A corrosion study and minority carrier diffusion length determination of n-type SnS2 and SnSSe

Corrosion behaviour of n-type SnS₂ and SnSSe single crystals in aqueous solutions has been studied. It has been shown that SnS₂ and SnSSe undergo a corrosion reaction in the dark when electrolytes contain oxidizing agents such as Fe(CN)³⁻₆ (KOH) and Ce⁴⁺ (H₂SO₄). Corrosion has a chemical nature. Values of absorption coefficient and hole diffusion length has been determined for both materials using the Gärtner model. A hole diffusion length of (2±0.5)×10⁻⁵ cm and (5±2)×10⁻⁷ cm was obtained, respectively, for samples prepared by Bridgman and Transport methods. The difference in hole diffusion length is explained by the existence of recombination centers produced by the transporting agent in the crystal bulk. A quantum yield of greater than one is found for SnSSe at high photon energies (greater than 2eV). This phenomenon has been explained by activation of a second electron from surface states above the valence band to the surface states below the conduction band.     

Discharge behaviour of plane nickel hydroxide electrodes

Plane nickel oxide electrodes were prepared by electrochemical deposition of nickel hydroxide on flexible nickel strips. Compact and adherent deposits were obtained, with thickness up to 4 × 10^?3 cm. They were cycled in 6 M KOH solution, and owing to the flexibility of the supporting nickel strips, did not show detaching. The results obtained from galvanostatic discharge curves fit the Peukert equation iⁿt = constant, giving an n value of 1.23 for the 1 × 10^?3 cm thick film and a value of 1.10 for the 4 × 10^?3 cm think film. The diffusion coefficients of moving species are in the order of magnitude of 10^?5 ?10^?6 cm²s^?1; the rate of discharge does not seem to be limited by proton diffusion. The proton diffusion in solid phase is not the only factor to be taken into account in the discharge process; diffusion and migration OH^? and H₂O species play an important role in plane thick nickel oxide film discharge.     

Branched-pore model applied to the adsorption of basic dyes on carbon

The branched-pore adsorption model, expressed by an external mass transfer coefficient k_f, a solid diffusivity D_s, a lumped micropore diffusion rate parameter k_b, and the fraction of macropores f, describes kinetic data from initial contact of adsorbent-adsorbate to the long-term ( > 24 hours) adsorption stages with reasonable accuracy.In this work the model is applied for three basic dye systems, namely Basic Red 22, Basic Yellow 21 and Basic Blue 69, all on carbon. A single value of each parameter describes each dye system. The k_f values are 0.18 × 10⁻²±28%, 0.3 × 10⁻²±17% and 0.2 × 10⁻² ± 20% cm s⁻¹, the D_s values are 0.33 × 10⁻⁹ 21%, 0.72 × 10⁻⁹ ± 9% and 0.72 × 10⁻⁹ ± 9% cm² s⁻¹, the k_b values are 0.65 × 10⁻⁶ ± 7.7%, 1.8 × 10⁻⁶ 0.2 × 10⁻⁶ 1% s⁻¹, while the f values are 0.55 ± 9%, 0.60 ± 10 % and 0.18 ± 11%, each for Basic Red 22, Basic Yellow 21 and Basic Blue 69 respectively.The model is based on the internal structure of the carbon particle being divided into a macropore and a micropore region. The latter has an upper-bound capacity of 241, 245 and 656 mg g⁻¹ for Basic Red 22, Basic Yellow 21 and Basic Blue 69 respectively. A sensitivity analysis for each parameter has been carried out.     

Biodegradable porous polylactic acid film as a separator for supercapacitors

A porous polylactic acid (PLA) film was investigated as a separator for supercapacitors (SCs) and compared with commercial separators, for example, NKK-MPF30AC and Celgard 2400. The porous PLA film was fabricated via a facile phase inversion method, and the cross-sectional scanning electron microscope images of the PLA separator film exhibited highly porous interconnected morphology for ion diffusion. The surface modification of separators was performed by radio frequency (RF) air plasma to improve wettability. The plasma modification enhanced the water uptake and swelling properties of the separators and decreased the water contact angles of PLA and Celgard 2400 films. The mechanical and dielectric properties of separators were also studied. The ionic conductivities of RF-PLA in 1 M H₂SO₄ and 1 M Na₂SO₄ were found to be 1.1 × 10⁻¹ S/cm and 0.6 × 10⁻² S/cm at room temperature, respectively. The electrochemical impedance spectroscopy of the RF-PLA SCs showed the lowest solution resistance and internal resistance.     

Copper separation from nitrate/nitric acid media using Acorga M5640 extractant: Part II. Supported liquid membrane study

The facilitated transport of copper(II) from nitrate/nitric acid media through a flat-sheet supported liquid membrane (FSSLM) is investigated, using the commercially available oxime Acorga M5640 as ionophore, as a function of hydrodynamic conditions, concentration of copper (7.9×10⁻⁵ to 1.3×10⁻³ M) and H⁺ (pH 1.0–2.0) and ionic strength in the feed solution, carrier concentration (5–40% v/v) in the membrane and support characteristics. The performance of the system is also compared using various diluents for the organic phase and against other available oxime extractants (MOC-55TD, LIX 860 and LIX 622). A model is presented that describes the transport mechanism, consisting of diffusion through a feed side aqueous diffusion layer, a fast interfacial chemical reaction, and diffusion of carrier and its metal complex through the organic membrane. The organic membrane diffusional resistance (Δ_o) and aqueous diffusional resistance (Δ_a) were calculated from the proposed model, and their values were 7.6×10⁶ and 273 s/cm, respectively. It was observed that the copper flux across the membrane tends to reach a plateau at high concentration of copper or a low concentration of H⁺ owing to carrier saturation within the membrane, and leads to a diffusion-controlled process. The values of the apparent diffusion coefficient (D_o^a) and limiting metal flux (J_lim) were calculated from the limiting conditions and found to be 2.0×10⁻⁸ cm²/s and 2.3×10⁻¹¹ mol/cm² s, respectively. The values of the bulk diffusion coefficient (D_o,b) and diffusion coefficient (D_o) calculated from the model were 5.9×10⁻⁹ and 1.6×10⁻⁹ cm²/s, respectively. The polymeric microporous solid support, Durapore GVHP 04700, was selected throughout the study as it gave the best performance.     

Diffusion and equilibrium properties of hydrogen in palladium measured by the stripping potentiostatic method

Theory and experiments on the (non-equilibrium) stripping potentiostatic method for evaluation of the diffusion coefficient and desorption isotherms of hydrogen in α-Pd are discussed. Diffusion coefficient of hydrogen D can be evaluated either under transient conditions, from the anodic stripping current (I_a) or under steady-state condition, from the anodic charge corresponding to the stripping of hydrogen held initially in Pd membrane (Q_a). Following data are reported: D = (3.60±0.06) × 10⁻⁷ cm² s⁻¹ (transient) and D = 3.41 × 10⁻⁷ cm² s⁻ (steady-state) at 20°C in 0.1 N H₂SO₄. Equilibrium concentration and equivalent pressure of hydrogen at the entrance side of Pd membrane can be calculated from the steady-state permeation current (I^∞_a or the anodic stripping charge (Q_a) and its open-circuit potential just after stopping hydrogen generation, E⁰_c. Reliable Sieverts' constants (K_s) have been calculated within 15 and 60°C, and the following thermodynamic values obtained: ΔH^o = −(2.6±0.1) kcal (mol H)⁻¹ and ΔS^o = −(14.5±0.4) cal K⁻¹ (mol H)⁻¹. These data agree well with those obtained in gas phase measurements.     

A study of the solid salt film on nickel and stainless steel

During steady state diffusion controlled dissolution of one-dimensional pit electrodes of stainless steel SS 302 and nickel, impedance and transient measurements were carried out to determine the ohmic potential drop across the salt film Δε_ΩF, the electric conductivity of the film σ_F and the film thickness d_F as a function of potential and solution composition. It was found that Δε_ΩF increases with decreasing diffusion limited current density, i_p, and with potential. For i_p → 0 it approaches a value which is independent on the bulk concentration. The critical potential for salt film formation is −0.9 and −0.08 V vs sce for SS 302 and nickel, respectively. The specific electric conductivity of the salt films is approximately 1.4 × 10⁻⁵ and 4.4 × 10⁻⁵ S cm⁻¹ for SS 302 and nickel, respectively. The salt film thickness linearly increases with potential and bulk concentration and is very thin compared to the pit depth (less than 1.5% at potentials < 1.2 V vs sce and chloride concentrations < 6 moll⁻¹).     

Sorption of dissolved organics from aqueous solution by polystyrene resins—II. External and internal mass transfer

External and internal mass transfer were characterized for the sorption of 2,4-dichlorophenol and p-nitrophenol on polystyrene resins. An evaluation method is presented which estimated the external mass-transfer coefficient, κ_L, from the concentration uptake in an integral fixed-bed reactor. The experimental κ_L values are compared with values predicted using four different empirical correlations. The effect of axial dispersion on the values of κ_L was shown to be small under the given conditions.To quantify the intraparticle mass transfer, an effective diffusion coefficient, D_eff, was estimated using the pore diffusion model interpretation of data from a differential column reactor within a recirculated batch system. The D_eff values depend on both resin structure and solute properties. Values of D_eff between 0.3 × 10⁻⁹ and 1.8 × 10⁻⁹ m²/s were observed for macroporous resins, which exceed values that are characteristic of pore diffusion, and a value of 0.6 × 10⁻¹¹ m²/s was estimated for a microporous resin.     

Selective growth and texturing of VO2(B) thin films for high-temperature microbolometers

Vanadium oxides exhibit a broad spectrum of physical properties due to their ability to form various compounds and polymorphs. To utilise a particular property, it is essential to selectively synthesise a desired phase. Herein, we demonstrate a method to selectively and reproducibly grow (00l)-textured VO₂(B) thin films using an amorphous SrTiO₃ buffer layer by sputtering at <350 °C, which enables their direct integration with read-out-integrated-circuits (ROICs), glass, and polymer substrates. The VO₂(B) films exhibit high temperature-coefficient-of-resistances (TCRs) (>−3.5%/K at 25 °C and >−1.5%/K at 95 °C) and low electrical resistivities (∼5 × 10⁻¹ Ω cm at 25 °C and <1 × 10⁻¹ Ω cm at 95 °C), which are favourable for realising highly-sensitive, low-noise, and high-temperature microbolometers. A robust thermal stability of these VO₂(B) thin films at ambient pressure will provide new opportunities to incorporate thermal sensing functions to various electronics.     

Temperature effect on diffusion of carbon dioxide through upper layers of Yucca Mountain

The effective diffusivities of carbon dioxide through the Tiva Canyon tuff and the lower lithophysal zone of the Topopah Spring tuff (outcrop samples of the layer above the proposed nuclear repository site layer) were determined using a steady-state method (counter diffusion). The diffusivity of carbon dioxide through the Tiva Canyon and lithopysal zone tuffs increased with temperature. The following correlation was obtained to estimate the effective diffusivity of carbon dioxide through the Tiva Canyon tuff in cm² s⁻¹ as a function of temperature (K). D_e = 1.22 × 10⁻² − 3.77 × 10⁻⁵T + 9.95 × 10⁻⁸T²The effective diffusivity of carbon dioxide through the lower lithophysal zone of the Topopah Spring tuff (layer right above the proposed repository site) also increased with temperature. For this layer, the following correlation was obtained to estimate the effective diffusivity of carbon dioxide in cm² s⁻¹ as a function of temperature (K). D_e = − 1.11 × 10⁻³ + 1.25 × 10⁻⁵T + 1.83 × 10⁻⁹T²     

Electrical properties of thick boron and nitrogen contained CVD diamond films

The acceptor and donor defects of thick (approx. 0.4 mm) free-standing boron and nitrogen containing microwave plasma CVD polycrystalline diamond films were investigated. Charge-based deep level transient spectroscopy (Q-DLTS) was applied to study impurity-induced defects, their density and energy distribution in the energy range of 0.01 eV≤E−E_v≤1.1 eV above the valence band. It was shown, that differential capacitance–voltage, and Hall effect measurements combined with DLTS data can be used to determine the degree of compensation, and the concentration of compensating donors (mostly the positively charged single-substitutional nitrogen (N⁺)) in p-type CVD polycrystalline diamond films. It was found, that incorporated boron atoms induce three levels of electrically active defects. Two of them with concentration (2–3)×10¹⁶ cm⁻³ each have activation energies of 0.36 and 0.25 eV with capture cross-sections of 1.3×10⁻¹³ and 4.5×10⁻¹⁹ cm², respectively. The third type of defect has an activation energy of 0.02 eV, capture cross-section 3×10⁻²⁰ cm² and concentration 10¹⁵ cm⁻³, this shallow trap being a probable general caterer of holes in low-doped films. The total concentration of electrically active uncompensated acceptors in all p-type diamond samples was approximately 2×10¹⁷ cm⁻³ with hole concentration of approximately 1.5×10¹⁴ cm⁻³ and hole mobility in the range of 30–40 cm² V⁻¹ s⁻¹ at room temperature. If assumed that compensating donors are mostly nitrogen, the films contained no less than 3×10¹⁶ cm⁻³ of N⁺.     

Fabrication of highly efficient TiO2/Ag/TiO2 multilayer transparent conducting electrode with N ion implantation for optoelectronic applications

Fabrication of highly conductive and transparent TiO₂/Ag/TiO₂ (referred hereafter as TAT) multilayer films with nitrogen implantation is reported. In the present work, TAT films were fabricated with a total thickness of 100 nm by sputtering on glass substrates at room temperature. The as-deposited films were implanted with 40 keV N ions for different fluences (1×10¹⁴, 5×10¹⁴, 1×10¹⁵, 5×10¹⁵ and 1×10¹⁶ ions/cm²). The objective of this study was to investigate the effect of N⁺ implantation on the optical and electrical properties of TAT multilayer films. X-ray diffraction of TAT films shows an amorphous TiO₂ film with a crystalline peak assigned to Ag (111) diffraction plane. The surface morphology studied by atomic force microscopy (AFM) and field emission scanning electron microscope (FESEM) revealed smooth and uniform top layer of the sandwich structure. The surface roughness of pristine film was 1.7 nm which increases to 2.34 nm on implantation for 1×10¹⁴ ions/cm² fluence. Beyond this fluence, the roughness decreases. The oxide/metal/oxide structure exhibits an average transmittance ~80% for pristine and ~70% for the implanted film at fluence of 1×10¹⁶ ions/cm² in the visible region. The electrical resistivity of the pristine sample was obtained as 2.04×10⁻⁴ Ω cm which is minimized to 9.62×10⁻⁵ Ω cm at highest fluence. Sheet resistance of TAT films decreased from 20.4 to 9.62 Ω/□ with an increase in fluence. Electrical and optical parameters such as carrier concentration, carrier mobility, absorption coefficient, band gap, refractive index and extinction coefficient have been calculated for the pristine and implanted films to assess the performance of films. The TAT multilayer film with fluence of 1×10¹⁶ ions/cm² showed maximum Haacke figure of merit (FOM) of 5.7×10⁻³ Ω⁻¹. X-ray photoelectron spectroscopy (XPS) analysis of N 1s and Ti 2p spectra revealed that substitutional implantation of nitrogen into the TiO₂ lattice added new electronic states just above the valence band which is responsible for the narrowing of band gap resulting in the enhancement in electrical conductivity. This study reports that fabrication of multilayer transparent conducting electrode with nitrogen implantation that exhibits superior electrical and optical properties and hence can be an alternative to indium tin oxide (ITO) for futuristic TCE applications in optoelectronic devices.     

Growth of CVD heteroepitaxial diamond on silicon (001) and its electronic properties

Microwave CVD heteroepitaxial diamond film on a 4° off-axis Si(100) substrate is obtained by two stages. The first one is to grow oriented 3c-SiC layers on Si(100) using a non-toxic and non-inflammable (CH₃)₆Si₂NH organic compound carried by hydrogen. The following stage is to grow oriented diamond films on them under the atmosphere of CH₄ and H₂. In each stage there are bias and growth processions. The micro-Raman and micro-Auger analyses prove that there is a perfect orientation relationship between the film and substrate as following: diamond 〈001〉//3c-SiC〈001〉//Si〈001〉. The Hall effect indicates that the film is a P type, whose resistivity is 9.4×10⁻³ Ω cm, the Hall coefficient is 2.9 cm³/Q, the hole mobility is 309 cm²/V s and the carrier concentration reaches 2.2×10¹⁸ cm⁻³.     

Preparation of drilling cuttings-coal fly ash based ceramic proppants: The roles of barite

This study presents the feasibility of preparing ceramic proppants (CPs) using drilling cuttings (DCs) and coal fly ash (CFA) via high-temperature sintering. The reaction behavior of barite in ceramic proppant precursors originating from DCs during the sintering process was investigated. The breakage ratio of the CPs (optimal group S3) met the requirements of Chinese standard SY/T 5108-2014 (2 K grade). The primary chemical reactions (7–8 in Table 4) between the barite and silica/alumina components resulted in a reduction of the eutectic point of the mixtures and the formation of aluminosilicates containing barium. However, these interactions also released gases (SO₂ and O₂), which created pores and weakened the CPs strength. The ideal temperature range for sintering is between 1170 and 1200 °C, during which there should be a gradual weight loss and minimal gas generation. This range will also ensure that the appropriate amount of liquid phase is present, which will have a moderate viscosity and aid in the densification of the ceramic proppants, as well as the formation of a dense enamel layer. The composite reactions of barite in the S3 sample follow a one-and-a-half-order chemical reaction mechanism within the temperature range of 950–1200 °C. The average activation energy and pre-exponential factor were 583.304 kJ mol⁻¹ and 5.81 × 10²⁰ min⁻¹, respectively. The kinetic and reaction rate equations for the composite reactions were (1 − α)^−1/2–1 = (5.81 × 10²⁰ × e^{−5.83 × 10^5/RT}) × t and dα/dt = (2(1 − α)^3/2) × (5.81 × 10²⁰ × e^{−(5.83 × 10^5)/RT)}), respectively. This study provides a theoretical basis and guidelines for large-scale production of CPs using DCs and CFA.     

Recombination lifetime of charge carriers in DLC thin films

Decay of photocurrent in diamond-like carbon (DLC) thin films and broadband dielectric measurements of rectifying n-Si/DLC junctions were used to find the recombination lifetime of charge carriers in DLC films. The recombination lifetime found from the two methods was between 10⁻⁴ and 10⁻³ s.     

Inactivation of microorganisms in a flow‐through photoreactor with an immobilized TiO2 layer

A laboratory flow‐through photoreactor with an immobilized layer of TiO₂ (total volume of the liquid 5000 cm ³, photoactive area 60 cm long and 30 cm wide; irradiation source UV lamps Eversun, Osram, light intensity from 0.9 to 6.2×10⁻⁹ Einstein cm⁻² s ⁻¹) was tested for the inactivation of Escherichia coli (strain DH5α) and bacteriophage λNM1149. The kinetics of the deactivation were approximately first order and the initial reaction rate depended on the light intensity. At maximum intensity, the rate constants of the bacteria and viruses inactivation were 2.3×10⁻⁴ and 7.2×10⁻⁴ s⁻¹, respectively. Bacterial inactivation was also accomplished with solar excitation. © 1999 Society of Chemical Industry     

Water sorption and water‐resistance properties of poly(vinyl alcohol)/clay nanocomposite films: Effects of chemical structure and morphology

A series of poly(vinyl alcohol)/sodium montmorillonite (PVA/NaMMT) nanocomposite films were prepared via a solution method, and their water sorption and water‐resistant properties were investigated as a function of clay content. The water sorption and water resistance properties were strongly dependent on the chemical structure and film morphology originating from the NaMMT content. The water diffusion coefficient and water uptake of the PVA/NaMMT nanocomposite films were obtained by best fits to a Fickian diffusion model. The diffusion coefficient and water uptake in the PVA/NaMMT nanocomposite films varied between 8.16 × 10⁻¹⁰ and 3.60 × 10⁻¹⁰ cm² s⁻¹ and 35.6 and 29.9 wt%, respectively. Both the diffusion coefficient and water uptake decreased as the content of NaMMT in pure PVA was increased. Additionally, the water resistance pressure (mm) of the PVA/NaMMT nanocomposite films increased with increasing NaMMT content. Contact angle analyses showed that the chemical affinity to water and the surface energy of the nanocomposite films decreased with increasing NaMMT content. Furthermore, the well‐dispersed and exfoliated structure in the nanocomposite films not only induced an increased tortuous path for water molecules to pass through, but also increased the molecular order. However, to enhance the water sorption properties and water resistance of hydrophilic PVA, further studies to increase the dispersion of clay particles and ensure desired morphological qualities such as crystallinity and molecular packing order in the PVA/clay nanocomposite films are required. POLYM. COMPOS., 36:660–667, 2015. © 2014 Society of Plastics Engineers     

Investigation of sorption and diffusion of supercritical carbon dioxide into poly(vinyl chloride)

The interaction of supercritical carbon dioxide (scCO₂) with poly(vinyl chloride) (PVC) was systematically investigated. PVC films of 0.5 mm thickness were treated with CO₂ at pressures between 5 and 40 MPa, at temperatures between 40 and 70°C and soaking times between 0.5 and 7 h. The gravimetric desorption data were kinetically and thermodynamically evaluated assuming Fickian diffusion and the morphology changes due to the CO₂ treatment investigated by microscopic methods. The sorbed amount of CO₂, q (q=g_CO2/g_polymer) ranged between 0.03 (5 MPa, 70°C) and 0.13 (15 MPa, 40°C). The desorption diffusivities, D_d, were in the order of 0.1×10⁻¹¹ m²/s and decreased with decreasing amounts of CO₂. In contrast, the sorption diffusivities, D_s, were markedly higher and varied between 0.7×10⁻¹¹ and 2.5×10⁻¹¹ m²/s (20 MPa, 40–70°C). The CO₂ treatment changed the polymer chain structure, macroscopically visualized by the film opaqueness and by the density decrease to 1.05 g/cm³. Microcellular structures were not detected.     

Diamond-like carbon films: electron spin resonance (ESR) and Raman spectroscopy

Tetrahedral diamond-like carbon (ta-C) films and hydrogenated a-C:H films were deposited onto Si substrates using filtered cathodic vacuum arc (FCVA) process and direct ion beam deposition from CH₄/C₂H₄ plasma, respectively. Stress of deposited films was varied in the range 2.8–8.5 GPa depending on deposition conditions. Stationary and pulse electron spin resonance (ESR), and Raman spectroscopy techniques were used to analyze sp² related defects in pseudo-gap of undoped as deposited and annealed 20–100 nm thick films.¹ High density of ESR active paramagnetic centers (PC) N_s=(1.0–4.5)×10²¹ cm⁻³ at g=2.0025 was observed in the films. The dependence of ESR line width and line shape vs. deposition conditions and internal film stress were investigated. The several actual mechanisms for ESR line width broadening were considered: spin–spin dipole–dipole and exchange interactions, super-hyperfine interaction (SHFI) with ¹H (for a-C:H), averaging of SHFI due to electron jumps between PC positions with different SHFI values, and broadening due to Mott's electron hopping process. Three types of samples were revealed depending on relative contribution of these mechanisms. Effects of annealing on mechanical and paramagnetic properties of films were studied. An electrical resistance anisotropy at room temperature for ta-C films and g-value anisotropy at low temperature (T<77 K) for both ta-C and a-C:H films were found for the first time. Nature and distribution details of paramagnetic defects in DLC films, anisotropy effects and Raman spectroscopy data are discussed.     

Electrochemical analysis of trace amounts of water in propylene carbonate electrolytes

Cyclic voltammetry and limiting currents to an rde have been used for the determination of the water in the 0.3–20 ppm range, in PC electrolytes. Carefully dried solutions yielded voltammetric peaks proportional to the amount of water added. In KPF₆ electrolytes, the cathodic current corresponding to the reduction of water was at 0.48 V, while in KAlCl₄ solutions the reduction occurred already starting at 2.8 V, both relative to a K/K⁺ reference. At these potentials, the current to an rde showed Levich type dependence on rpm and was proportional to the concentration of water in the range 0.5–20 ppm. The calculated diffusion coefficients of water are higher than expected: 25°C, D_H2O = 8.5±2 × 10⁻⁶ cm² s⁻¹ in 0.5 M KPF₆, while in 0.25 M KAlCl₄D_H2O, 10±2 × 10⁻⁶ cm² s⁻¹.