Experimental measurement of vapor-liquid equilibrium for (trans-1,3,3,3-tetrafluoropropene (R1234ze(E)) + propane (R290))

The VLE data for the binary system of R1234ze(E) + R290 were measured with a recirculation method at four temperatures (258.150, 263.150, 273.150 and 283.150 K). The measured uncertainties of the temperature, pressure, and compositions are ±5 mK, ±0.0005 MPa, and ±0.005, respectively. All the experimental data were correlated by the Peng-Robinson (PR) EoS with the Huron-Vidal (HV) mixing rule involving the non-random two-liquid (NRTL) activity coefficient (PR-HV-NRTL) model. Azeotropic behavior can be found at the measured temperature range.     

Measurement of Vapor–Liquid Equilibrium for the DME + Diisopropyl Ether Binary System and Correlation for the DME + CO<Subscript>2</Subscript> + Diisopropyl Ether Ternary System

Vapor–liquid equilibrium (VLE) data have been measured with a static-type VLE apparatus for the dimethyl ether (DME)–diisopropyl ether (DIPE) binary system at five temperatures within the range from 293.04 K to 352.70 K. An isothermal correlation for the experimental data has been carried out based on the Peng-Robinson equation of state. The regressed binary interaction parameters were used to estimate VLE for the DME–CO₂–DIPE ternary system at 298.15 K. From the study, it is demonstrated that DIPE is an excellent absorbent for separation in the DME synthesis process from syngas.     

Simulations of Si and SiO2 etching in SF6 + O2 plasma

Chemical etching of Si and SiO₂ in SF₆ + O₂ plasma is considered. The concentrations of plasma components are calculated using values extrapolated from experimental data. Resulting calculations of plasma components are used for the calculation of Si and SiO₂ etching rates. It is found that the reaction constants for reactions of F atoms with Si atoms and SiO₂ molecules are equal to (3.5 ± 0.1) × 10⁻² and (3.0 ± 0.1) × 10⁻⁴, respectively. The influence of O₂ addition to SF₆ plasma on the etching rate of Si is quantified.     

Fabrication and characterization of all-oxide heterojunction p-CuAlO2 + x/n-Zn1 − xAlxO transparent diode for potential application in “invisible electronics”

Transparent p-n heterojunction diodes have been fabricated by p-type copper aluminum oxide (p-CuAlO_2 + x) and n-type aluminum doped zinc oxide (n-Zn_1 − xAl_xO) thin films on glass substrates. The n-layers are deposited by sol-gel-dip-coating process from zinc acetate dihydrate (Zn(CH₃COO)₂·2H₂O) and aluminum nitrate (Al(NO₃)₃·9H₂O). Al concentration in the nominal solution is taken as 1.62 at %. P-layers are deposited onto the ZnO:Al-coated glass substrates by direct current sputtering process from a prefabricated CuAlO₂ sintered target. The sputtering is performed in oxygen-diluted argon atmosphere with an elevated substrate temperature. Post-deposition oxygen annealing induces excess oxygen within the p-CuAlO_2 + x films, which in turn enhances p-type conductivity of the layers. The device characterization shows rectifying current-voltage characteristics, confirming the proper formation of the p-n junction. The turn-on voltage is obtained around 0.8 V, with a forward-to-reverse current ratio around 30 at ± 4 V. The diode structure has a total thickness of 1.1 μm and the optical transmission spectra of the diode show almost 60% transmittance in the visible region, indicating its potential application in ‘invisible electronics’. Also the cost-effective procedures enable the large-scale production of these transparent diodes for diverse device applications.     

Surface reactions between CO2 and H over K-modified Cu(0 0 1)

Low temperature (115-160 K) adsorption of CO on clean Cu(0 0 1), CO₂ on potassium modified Cu(0 0 1) and surface reactions between H₂ and CO₂ were studied. Pre-adsorption of K leads to strong interaction of the interface with arriving carbon dioxide molecules and linear CO₂(phys), bent , CO and are observed as adsorbed species. Annealing of the CO₂/K/Cu(0 0 1) interface causes, successively, desorption of the reaction products. Pre-adsorbed hydrogen on the alkali-modified substrate changes the surface reaction channels, mainly with no presence of CO and creation of surface formate species. Details of surface reactions are compared with results for thick potassium film on a copper substrate.     

A comparative study of the properties of thermally evaporated CuIn2n + 1S3n + 2 (n = 0, 1, 2 and 3) thin films

CuInS₂, CuIn₃S₅, CuIn₅S₈ and CuIn₇S₁₁ compounds were synthesized by the horizontal Bridgman method using high-purity copper, indium and sulphur elements. Crushed powders of these ingots were used as raw materials for the vacuum thermal evaporation. So, CuIn_2n + 1S_3n + 2 (n = 0, 1, 2, and 3) thin films were deposited by single source vacuum thermal evaporation onto glass substrates heated at 150 °C. The structural, compositional, morphological, electrical and optical properties of the deposited films were studied using X-ray diffraction (XRD), energy dispersive X-ray, atomic force microscopy and optical measurement techniques. XRD results revealed that all the films are polycrystalline. However, CuInS₂ and CuIn₃S₅ films had a chalcopyrite structure with preferred orientation along 112 while CuIn₅S₈ and CuIn₇S₁₁ films exhibit a spinel structure with preferred orientation along 311. The absorption coefficients of the all CuIn_2n + 1S_3n + 2 films are in the range of 10⁻⁴ and 10⁻⁵ cm⁻¹. The direct optical band gaps of CuIn_2n + 1S_3n + 2 layers are found to be 1.56, 1.78, 1.75 and 1.30 eV for n = 0, 1, 2, and 3, respectively. CuIn₃S₅ and CuIn₅S₈ films are p type with electrical resistivities of 4 and 12 Ω cm whereas CuInS₂ and CuIn₇S₁₁ are highly compensated with resistivities of 1470 and 1176 Ω cm, respectively.     

One-step synthesis and double emission (Ca1 + x − yEuy)Ga2S4 + x phosphor for white LEDs

(Ca_{1 + x − y}Eu_y)Ga₂S_4 + x phosphors have been synthesized one step by solid state reaction. The photoluminescence excitation and emission spectra of phosphors have been studied; the influence of host composition and Eu²⁺ concentration on emission spectra has also been investigated. The emission spectrum consists of yellow emission at 550 nm and red emission at 650 nm. It also indicates that the excitation spectrum is a broadband and can be well matched with the emission of GaN chip. Combined these phosphors with 460 nm-emitting GaN chips, White LEDs have been fabricated. Their electroluminescence spectra have been measured under 20 mA forward-bias current. Their CIE chromaticity coordinates and color temperature indicate that (Ca_{1 + x − y}Eu_y)Ga₂S_4 + x phosphors are promising phosphors for GaN-based white LEDs.     

Growth and magnetic properties of ultrathin Ni1 + xFe2 − xO4 films for spin filter junctions

We investigated the spin filter effect in tunnel junctions with a Ni_1 + xFe_2 − xO₄ ferrimagnetic tunnel barrier. For higher T_c above room temperature, Ni_1 + xFe_2 − xO₄ film should be thicker than 4.0 nm and grown above 400 °C. The spin filter junctions (SFJs) of Fe₃O₄(001)/Ni_1 + xFe_2 − xO₄(001)/Al₂O₃/Fe/Au grown on MgO(001) substrates exhibited an inverse magnetoresistance effect at room temperature, which is consistent with the band calculation of NiFe₂O₄.     

Phase stabilities of self-organized nc-TiN/a-Si3N4 nanocomposites and of Ti1 − xSixNy solid solutions studied by ab initio calculation and thermodynamic modeling

Bulk properties of stable binary fcc-TiN and hcp(β)-Si₃N₄, hypothetical fcc-SiN and hcp(β)-Ti₃N₄, and ternary Ti_1 − xSi_xN_y phases are calculated by ab initio method. The values of total energies are then used for thermodynamic calculations of the lattice instabilities of hypothetical binary phases of fcc-SiN and hcp-Ti₃N₄, and of the interaction parameters of ternary Ti_1 − xSi_xN_y phases. Based on these data, Gibbs free energy diagrams of the quasi-binary TiN_y-SiN_y system are constructed in order to study the relative phase stability of the metastable ternary fcc- and hcp-Ti_1 − xSi_xN_y phases over the entire range of compositions. The results are supported by the published data from chemical and physical vapor deposition experiments. The constructed Gibbs free energy diagram and phase selection diagram of quasi-binary TiN_y-SiN_y system in fcc structure show that metastable fcc-Ti_1 − xSi_xN coatings should undergo chemically spinodal decomposition into coherent fcc-TiN and fcc-SiN. Due to a high lattice mismatch between fcc-TiN and hcp-Si₃N₄, and to much higher lattice instability of fcc-SiN with respect to stable hcp-Si₃N₄, only about one monolayer of pseudomorphic SiN_y interfacial phase is stable.     

Phase equilibria of the Co-Ni-Zr system at 1198 K

The isothermal section of the phase diagram of the Co-Ni-Zr ternary system at 1198 K has been investigated by means of diffusion triple and electron microprobe analysis. This isothermal section consists of six three-phase regions. The homogeneity ranges of Co₂₃Zr₆, Co₂Zr, CoZr, Ni₅Zr, Ni₇Zr₂ and NiZr are about 16.7%-18.8 at.%Zr, 28.6%-32.3 at.%Zr, 49.2%-51.7 at.%Zr, 16.0%-18.7 at.%Zr, 22.3%-24.1 at.%Zr and 49.8%-52.1 at.%Zr, respectively; CoZr₂ and NiZr₂ are nearly linear compounds. The largest solubilities of Ni in Co₂₃Zr₆, Co₂Zr and CoZr are about 4.9 at.%Ni, 5.4 at.%Ni and 4.5 at.%Ni, respectively. CoZr₂ and NiZr₂ form a continuous solid solution (Co,Ni)Zr₂. No ternary compound is observed.     

Structural and optical properties of polycrystalline CdSexTe1−x (0 ≤ x ≤ 0.4) thin films

CdSe_xTe_1−x (0 ≤ x ≤ 0.4) ternary thin films have been deposited on quartz substrates at room temperature by a single source thermal evaporation. X-ray diffraction patterns and transmission electron microscope micrographs of these films showed that the films were of polycrystalline texture over the whole range studied and exhibit predominant cubic (zinc blende) structure with strong preferential orientation of the crystallites along (1 1 1) direction. Linear variation of the lattice constant with mole fraction x is observed obeying Vegard's law. The dependence of the optical constants, the refractive index n and extinction coefficient k, of the films on the mole fraction x was studied in the spectral range of 400-2500 nm. The normal dispersion of the refractive index of the films could be described using the Wemple-DiDomenco single-oscillator model. CdSe_xTe_1−x thin films of different composition have two direct and indirect transitions corresponding to energy gaps and . The variation in either or with x indicates that this system belongs to the amalgamation type. The variation follows a subquadratic dependence and the bowing parameters were found to be 0.36 and 0.48 eV for the direct, and indirect energy gaps, respectively. Direct linear variation of the ratio N/m^* with x is observed.     

The variation of tensile characteristics of Al-2 wt.%Ag and Al-2 wt.%Ag-1 wt.%Sn alloys during transformation

Effect of tin addition and heat treatment on the work hardening characteristics of Al-2 wt.%Ag alloy during phase transformation has been studied in the deformation temperature range from 503 K to 583 K. The fracture strain ?_f, and dislocation slip distance L increased with increasing deformation temperature. On the other hand the coefficient of work hardening χ = δσ²/δ?, the fracture time t_f, yield stress, σ_y fracture stress, σ_f decreased with increasing deformation temperature and exhibited an abrupt increase at about 553 K. The Sn-free samples were generally harder than the ternary alloy. The activation energy of the fracture mechanism in both alloys was around 26.8 ± 3 kJ/mol and 34.6 ± 3 kJ/mol before and after transformation temperature (553 K), respectively. The quenched samples are harder than those of slowly cooled samples. From X-ray analyses it is clear that when lattice strain ? and dislocation density ρ increases, the crystallite size η decreases.     

Preferentially oriented thin-film growth of CuO(1 1 1) and Cu2O(0 0 1) on MgO(0 0 1) substrate by reactive dc-magnetron sputtering

Copper oxide films deposited on MgO(0 0 1) substrates by reactive magnetron sputtering under the metal-mode condition were studied by X-ray diffraction (XRD) and reflection high-energy electron diffraction (RHEED) analyses for structural analysis, and X-ray-excited Auger electron spectroscopy (XAES) for chemical bonding analysis. CuO(1 1 1) thin films grew from their initial growth stage maintaining the same crystallinity on MgO(0 0 1) substrates at 400°C. When the substrate temperature was increased to 600 °C, the as-sputtered films comprise Cu(0 0 1), amorphous Cu₂O phase, and Cu₂O(0 0 1) phase. The Cu(0 0 1) phase was observed at initial growth stage. This is probably because O₂ gas molecules could not sufficiently stick to the MgO substrate at 600 °C. Single phase of Cu₂O(0 0 1) was obtained by the cooling of the as-sputtered films in O₂ atmosphere. The growth of single phase Cu₂O(0 0 1) is considered as a solid-phase heteroepitaxial growth on MgO(0 0 1) surface, which was caused by incorporating O₂ gas into the as-sputtered films.     

Enhancing the oxygen permeability of Ba0.5Sr0.5Co0.8Fe0.2O5 + δ membranes by coating RBaCo2O5 + δ(R= Pr, Nd, Sm, Gd) layers

The effects of a thin RBaCo₂O_5 + δ (R= Pr, Nd, Sm, Gd) layer coating on the oxygen permeation flux through Ba_0.5Sr_0.5Co_0.8Fe_0.2O_5 + δ(BSCF) membrane were investigated. Due to the high oxygen adsorption and desorption rate constants k_a and k_d of the RBaCo₂O_5 + δ (R112) materials and the porous structure of the coating layers, the oxygen permeation flux through the BSCF membranes can be enhanced remarkably. It was found that the reaction between Pr112 and BSCF also has significant influence on the oxygen permeation flux. The reaction between Pr112 and BSCF forms impurities which may block oxygen permeation flux. However, Nd112, Sm112, and Gd112 do not react seriously with BSCF, therefore, coating layers of these materials can significantly enhance the oxygen permeation flux of BSCF membranes.     

The Mn + 1AXn phases: Materials science and thin-film processing

This article is a critical review of the M_n + 1AX_n phases (“MAX phases”, where n = 1, 2, or 3) from a materials science perspective. MAX phases are a class of hexagonal-structure ternary carbides and nitrides (“X”) of a transition metal (“M”) and an A-group element. The most well known are Ti₂AlC, Ti₃SiC₂, and Ti₄AlN₃. There are ~ 60 MAX phases with at least 9 discovered in the last five years alone. What makes the MAX phases fascinating and potentially useful is their remarkable combination of chemical, physical, electrical, and mechanical properties, which in many ways combine the characteristics of metals and ceramics. For example, MAX phases are typically resistant to oxidation and corrosion, elastically stiff, but at the same time they exhibit high thermal and electrical conductivities and are machinable. These properties stem from an inherently nanolaminated crystal structure, with M_n + 1X_n slabs intercalated with pure A-element layers. The research on MAX phases has been accelerated by the introduction of thin-film processing methods. Magnetron sputtering and arc deposition have been employed to synthesize single-crystal material by epitaxial growth, which enables studies of fundamental material properties. However, the surface-initiated decomposition of M_n + 1AX_n thin films into MX compounds at temperatures of 1000-1100 °C is much lower than the decomposition temperatures typically reported for the corresponding bulk material. We also review the prospects for low-temperature synthesis, which is essential for deposition of MAX phases onto technologically important substrates. While deposition of MAX phases from the archetypical Ti-Si-C and Ti-Al-N systems typically requires synthesis temperatures of ~ 800 °C, recent results have demonstrated that V₂GeC and Cr₂AlC can be deposited at ~ 450 °C. Also, thermal spray of Ti₂AlC powder has been used to produce thick coatings. We further treat progress in the use of first-principle calculations for predicting hypothetical MAX phases and their properties. Together with advances in processing and materials analysis, this progress has led to recent discoveries of numerous new MAX phases such as Ti₄SiC₃, Ta₄AlC₃, and Ti₃SnC₂. Finally, important future research directions are discussed. These include charting the unknown regions in phase diagrams to discover new equilibrium and metastable phases, as well as research challenges in understanding their physical properties, such as the effects of anisotropy, impurities, and vacancies on the electrical properties, and unexplored properties such as superconductivity, magnetism, and optics.     

Preparation and microstructure characterization of novel La2 − xSr2 − xNb2O10 − x oxides

The aim of the present work is to report the study of samples with the La_2 − xSr_2 − xNb₂O_10 − x stoichiometry obtained under different synthesis conditions. The materials were characterized and studied by means of Scanning Electron Microscopy (SEM), High Resolution Transmission Electron Microscopy (HRTEM), X-ray diffraction analysis (XRD), and AC Susceptibility. A preliminary identification of the main peaks appearing in the diffraction patterns is shown for the synthesized phases. The La_2 − xSr_2 − xNb₂O_10 − x compound undergoes a structural change as a function sintering temperature, with three kinds of the stabilized structure, one is from 1173 < T ≤ 1373 K, another from 1423 < T ≤ 1573 K and the last one from 1623 < T ≤ 1723 K.     

Towards an electronic model for CuIn1 − xGaxSe2 solar cells

We model some aspects of highly efficient CuIn_1 − xGa_xSe₂ solar cells with x ≈ 0.3 as well as wide band gap cells with x = 1 and ask for the dominant recombination mechanism which limits the V_oc of these devices. For CuIn_1 − xGa_xSe₂ solar cells with x ≈ 0.3, interface recombination combined with Fermi-level pinning is a possible but unlikely recombination mechanism. We argue that these cells are rather limited by recombination in the quasi-neutral region (QNR) including the back contact. Using the expression for the QNR recombination rate we calculate the derivative of the collection function in the absorber at the space charge region edge which is in reasonable agreement with the experiment. It turns out that the diffusion length must approximate the absorber thickness. Based on this information, we draw a band diagram for a CuIn_1 − xGa_xSe₂ solar cells with x ≈ 0.3 and plot the simulated collection function. For cells with x = 1 (Cu-poor CuGaSe₂), the experimental activation energy of the recombination rate mostly equals the absorber band gap, i.e. E_a ≈ E_g,a = 1.67 eV. As the experimental interface band gap is smaller than E_a, interface recombination must be ruled out. Thus, the carrier lifetime in the Cu-poor CuGaSe₂ absorber should be so small that bulk recombination is more efficient than interface recombination. From this consideration, we postulate an electron lifetime value of 10⁻¹² s for CuGaSe₂.     

Synthesis of spherical nanostructured LiMxMn2−xO4 (M = Ni, Co, and Ti; 0 ≤ x ≤ 0.2) via a single-step ultrasonic spray pyrolysis method and their high rate charge-discharge performances

LiM_xMn_2−xO₄ (M = Ni²⁺, Co³⁺, and Ti⁴⁺; 0 ≤ x ≤ 0.2) spinels were prepared via a single-step ultrasonic spray pyrolysis method. Comparative studies on powder properties and high rate charge-discharge electrochemical performances (from 1 to 15 C) were performed. XRD identified that pure spinel phase was obtained and M was successfully substituted for Mn in spinel lattice. SEM and TEM studies confirmed that powders had a feature of ‘spherical nanostructural’, that is, powders consisted of spherical secondary particles with the size of about 1 μm, which were developed from close-packed primary particles with several tens of nanometers. Substitutions enhanced density of second particles to different extents, depending on M and its content. Charge-discharge tests showed that as-prepared LiMn₂O₄ could deliver excellent rate performance (around 100 mAh/g at 10 C). Ni substitution contributed to improving electrochemical performances. In the voltage range of 4.95-3.5 V, the materials showed much better electrochemical performances than LiMn₂O₄ in terms of capacity, cycleability and rate capability.     

Study of flash evaporated CuIn1 − xGaxTe2 (x = 0, 0.5 and 1) thin films

CuIn_1 − xGa_xTe₂ thin films with x = 0, 0.5 and 1, have been prepared by flash evaporation technique. These semiconducting layers present a chalcopyrite structure. The optical measurements have been carried out in the wavelength range 200-3000 nm. The linear dependence of the lattice parameters as a function of Ga content obeying Vegard's law was observed. The films have high absorption coefficients (4 · 10⁴ cm^− 1) and optical band gaps ranging from 1.06 eV for CuInTe₂ to 1.21 eV for CuGaTe₂. The fundamental transition energies of the CuIn_1 − xGa_xTe₂ thin films can be fitted by a parabolic equation namely E_g1(x) = 1.06 + 0.237x − 0.082x². The second transition energies of the CuInTe₂ and CuGaTe₂ films were estimated to be: E_g2 = 1.21 eV and E_g2 = 1.39 eV respectively. This variation of the energy gap with x has allowed the achievement of absorber layers with large gaps.     

Sputter-epitaxy and electric properties of multiferroic Bim + 1Fem-3Ti3O3m + 3 thin films

Growth conditions suitable for sputter-epitaxy of Bi_m + 1Fe_m-3Ti₃O_3m + 3 (BFTO) thin films with layered structure have been investigated. The amount of oxygen during deposition was found to be specifically essential for obtaining a good-quality thin film of BFTO with a large m. The (001) epitaxial thin films of BFTO with m of nearly 10 which is expected to retain magnetic order up to room temperature have been successfully grown on (001) SrTiO₃ substrates under the determined optimum condition. The film exhibited leakage current as low as order of 10⁻²-10⁻¹ A/m² limited by Schottky emission at the interfaces between the electrodes and the film. In addition, the film showed a ferroelectric polarization curve with Pr = 6 μC/cm² for applied field of 35 MV/m at room temperature though the curve was unsaturated. These indicate that the BFTO (m = 10) thin films are promising as multiferroics at room temperature.