Role of thermal stability and vapor pressure of bis(2,2,6,6-tetramethyl-3,5-heptanedionato)magnesium(II) and its triamine adduct in producing magnesium oxide thin film using a plasma-assisted LICVD process

Thin films of magnesia were deposited on various substrates using plasma-assisted liquid injection chemical vapor deposition with volatile Mg(tmhd)₂·2H₂O (1) (tmhd = 2,2,6,6-tetramethyl-3,5-heptanedione). The precursor complexes, Mg₂(tmhd)₄·(2), and Mg(tmhd)₂·pmdien (3) (pmdien; N,N,N′,N″,N″-pentamethyldiethylenetriamine) were prepared from Mg(tmhd)₂·2H₂O (1). The temperature dependence equilibrium vapor pressure (p_e)_T data yielded a straight line when log p_e was plotted against reciprocal temperature in the range of 360–475 K, leading to standard enthalpy of vaporization (Δ_vapH°) values of 59 ± 1 and 67 ± 2 kJ mol^− 1 for (2) and (3) respectively. Thin films of magnesium oxide were grown at 773 K using complex (1) on various substrate materials. These films were characterized by X-ray diffraction, scanning electron microscopy and energy dispersive X-ray for their composition and morphology.     

Preparation of platinum-iridium nanoparticles on titania nanotubes by MOCVD and their catalytic evaluation

Pt based catalysts are commonly used in several industrial processes involving hydrogenation and dehydrogenation reactions. New deposition methods as well as support materials are being investigated to generate new catalysts with superior catalytic activity. In this work, platinum-iridium (Pt-Ir) nanoparticles of about 5 nm in size were supported on titania (TiO₂) nanotubes by metal organic chemical vapor deposition (MOCVD). The TiO₂ nanotubes were prepared by an alkali hydrothermal method using sodium hydroxide solution at 100 °C, during 64.8 ks. Pt-Ir nanoparticles were obtained by controlling the MOCVD conditions at 400 °C and 66.6 kPa.Textural properties and particle size were investigated by nitrogen physisorption (BET method), X-ray diffraction, Raman spectroscopy and high resolution transmission electron microscopy. Catalytic activity was measured in cyclohexene disproportion as the test molecule for hydrogenation/dehydrogenation reactions. The TiO₂ nanotubes exhibit a considerable high surface area of about 425,000 m²/kg, however, after calcination at 400 °C their nanotubular morphology was partially transformed. In spite of this change, the 5 nm Pt-Ir nanoparticles supported on TiO₂ nanotubes were more active in the cyclohexene disproportion reaction than conventional Pt-Ir/alumina catalysts in the whole range of temperatures investigated (50–250 °C). Hydrogenation reactions (high selectivity to cyclohexane) predominate at temperatures below 150 °C.     

Thermo-physical and thermal cycling properties of plasma-sprayed BaLa2Ti3O10 coating as potential thermal barrier materials

Increased turbine inlet temperature in advanced turbines has promoted the development of thermal barrier coating (TBC) materials with high-temperature capability. In this paper, BaLa₂Ti₃O₁₀ (BLT) was produced by solid-state reaction of BaCO₃, TiO₂ and La₂O₃ at 1500 °C for 48 h. BLT showed phase stability between room temperature and 1400 °C. BLT revealed a linearly increasing thermal expansion coefficient with increasing temperature up to 1200 °C and the coefficients of thermal expansion (CTEs) are in the range of 1 × 10^− 5–12.5 × 10^− 6 K^− 1, which are comparable to those of 7YSZ. BLT coatings with stoichiometric composition were produced by atmospheric plasma spraying. The coating contained segmentation cracks and had a porosity of around 13%. The microhardness for the BLT coating is 3.9–4.5 GPa. The thermo-physical properties of the sprayed coating were investigated. The thermal conductivity at 1200 °C is about 0.7 W/mK, exhibiting a very promising potential in improving the thermal insulation property of TBC. Thermal cycling result showed that the BLT TBC had a lifetime of more than 1100 cycles of about 200 h at 1100 °C. The failure of the coating occurred by cracking at the thermally grown oxide (TGO) layer due to severe oxidation of bond coat. Based on the above merits, BLT could be considered as a promising material for TBC applications.     

Fabrication and study on Ni1−xFexO-YSZ anodes for intermediate temperature anode-supported solid oxide fuel cells

Bimetal oxides Ni_1−xFe_xO (x = 0.01, 0.04, 0.08, 0.1, 0.15, 0.2, 0.4, 0.5) were synthesized and studied as anodes for intermediate temperature solid oxide fuel cells (SOFCs) based on yttria-stabilized zirconia (YSZ) film electrolyte. A single cell consisted of Ni_1−xFe_xO-YSZ anode, YSZ electrolyte film, LSM–YSZ composite cathode was prepared and tested at the temperature from 600 °C to 850 °C with humidified hydrogen (75 ml min⁻¹) as fuel and ambient air as oxidant. It was found that the cell with Ni_0.9Fe_0.1O-YSZ anode showed the highest power density, 1.238 W cm⁻² at 850 °C, among the cells with different anode composition. The promising performance of Ni_1−xFe_xO as anode suggests that bimetal anodes are worth studied for SOFCs in future.     

La2O3-modified YSZ coatings: High-temperature stability and improved thermal barrier properties

Lanthana precursor was coated on yttria-stabilized-zirconia (YSZ) powders by wet chemical infiltration, and was introduced to the crystalline structure and grain boundaries of YSZ after plasma spraying of thermal barrier coatings (TBCs). The microstructural stability and thermal barrier properties of this new kind of TBCs were studied under different annealing conditions. It demonstrates that the La₂O₃ surface coating restrains grain growth of YSZ during both deposition and post-annealing processes, compared to a TBC obtained from commercially available unmodified YSZ powders. According to the composition analysis, lanthana partially dissolved in the zirconia matrix after heat treatment. The thermal diffusivity of YSZ coating significantly decreased after lanthana modification, typically from 0.354 mm² s^− 1 for an unmodified sample to 0.243 mm² s^− 1, reflecting a decrease of 31%. Even after annealed at 1200 °C for 50 h, the thermal diffusivity of modified coatings still shows a reduction of 25% than unmodified samples.     

Synthesis and characterization of a series of bis(dimethyl-n-octylsilyl)oligothiophenes for organic thin film transistor applications

A series of bis-dimethyl-n-octylsilyl end-capped oligothiophenes consisting of two to six thiophene units has been synthesized and characterized to develop novel organic semiconductor materials. The UV–vis spectral data indicate that these silyl end-capped oligothiophenes have longer conjugation lengths as evidenced by the higher λ_max values than the corresponding unsubstituted thiophene oligomers. The thermal analyses indicate that the bis-silylated oligothiophenes show lower melting point (DSi-4T = 80 °C; DSi-5T = 115 °C; DSi-6T = 182 °C) than the corresponding dialkylated thiophene oligomers by 100 °C and hexamer DSi-6T exhibits a liquid crystalline mesophase at 143 °C. The α,ω-bis(dimethyl-n-octylsilyl)oligothiophenes (DSi-6T) have a remarkably high solubility in chloroform which are comparable to the corresponding α,ω-dihexyloligothiophenes. The remarkably increased solubility by these silyl end groups leads bis-silylated oligothiophenes to be applicable to solution processable devices for thin film transisitor (TFT) by utilizing a spin-coating technique. α,ω-Bis(dimethyl-n-octylsilyl)sexithiophene can be deposited as active semiconducting layer in thin film transistors, either by vacuum evaporation or by spin-coating. A high charge-carrier mobility has been obtained for both deposition techniques, μ = 4.6 × 10⁻² and 1.4 × 10⁻² cm² V⁻¹ s⁻¹, respectively.     

Thermophysical properties of lanthanum zirconate coating prepared by plasma spraying and the influence of post-annealing

Nano-scaled lanthanum zirconate powder prepared by co-precipitation–calcination method was plasma-sprayed into a thick coating on an alloy substrate. We investigated the thermophysical properties of the free-standing coating, including thermal conductivity and thermal expansion coefficients (TECs). Minimum value of the thermal conductivity (at 900 °C) of the coating was about 0.73 W m⁻¹ K⁻¹, and the average TEC in the measurement range was about 9.45 × 10⁻⁶ K⁻¹. Although the TEC value was similar to that of the bulk material, the change tendency versus temperature was different. After annealing at 1300 or 1400 °C for 50 h, we found that the heat insulation performance of the coating decreased with the heat treatment temperature, while the hardness and fracture toughness increased. A peak of sudden decrease in TEC value can be observed in the curve, and with increasing temperature, the peak shifted to high-temperature direction.     

Studies on accumulation of chloride ions in pits growing during anodic polarization

The concentration of Cl⁻ ions within pits grown on 18Cr---12Ni---2Mo---Ti austenitic stainless steel specimens immersed in vertical position in 0·5N NaCl + 0·1N H₂SO₄ and polarized to 860 mV_NHE was studied at 20°C. The Cl⁻ concentration within pits increases with time to a maximum and then decreases (for example, after 6 h 2N Cl⁻ is observed). The higher accumulation of Cl⁻ within pits, the slower their development. For slowly growing pits a maximum value of about 12N Cl⁻ was observed. The low pH values of the solution within pits are the consequence of high Cl⁻ contents occurring there.     

On the wide range of mechanical properties of ZTA and ATZ based dental ceramic composites by varying the Al2O3 and ZrO2 content

In this work the influence of pressureless sintering on the Vickers hardness and fracture toughness of ZrO₂ reinforced with Al₂O₃ particles (ATZ) and Al₂O₃ reinforced with ZrO₂ particles (ZTA) has been investigated. The ceramic composites were produced by means of uniaxial compacting at 50 MPa and the green compacts were heated to 1250 °C using a heating rate of 10 °C min⁻¹, then to 1500 °C at 6 °C min⁻¹ and maintained at this temperature during 2 h. After sintering, relative density over 94%, hardness values between 9.5 and 21.9 GPa, and fracture toughness as high as 3.6 MPa m^1/2 were obtained. The presence of TZ-3Y particles on the grain boundaries suggests that they inhibit notably the alumina grain growth. The grain sizes of pure Al₂O₃ and TZ-3Y as well as Al₂O₃ and TZ-3Y in the 20 wt% Al₂O₃+80 wt% TZ-3Y composite were 1.27 ± 0.51 μm, 0.57 ± 0.12 μm, 0.65 ± 0.19 μm and 0.41 ± 0.14 μm, respectively. The 20 wt% Al₂O₃ + 80 wt% ZrO₂ + 3 mol% Y₂O₃ (TZ-3Y) composite showed a hardness of 16.05 GPa and the maximum fracture toughness (7.44 MPa m^1/2) with an average grain size of 0.53 ± 0.17 μm. On the other side, the submicron grain size and residual porosity seem to be responsible for the high hardness and fracture toughness obtained. The reported values were higher than those obtained by other authors and are in concordance with international standards that could be suitable for dental applications.     

Crystal structure of single phase and low sintering temperature of α-cordierite synthesized from talc and kaolin

Cordierite body with the formulation of 2.8MgO·1.5Al₂O₃·5SiO₂ was prepared from talc and kaolin as the basic raw materials. Following glass crystallization technique the glass powder was successfully heat treated at 900 °C for 2 h to form a single-phase α-cordierite. The crystal structure of α-cordierite was analysed using X-ray diffraction technique and the Rietveld structural refinement method. Differential thermal analysis (DTA), Fourier-transform infrared (FTIR), field emission scanning electron microscopy (FESEM), coefficient of thermal expansion (CTE) and dielectric properties were also performed. Results show that the materials crystallized as a hexagonal structure with space group of P6/mcc and the room temperature lattice parameters are a = 9.743742 (Å) and c = 9.389365 (Å). FTIR analysis on the glass revealed that only silicate species is the only unit that exists in the glass network. DTA also confirmed that α-cordierite completely formed after 13.5 min of isothermal heating at 900 °C. Coefficient of thermal expansion of synthesized α-cordierite is 2.5 × 10⁻⁶ °C⁻¹. The dielectric constant is between 5.0 and 5.5 for 1 MHz and 1.8 GHz, respectively, and the dielectric loss is in the range 10⁻². FESEM micrographs revealed that the material is fully densified.     

Microstructure evolution and thermal stability of an Fe-based amorphous alloy powder and thermally sprayed coatings

High velocity oxy-fuel (HVOF) thermal spraying has been used to produce coatings of an Fe–18.9%Cr–16.1%B–4.0%C–2.8%Si–2.4%Mo–1.9%Mn–1.7%W (in at.%) alloy from a commercially available powder (Nanosteel SHS7170). X-ray diffraction (XRD), differential scanning calorimetry (DSC) and scanning electron microscopy (SEM) were employed to investigate the powder, as-sprayed coatings and annealed coatings which had been heated to temperatures in the range of 550–925 °C for times ranging from 60 to 3900 min. Microhardness changes of the coatings were also measured as a function of annealing time and temperature. The powder was found to comprise amorphous and crystalline particles; the former had a maximum diameter of around 22 μm. The coating was composed of splat like regions, arising from rapid solidification of fully molten powder, and near-spherical regions from partially melted powder which had a largely retained its microstructure. The amorphous fraction of the coating was around 50% compared with 18% for the powder. The enthalpies and activation energies for crystallization of the amorphous phase were determined. Crystallization occurred in a two stage process leading to the formation of α-Fe (bcc), Fe_1.1Cr_0.9B_0.9 and M₂₃C₆ phases. DSC measurements showed that the first stage occurred at 650 °C. Annealing the coating gave a hardening response which depended on temperature and time. The as-sprayed coating had a hardness of 9.2 GPa and peak hardnesses of 12.5 and 11.8 GPa were obtained at 650 and 750 °C, respectively. With longer annealing times hardness decreased rapidly from the peak.     

Effect of CrB2 addition on densification, properties and oxidation resistance of TiB2

This paper presents the results of detailed studies carried out on the densification of TiB₂ with CrB₂ as sinter additive by hot pressing. The dense compacts were characterized by measurement of hardness, indentation fracture toughness, flexural strength, coefficient of thermal expansion and electrical resistivity. Oxidation characteristics were investigated between 600 °C and 1000 °C and isothermal oxidation kinetics at 850 °C. Phase identification and surface morphology analysis of hot pressed and oxidized samples were done using XRD and SEM. A high density of 96.61% Τ.D was obtained with the addition of 2.5% CrB₂ by hot pressing at 1750 °C under 35 MPa pressure. Hardness values of composites with 2.5–10% CrB₂ were close to 24 GPa and fracture toughness in the range of 3–5 MPa m^1/2. Coefficient of thermal expansion of the composite with 10% CrB₂ was measured in the range of 6.21–7.43 × 10⁻⁶/K from room temperature to 1000 °C. Electrical resistivity of TiB₂ + 10%CrB₂ was measured as 32.83, 75.97 and 120 μΩ cm at 25 °C, 500 °C and 900 °C, respectively. Observed nature of oxidation was parabolic for all composites. Formation of continuous and thick glassy film was observed with increased CrB₂ content in the composite. TiO₂ and CrBO₃ phases were identified on the oxidized surface which are responsible for the improved oxidation resistance of this composite.     

Investigation of the microwave dielectric properties of Ca1−xMgxLa4Ti5O17 ceramics for application in coplanar patch antenna

In this paper, the dielectric properties of Ca_1−xMg_xLa₄Ti₅O₁₇ ceramics at microwave frequency have been studied. The diffraction peaks of Ca_(1−x)Mg_xLa₄Ti₅O₁₇ ceramics nearly unchanged with x increasing from 0 to 0.03. Similar X-ray diffraction peaks of Ca_0.99Mg_0.01La₄Ti₅O₁₇ ceramic were observed at different sintering temperatures. A maximum density of 5.3 g/cm³ can be obtained for Ca_0.99Mg_0.01La₄Ti₅O₁₇ ceramic sintered at 1500 °C for 4 h. A maximum dielectric constant (_r) and quality factor (Q × f) of Ca_0.99Mg_0.01La₄Ti₅O₁₇ ceramic sintered at 1500 °C for 4 h are 56.3 and 12,300 GHz (at 6.4 GHz), respectively. A near-zero temperature coefficient of resonant frequency (τ_f) of −9.6 ppm/°C can be obtained for Ca_0.99Mg_0.01La₄Ti₅O₁₇ ceramic sintered at 1500 °C for 4 h. The measurement results for the aperture-coupled coplanar patch antenna at 2.5 GHz are presented. With this technique, a 3.33% bandwidth (return loss <−10 dB) with a center frequency at approximately 2.5 GHz has been successfully achieved.     

Thermodynamic studies on LaFeO3(s)

The enthalpy increments and the standard molar Gibbs energies in the formation of LaFeO₃(s) have been measured using a high-temperature Calvet micro-calorimeter and a solid oxide galvanic cell, respectively. The corresponding expression for enthalpy increments is given as:

H°(T)−H°(298.15 K)(J mol⁻¹)(±1.2%)=−36887.27+103.53 T(K)+25.997×10⁻³T²(K)+11.055×10⁵/T(K).

The heat capacity, the first differential of H°(T)−H°(298.15 K) with respect to temperature, is given as:

C_p,m°(T)(JK⁻¹mol⁻¹)=103.53+51.994×10⁻³T(K)−11.055×10⁵/T²(K).

From the measured e.m.f. of the cell, (−)Pt/(LaFeO₃(s)+La₂O₃(s)+Fe(s))//CSZ//(Ni(s)+NiO(s))/Pt(+), and the relevant Δ_fG_m°(T) values from the literature, the Δ_fG_m°(LaFeO₃, s, T) was calculated, and is given as:

Δ_fG_m°(LaFeO₃, s, T)(kJmol⁻¹)(±0.72)=−1319.2+0.2317T(K).

The calculated Δ_fH_m°(LaFeO₃, s, 298.15 K) and S°(298.15 K) values obtained using the second law method are −1334.7 kJ mol⁻¹ and 128.9 J K⁻¹ mol⁻¹, respectively.     

Elastic properties of epoxy system coatings on aluminum substrate

In the present work elastic properties of the epoxy system coatings deposited on aluminum-based alloy substrate were investigated using internal friction methods i.e. i) vibrating reed technique (frequency about 100 Hz) and ii) torsion pendulum (1 Hz). The apparent Young's modulus γ²E (γ — adhesion coefficient, E — Young's modulus of the coating) was determined for different state of substrate surface and curing temperatures. It was shown that γ²E correlates linearly with the bond shear strength obtained from tensile tests by applying Instron machine (destructive method). Moreover, the dependence γ²E versus curing temperature shows a maximum at 350 K. Isothermal measurements of mechanical loss tangent Q^− 1(t) versus curing time show that the curing reaction of the epoxy material is observed as an asymmetric peak whose position shifts towards shorter times with increasing curing temperatures. Activation energy of the curing process determined from this shift is found to be E_a = (51 ± 3) kJ/mol.     

Stress analysis of ceramic insulation coating on Cu/MgB2 wires for W&R MgB2 coils

Ceramic insulation coatings were produced on Cu/MgB₂ wires, which were fabricated by Hyper Tech Research Inc., using Continuous Tube Forming and Filling (CTFF) process, from the solution of Zr, and Y based organometalic compounds, solvent and chelating agent using reel-to-reel sol–gel technique for MgB₂ coils. Y₂O₃–ZrO₂/Cu/MgB₂ wires were annealed at 700 °C for 30 min with 5.8 °C/min heating rate under 4% H₂–Ar gas flow. Residual stresses were examined for Cu/MgB₂ wire and YSZ coatings with varying thicknesses. It was observed that displacement values are independent from YSZ thicknesses and the maximum effective stress value is in the Cu region. The surface morphologies and microstructure of samples were characterized using SEM. SEM micrographs of the insulation coatings revealed cracks, pinholes and mosaic structure.     

Oxidation behaviour of PACVD TiBN coating at elevated temperatures

The elevated-temperature oxidation behaviour of a TiBN coating on a plasma-nitrided hot-work tool steel (DIN 1.2367) by means of plasma-assisted chemical vapour deposition (PACVD) was investigated under the condition where a coated die would be preheated prior to being mounted on the press for aluminium extrusion. The TiBN coating was found to possess good resistance to oxidation up to 400 °C. Rapid oxidation started to occur at 450 °C. Radio frequency glow discharge optical emission spectroscopy (rf-GDOES) indicated that the oxidised layer was thickened from 100 nm to 1.0 μm, as the soaking time at 500 °C was prolonged from 2 to 16 h, which was attributed to the high temperature that promoted the penetration of oxygen into the coating. rf-GDOES also showed that boron initially in the coating vanished from the oxidised layer when the temperature was 450 °C or higher. X-ray diffractometry confirmed that the oxidised layer was composed mainly of TiO₂. SEM revealed that the TiO₂ layer was pulverised, leaving many microcracks and cavities, as a result of the losses of boron oxide and nitrogen. The rapid oxidation at above 450 °C was attributed to the pulverised TiO₂ layer that was unable to hinder the diffusion of oxygen into the coating. It is therefore recommended to apply a protective gas during the preheating of the TiBN-coated die for aluminium extrusion. Alternatively, an advanced TiBN coating with enhanced resistance to oxidation must be developed, which will be conducive to its application for aluminium extrusion dies.     

Polymer-induced generation and characterization of electrophoretic properties of hollow TiOX nanospheres for electronic paper

Hollow TiO_X nanospheres have been successfully prepared using hollow core–double shell latex particles (poly(styrene-co-methyl methacrylate-co-butyl acrylate-co-methacrylic acid) (abbreviated in poly(St-co-MMA-co-BA-co-MAA)) as template, which involves the deposition of inorganic coating on the surface of hollow core–shell latex particles and subsequent removal of the latex by calcinations in air or ammonia gas. Ti(OBu)₄ was used as precursor for the preparation of hollow TiO_X nanospheres. TEM of white hollow core–double shell polymers particles with an aperture of approximately 225 nm displays the perfect characteristic hollow nanospheres structure of primary core–double shell particles. The formation of TiO_X was confirmed by XRD analysis and hollow structure of the particles was revealed by transmission electron microscopy (TEM). When the calcined temperature was at 800 °C, hollow TiO₂ nanospheres were arranged regularly with the diameter range of 130–170 nm. The electrophoretic properties were characterized by JS94J micro-electrophoresis apparatus. The electrophoretic mobility of white TiO₂ and black TiO hollow spheres in tetrachloroethylene were 1.09 × 10⁻⁵ and 3.12 × 10⁻⁵ cm²/V s, and the zeta potentials were 7.10 and 20.24 mV, respectively. The results show that white TiO₂ particles and black TiO hollow nanoparticles are suitable as electrophoretic particles and possess the application potential in the future electrophoretic display.     

A study of the growth of iron oxides by Mössbauer spectroscopy

The rate of oxidation of Fe₃O₄ to α-Fe₂O₃ in 1 atm of oxygen has been measured at 592°, 629° and 667°C by Mössbauer transmission spectroscopy. Taken together with our earlier measurements, the data lead to an activation energy for α-Fe₂O₃ growth of 44 kcal mole⁻¹ for the temperature interval 475–670°C. That the Mössbauer technique should prove useful in the study of reactions in oxide scales containing wüstite is also demonstrated.     

The anodic behaviour of copper in static and flowing hydrochloric acid solutions

The dissolution of copper in 0·36 to 3·6 HCl was studied both in static and in flowing solutions using flow rates between 0·098 and 1·14 ms⁻¹, all in the region of laminar flow.Steady state anode potential current curves, potentiodynamic sweep and potentiostatic pulse techniques and impedance measurements, in the range of 0·02–7 kHz, were used. In both static and flowing solutions dissolution of copper occurs to a monovalent state, as chloro-complexes CuCl⁻₂ and CuCl²⁻ with exchange currents for the two reactions of 1·9 × 10⁻⁵ A mm⁻² and 8 × 10⁻⁷ Amm⁻² respectively in 1·44 MHCl. The cuprous chloride layer first forms a monolayer and subsequently grows to considerable thicknesses. The double layer capacity is constant at 0·17 ± 0·03 μFmm⁻² at potentials below multilayer formation and this is interpreted as implying that there is no specific adsorption of chloride ions prior to formation of the cuprous chloride layer. As the flow rate increases the film becomes thinner so delaying the formation of the film of critical thickness required for passivation.