mechanism of texture development

Textured SrBi₂Ta₂O₉ (SBT) ceramics were fabricated via templated grain growth (TGG) technique using platelet-like SBT single crystal templates. The templates (5 wt%) were embedded in a fine-grain SBT powder matrix containing 3 wt% of Bi₂O₃ excess that were subjected to uniaxial pressing and sintering at 1000–1250 °C for up to 24 h. Microstructural characterization by SEM was performed to establish the effect of sintering parameters on the grain growth and texture development. It was found that the ceramics developed a bimodal microstructure with notable concentration of large (longer than 90 μm) aligned grains with c-axis oriented parallel to the pressing direction. The mechanism controlling the texture development and grain growth in SBT ceramics is discussed.     

Analysis of the tensile behaviour of viscoelastically prestressed polymeric matrix composites

A novel composite material is reported, in which tension, applied to polymeric fibres, is released prior to moulding them into a matrix. Following matrix solidification, compressive stresses imparted by the viscoelastically strained fibres impede crack propagation. Previous Charpy impact studies had demonstrated that these viscoelastically prestressed composites could absorb typically 25–30% more energy than control (unstressed) counterparts and the current study focuses on their tensile behaviour as a function of fibre volume fraction, V_f. Tensile testing was performed on continuous unidirectional nylon 6,6 fibre–epoxy resin samples. Compared with control counterparts, the results showed that viscoelastic prestressing improved tensile properties, the effects being V_f-dependent. Increases in tensile strength, modulus and energy absorbed (to 0.25 strain) exceeded 15%, 30% and 40%, respectively, at an optimum V_f, this being 35–40%. Strain-to-failure was reduced by 10–20%, thereby lowering any improvement in tensile toughness (energy absorbed to fracture) to <10%. Mechanical properties of the fibres themselves were not significantly influenced by the treatment used for generating composite prestress, and we propose that the observed improvements to tensile properties may be attributed to: (i) direct contribution from compressive stress, (ii) attenuation of the dynamic overstress effect on fibre fracture and (iii) improved mechanical integrity through a more collective response from fibres to tensile loads.     

Temperature dependence of fracture toughness of silica/epoxy composites: Related to microstructure of nano- and micro-particles packing

Temperature dependence of the fracture toughness of epoxy composites reinforced with nano- and micro-silica particles was evaluated. Epoxy composites containing varied composition ratios Φ_SP of spherical nano- and micro-silica particles, 240 nm and 1.56 μm, were prepared at a fixed volume fraction (V_P = 0.30). The thermo-viscoelasticity and fracture toughness of the composites and neat epoxy were measured at 143 K, 185 K, 228 K, 296 K, 363 K, and 399 K. Experimental results revealed that fracture toughness strongly depended on the microstructure of nano- and micro-particles bidispersion as well as its interactions with the matrix at all temperature, but depended on toughened matrix due to increase in mobility of matrix at the relaxation temperatures.     

Fabrication of β-Si3N4 whiskers by combustion synthesis with MgSiN2 as additives

β-Si₃N₄ whiskers with diameter of 0.5–2 μm and aspect ratio of 10–15 have been successfully prepared by combustion synthesis under 30–50 atm nitrogen pressure. The addition of MgSiN₂ powder plays a significant role in the growth of β-Si₃N₄ whiskers. The as-prepared products were characterized by X-ray powder diffraction (XRD) and scanning electron microscopy (SEM).     

Fracture-resistant ultralloys for space-power applications: Normal-spectral-emissivity and electron-emission studies of tungsten, rhenium, hafnium-carbide alloys at elevated temperatures

A series in this journal on high-temperature properties of “fracture-resistant ultralloys for space-power systems” preceded the present paper: the antecedent publications covered tungsten(W), rhenium(Re) alloys with and without thoria(ThO₂) (W, 23Re; W, 27Re; W, 30Re and W, 30Re, 1ThO₂). This paper reports radiative and thermionic effects of hafnium carbide(HfC) and Re variation in W alloys: normal spectral emissivity(ε_λ) is used in pyrometry to determine the true temperature of a surface. Effective work function (φ_e) is an important consideration in the selection of the electrode materials for high-temperature thermionic energy converters in space-power applications. The _0.535μ, ε_0.65μ and φ_e trends of W, Re, 0.35HfC with 5–20% Re were measured in the range of 1700–2500K. The results indicate that ε_λ decreases with increasing temperatures and Re contents. The presence of HfC produced higher ε_λ values than those of sintered materials with comparable W,Re alloy contents. The results also indicate that φ_e increases with rhenium contents. This can be explained as growth of the potential barrier at the metal, vacuum boundary associated with a volume effect—the decrease in the lattice constant of W.     

Validation and calibration of a lateral confinement model for long-rod penetration at ordnance and high velocities

In designing targets for laboratory long-rod penetration tests, the question of lateral confinement often arises, “How wide should the target be to exert enough confinement?” For ceramic targets, the problem is enhanced as ceramics are usually weak in tension and therefore have less self-confinement capability. At high velocities the problem is enhanced even more as the crater radius and the extent of the plastic zone around it are larger. Recently we used the quasistatic cavity expansion model to estimate the resistance of ceramic targets and its dependence on impact velocity [1]. We validated the model by comparing it to computer simulations in which we used the same strength model. Here we use the same approach to address the problem of lateral confinement.

We solved the quasistatic cavity expansion problem in a cylinder with a finite outside radius “b” at which σ_r (b) = 0 (σ_r = radial stress component). We did this for three cases: ceramic targets, metal targets, and ceramic targets confined in a metal casing. Generally, σ_r (a) is a decreasing function of “a” (“a” = expanding cavity radius, and σ_r (a) = the stress needed to continue opening the cavity). In the usual cavity expansion problem b → ∞, σ_r (a) = const., R =−σ_r (a) (R = resistance to penetration). For finite “b” we estimate R by averaging σ_r (a) over a range o ≤ a ≤ a_r, (where a_r, the upper bound of the range, is calibrated from computer simulations).

We ran 14 computer simulations with the CTH wavecode and used the results to calibrate a_r for the different cases and to establish the overall validity of our approach.

We show that generally for D_t/D_p > 30, the degree of confinement is higher than 95% (D_t = target diameter; D_p = projectile diameter; and degree of CONFINEMENT = R/R_∞; R∞ = resistance of a laterally infinite target). We also show the tensile strength of ceramic targets (represented by the spall strength P_min) has a significant effect on the degree of confinement, while other material parameters have only a minor effect.     

Domain patterns on ferroelectric Rh:BaTiO3 single crystals

Single crystal growth and domain structure of Rh:Barium titanate (BaTiO₃) have been investigated. Rh doping in BaTiO₃ is effective for the growth of bulk crystals without twin formation. Atomic force microscope (AFM) and optical microscope studies reveal the formation 180° and 90° domains on the grown crystals. It has been observed that the complex 180° domain structure with typical size of around 20 μm exists in the c-domain of {0 0 1} face of Rh doped BaTiO₃ crystals.     

Epitaxial growth of AB type compounds under quasi-equilibrium conditions

Single-crystal films of CdS, CdSe and CdTe have been grown in vacuum on mica (fluophlogopite and muscovite) under isothermal conditions, i.e. with T_ev ≈ T_ep ≈ T_gr where T_ev and T_ep are the evaporation and epitaxial temperatures respectively and T_gr is the growth temperature. The synthesis was carried out in the temperature range 430°–800°C in the case of CdS, 300°–650°C for CdSe and 270°–550°C for CdTe. It is shown that the growth rate of single crystal layers (V_gr) depends exponentially on the growth temperature: V_gr (Å/sec) = D exp (−E/RT_gr) Perfect epitaxial CdS, CdSe and CdTe films have a wide range of electrophysical properties. Co-evaporation of CdS and sulphur and of CdSe and selenium allowed high-resistance films of cadmium sulphide and cadmium selenide of both n- and p-types to be obtained.     

A novel gamma-ray imaging concept using “edge-on” microchannel plate detector

The “edge-on” illuminated microchannel plate (MCP) position-sensitive detector (PSD) is used for gamma-ray imaging for the first time. The superior position resolution of the MCP is combined with high detection efficiency due to the “edge-on” illumination mode. The results of imaging a 15 μCi ¹³⁷Cs source (662 keV quantum energy) are presented.     

Scaling flow fields from the impact of thin plates

A dimensional analysis is performed to obtain velocity scaling relationships for the perforation of thin plates. The approach used is an extension of Dienes and Walsh's “late-stage equivalence” and Holsapple and Schmidt's “coupling parameter” concepts, used to simplify velocity scaling of impact phenomena. The coupling parameter C for plate perforation, is shown to have the form C=dU^μδ^ν for the perforation of thick plates and the form C=dU^μδ^ν f(t/d) for the perforation of thin plates (d is the projectile diameter, t is the plate thickness, U is the impact velocity and δ is the projectile density). It is shown that μ=1/2 for momentum scaling and μ=1 for energy scaling, however, from scaled hydrocode output it is found that, for aluminum impacting aluminum, the value of μ is equal to 0.83±0.03, which is neither energy nor momentum scaling. It is also shown that velocity scaling of thick plate perforation, using the same materials in the model and prototype and the same t/d, is not possible. An example of velocity scaling hydrocode output is given where the radial particle velocity wave profiles from the model calculation at U=55.6km/s and t/d=0.675 are similar to those from the prototype calculation with U=100km/s and t/d=1.08.     

Ultrasonic studies of the binary mixtures of ethyl acetate and cresols—application of Kosower and Dimroth treatments

The ultrasonic velocity (ν) studies were carried out at a frequency of 2 MHz (transducer of x-cut quartz crystal) using ultrasonic pulse echo system (model UX4400-M) on cresols in ethyl acetate at constant temperature of 311 K. The values of internal pressure ( π_i) and molar free volume (V_f) were calculated from measured values of ultrasonic velocity (ν), viscosity (η) and density (ρ). An attempt is made to rationalize the ultrasonic velocity (ν), internal pressure ( π_i) and free volume (V_f) of binary mixtures using Kosower solvent parameter (Z), Dimroth solvent parameter (E_T) and Dielectric constant (). It is found that there is linear correlation between ultrasonic velocity and acidity constant pk⁻¹a, indicating the dependence of acidity. Correlation of Ksower and Dimroth parameters with ultrasonic velocity confirms that solvent polarity is an important factor in the variation of ultrasonic velocity in the present investigation.