Synthesis of silicate coating by layer-by-layer self-assembly of Yb2O3 and SiO2 particles

Multilayer particle assemblies that contained both Yb₂O₃ and SiO₂ particles were prepared on Si substrates by layer-by-layer self-assembly (LBLSA) as a new non-line-of-sight avenue of producing dense and uniform Yb₂O₃-SiO₂ coating microstructures. Morphological characteristics of the multilayer particle assemblies upon viscous sintering in the temperature range of 1300 to 1350 °C were evaluated in reference to those of multilayer assemblies that only contained SiO₂ or Yb₂SiO₅ particles. A 4-layer 0.5-μm SiO₂ particle assembly could be easily transformed to a dense and continuous coating structure after sintering. In contrast, a 4-layer 1.7-μm Yb₂SiO₅ particle assembly could not be consolidated and densified, as anticipated from the absence of the viscous sintering mechanism provided by the SiO₂ phase. Most of the coatings produced from sintering of Yb₂O₃-SiO₂ (0.5 μm) particles assemblies were dense and continuous with Yb₂Si₂O₇ and Yb₂SiO₅ as two predominant phases. The results suggest the feasibility of producing dense and uniform silicate coating structures by integrating the LBLSA concept with the viscous flow sintering mechanism provided by the SiO₂ particles.     

Hot corrosion behaviour of Yb2Zr2O7 ceramic coated with V2O5 at temperatures of 600-800 °C in air

To better understand the hot corrosion behaviour of Yb₂Zr₂O₇ ceramic in molten V₂O₅, hot corrosion experiments were performed in a temperature range of 600-800 °C in air. Different reaction products of ZrV₂O₇, YbVO₄ and m-ZrO₂ were identified depending upon the hot corrosion conditions, for example, ZrV₂O₇ and YbVO₄ at 600 °C for 2 h and 8 h; ZrV₂O₇, m-ZrO₂ and YbVO₄ at 700 °C for 2 h; m-ZrO₂ and YbVO₄ either at 800 °C for 2 h or at 700-800 °C for 8 h. The hot corrosion reaction mechanisms were further discussed based on the thermal instability of ZrV₂O₇ at elevated temperatures.     

Oxidation and corrosion of silicon nitride ceramics with different sintering additives at 1200 and 1500 °C in air, water vapour, SO2 and HCl environments - A comparative study

The effect of different sintering additives on the high temperature oxidation and corrosion behaviour of silicon nitride based ceramics was investigated. Comparative tests were conducted at 1200 and 1500 °C in air, in water vapour, and with the highly corrosive gases HCl and SO₂. Si₃N₄ was prepared with MgO, Al₂O₃, Y₂O₃ and Al₂O₃ + Y₂O₃ sintering additives. Hot pressed discs were tested for a total time of up to 128 h. The electrically conductive ceramic composites Si₃N₄ + TiN and Si₃N₄ + MoSi₂ were also tested under the same conditions. The effects that the different corrosion environments have on the different ceramics are presented. SEM studies of the oxidised ceramics show the direct transformation of Si₃N₄ grains into SiO₂ through a reaction interface layer.     

Oxidation behavior of Ti3AlC2 at 1000-1400 °C in air

The isothermal oxidation behavior of bulk Ti₃AlC₂ has been investigated at 1000-1400 °C in air for exposure times up to 20 h by means of TGA, XRD, SEM and EDS. It has been demonstrated that Ti₃AlC₂ has excellent oxidation resistance. The oxidation of Ti₃AlC₂ generally followed a parabolic rate law with parabolic rate constants, k_p that increased from 4.1×10⁻¹¹ to 1.7×10⁻⁸ kg² m⁻⁴ s⁻¹ as the temperature increased from 1000 to 1400 °C. The scales formed at temperatures below 1300 °C were dense, adherent, resistant to cyclic oxidation and layered. The inner layer of these scales formed at temperatures below 1300 °C was continuous α-Al₂O₃. The outer layer changed from rutile TiO₂ at temperatures below 1200 °C to a mixture of Al₂TiO₅ and TiO₂ at 1300 °C. In the samples oxidized at 1400 °C, the scale consisted of a mixture of Al₂TiO₅ and, predominantly, α-Al₂O₃, while the adhesion of the scales to the substrates was less than that at the lower temperatures. Effect of carbon monoxide at scale/substrate was involved in the formation of the continuous Al₂O₃ layers.     

Effect of SnO2 doping on microstructural and electrical properties of ZnO-Pr6O11 based varistor ceramics

ZnO-Pr₆O₁₁ based varistor ceramics doped with 0-2.0 mol% SnO₂ were fabricated by sintering samples at 1300 °C for 2 h with conventional ceramic processing method. X-ray diffraction analysis indicated that the doped SnO₂ reacted with praseodymium oxides during sintering, generating Pr₂Sn₂O₇ phase. Through scanning electron microscopy, it was found that the doping of SnO₂ played a role against the growth of ZnO grains. Capacitance-voltage analysis revealed that the doped SnO₂ acted as a donor in the varistor. The measured electric-field/current-density characteristics of the samples showed that the varistor voltage increased with the increase of SnO₂ doping content, when the SnO₂ content was no more than 1.0 mol%; with the SnO₂ content up to no more than 0.5 mol%, the doping of SnO₂ could increase the nonlinear coefficient; but, when the SnO₂ doping content was further increased, the nonlinear coefficient and varistor voltage of the samples decreased, and the leakage current increased.     

Preparation of Ni0.5Zn0.5Fe2O4/SiO2 nanocomposites and their adsorption of bovine serum albumin

The magnetic nanocomposites of (1 − x)Ni_0.5Zn_0.5Fe₂O₄/xSiO₂ (x = 0-0.2) were synthesized by the citrate-gel process and their absorption behavior of bovine serum albumin (BSA) was investigated by UV spectroscopy at room temperature. The gel precursor and resultant nanocomposites were characterized by FTIR, XRD, TEM and BET techniques. The results show that the single ferrite phase of Ni_0.5Zn_0.5Fe₂O₄ is formed at 400 °C, with high saturation magnetization and small coercivity. A porous, amorphous silica layer is located at the ferrite nanograin boundaries, with the silica content increasing from 0 to 0.20, the average grain size of Ni_0.5Zn_0.5Fe₂O₄ calcined at 400 °C reduced from about 18-8 nm. Consequently, the specific surface area of the nanocomposites ascends clearly with the increase of silica content, which is largely contributed by the increase in the thickness of the porous silica layer. The Ni_0.5Zn_0.5Fe₂O₄/SiO₂ nanocomposites demonstrate a better adsorption capability than the bare Ni_0.5Zn_0.5Fe₂O₄ nanoparticles for BSA. With the increase of the silica content from 0 to 0.05 and the specific surface area from about 49-57 m²/g, the BSA adsorption capability of the Ni_0.5Zn_0.5Fe₂O₄/SiO₂ nanocomposites calcined at 400 °C improve dramatically from 22 to 49 mg/g. However, with a further increase of the silica content from 0.05 to 0.2, the specific surface area increase from about 57-120 m²/g, the BSA adsorption for the nanocomposites remains around 49 mg/g, owing to the pores in the porous silica layer which are too small to let the BSA protein molecules in.     

Formation of WSi2 coating on tungsten and its short-term cyclic oxidation performance in air

Microstructural aspects of WSi₂ coating on pure W and its short-term oxidation performance under cyclic heating and cooling conditions in air at 1100 and 1300 °C have been studied. Cyclic oxidation performance of this coating has been compared with its performance under isothermal oxidation. The coating was applied by using a pack siliconization method. The as-formed coating consisted of an outer WSi₂ layer and an inner W₅Si₃ layer. The WSi₂ layer had a columnar structure and had several through-thickness cracks generated due to the mismatch of coefficient of thermal expansion between the coating and the substrate. Based on the coating microstructure, the mechanism of coating growth during siliconizing has been suggested. Weight change data obtained under cyclic oxidation in air at 1100 and 1300 °C suggested that the above coating can provide protection to W substrate against oxidation for about 2 h. The oxide scale that formed on the coating during oxidation exposure consisted of SiO₂ and WO₃ at 1100 °C and only SiO₂ at 1300 °C. The protective silica layer underwent spallation during thermal cycling, leading to a diminishing of the protective capability of the coating. More importantly, localized oxidation of the W substrate through discontinuities present in the coating at sharp corners caused severe damage to the coated samples. Isothermal oxidation exposure of the coating, in comparison, resulted in a much lower degree of damage and the coating provided protection for a much longer duration (up to 10 h) at the above temperatures. In this study, apart from reporting a hitherto unreported oxide scale morphology, the microstructural degradation of the coating during oxidation has been linked to the columnar structure of the WSi₂ layer.     

Microstructural evolution during high-temperature oxidation of spark plasma sintered Ti2AlN ceramics

Microstructures of Ti₂AlN ceramics synthesized and simultaneously consolidated from starting mixtures of Ti/Al/TiN powders by spark plasma sintering (SPS) were characterized using X-ray diffraction, scanning electron microscopy, focused ion beam (FIB) and transmission electron microscopy (TEM). When sintered for 10 min at 1300 °C, nearly single-phase Ti₂AlN ceramics with elongated (∼22 × 6 × 6 μm) grains were obtained. After sintering for 10 min at 1200 °C and chemical etching, Ti₂AlN nanowhiskers (150-200 nm dia., 1-5 μm long) were exposed in pores coexisting with TiAl, TiN and Ti₂AlN grains. FIB-TEM studies revealed single-crystal Ti₂AlN nanowhiskers in a TiAl matrix with orientation relationship [1 1 −2 0]_H//[−1 0 1]_γ, (0 0 0 1)_H//(1 1 1)_γ, γ = TiAl, H = Ti₂AlN. The nanowhiskers are believed to form by diffusion of TiN into TiAl during SPS and to be exposed during the chemical etch. Microstructural development during high-temperature oxidation of dense Ti₂AlN ceramics for 1 h at <1200 °C involves gradual formation on the surface of layered microstructures containing anatase, rutile and α-Al₂O₃. After 1 h at >1200 °C, more complex layered microstructures containing Al₂TiO₅, rutile, α-Al₂O₃ and continuous voids layers form. After heating to 1100 °C for 1 h and cooling to room temperature, planar defects are observed in surface TiO₂ grains identified as stacking faults bounded by partial dislocations. After heating for 1 h at 1400 °C and cooling to room temperature, cracks propagate in TiO₂ grains. It is believed that planar defects and cracks arise from stress generation in the oxide scale. Thermal stresses formed on cooling may arise from thermal expansion mismatch of phases (TiO₂, Al₂O₃ and Al₂TiO₅) in the oxide scale, the high anisotropy of thermal expansion in Al₂TiO₅ and thermal expansion mismatch between the oxide scale and Ti₂AlN substrate. Growth stresses formed during the isothermal oxidation treatment may arise from the volume changes associated with oxidation reactions of Ti₂AlN. An oxidation mechanism for Ti₂AlN ceramics is proposed, which involves initial reaction with atmospheric oxygen to form oxide phases, demixing of the mixed oxide phases, void formation due to the Kirkendall effect and gaseous NO_x release. Oxidation of Ti₂AlN <1200 °C with 1 h hold times is limited, while above this temperature the oxide scale grows rapidly, and Ti₂AlN ceramics undergo heavy oxidation.     

Dielectric and microwave properties of ZrO2 doped CaO-SiO2-B2O3 ceramic matrix composites

The behavior of dielectric and microwave properties against sintering temperature has been carried out on CaO-SiO₂-B₂O₃ ceramic matrix composites with ZrO₂ addition. The results indicated that ZrO₂ addition was advantageous to improve the dielectric and microwave properties. X-ray diffraction (XRD) patterns show that the major crystalline β-CaSiO₃ and a little SiO₂ phase existed at the temperature ranging from 950 °C to 1050 °C. At 0.5 wt% ZrO₂, CaO-SiO₂-B₂O₃ ceramic matrix composites sintered at 1000 °C possess good dielectric properties: ?_r = 5.85, tan δ = 1.59 × 10⁻⁴ (1 MHz) and excellent microwave properties: ?_r = 5.52, Q · f = 28,487 GHz (11.11 GHz). The permittivity of Zr-doped CaO-SiO₂-B₂O₃ ceramic matrix composites exhibited very little temperature dependence, which was less than ±2% over the temperature range of −50 to 150 °C. Moreover, the ZrO₂-doped CaO-SiO₂-B₂O₃ ceramic matrix composites have low permittivity below 5.5 over a wide frequency range from 20 Hz to 1 MHz.     

Effects of K2O-Li2O doping on surface and catalytic properties of Fe2O3/Cr2O3 system

The effects of K₂O and Li₂O-doping (0.5, 0.75 and 1.5 mol%) of Fe₂O₃/Cr₂O₃ system on its surface and the catalytic properties were investigated. Pure and differently doped solids were calcined in air at 400-600 °C. The formula of the un-doped calcined solid was 0.85Fe₂O₃:0.15Cr₂O₃. The techniques employed were TGA, DTA, XRD, N₂ adsorption at −196 °C and catalytic oxidation of CO oxidation by O₂ at 200-300 °C. The results revealed that DTA curves of pure mixed solids consisted of one endothermic peak and two exothermic peaks. Pure and doped mixed solids calcined at 400 °C are amorphous in nature and turned to α-Fe₂O₃ upon heating at 500 and 600 °C. K₂O and Li₂O doping conducted at 500 or 600 °C modified the degree of crystallinity and crystallite size of all phases present which consisted of a mixture of nanocrystalline α- and γ-Fe₂O₃ together with K₂FeO₄ and LiFe₅O₈ phases. However, the heavily Li₂O-doped sample consisted only of LiFe₅O₈ phase. The specific surface area of the system investigated decreased to an extent proportional to the amount of K₂O and Li₂O added. On the other hand, the catalytic activity was found to increase by increasing the amount of K₂O and Li₂O added. The maximum increase in the catalytic activity, expressed as the reaction rate constant (k) measured at 200 °C, attained 30.8% and 26.5% for K₂O and Li₂O doping, respectively. The doping process did not modify the activation energy of the catalyzed reaction but rather increased the concentration of the active sites without changing their energetic nature.     

Fabrication of GdBa2Cu3O7−x films by TFA-MOD process

GdBa₂Cu₃O_7−x (GdBCO) films have been deposited on LaAlO₃ (LAO) (0 0 l) single crystal substrates by trifluoroacetate metal organic deposition (TFA-MOD) method. The effects of oxygen partial pressure and firing temperature on microstructure and critical properties of GdBCO films were discussed. The phase formation, texture and microstructure of films were characterized by X-ray diffraction and scanning electron microscopy. The oxygen partial pressure was considered to play a great role for formation of impurity phase and a-axis oriented grains. The degree of c-axis orientation was also influenced by the firing temperature. The highly c-axis oriented GdBCO film obtained at 815 °C under an oxygen partial pressure of 100 ppm has a high performance critical current density J_c (77 K, self field) = 1.8 MA/cm².     

Characteristics of ZnO-B2O3-SiO2-CaO glass frits prepared by spray pyrolysis as inorganic binder for Cu electrode

ZnO-B₂O₃-SiO₂-CaO glass frits were directly prepared by high temperature spray pyrolysis for use in Cu electrodes. The frits prepared at temperatures above 1400 °C were spherical, amorphous, of fine size and dense structure. The mean particle size and geometric standard deviation of the frits prepared at 1400 °C were 0.87 μm and 1.37, respectively. The temperatures of glass transition, crystallization and melting were 454, 534 and 800 °C, respectively. The glass layer fired at 800 °C had a dense structure due to the material's complete melting, despite some crystals being observed by SEM. A copper electrode formed from copper paste with glass frits had a dense structure when fired at 800 °C. The specific resistances of electrodes formed from copper paste with and without glass frits were 2.5 and 8.5 μΩ cm, respectively.     

Dielectric properties of soft chemical method derived CaCu3Ti4O12 thin films onto Pt/TiO2/Si(1 0 0) substrates

Calcium copper titanate, CaCu₃Ti₄O₁₂ (CCTO), thin film has been deposited by the soft chemical method on Pt/Ti/SiO₂/Si (1 0 0) substrates at 700 °C for 2 h. The peaks were indexed as cubic phase belonging to the Im−3 space group. The film exhibited a duplex microstructure consisting of large grains of 130 nm in length and regions of fine grains (less than 80 nm). The CCTO film capacitor showed a dielectric loss of 0.031 and a dielectric permittivity of 1020 at 1 MHz. The J-V behavior is completely symmetrical, regardless of whether the conduction is limited by interfacial barriers or by bulk-like mechanisms. Based on impedance analyses, the equivalent circuit of CCTO film consisting of a resistor connected in series with two resistor-capacitor (RC) elements.     

Structural and dielectric properties of Bi2Zn2/3Nb4/3O7 thin films prepared by pulsed laser deposition at low temperature for embedded capacitor applications

Bi₂Zn_2/3Nb_4/3O₇ thin films were deposited on Pt/TiO₂/SiO₂/Si(1 0 0) substrates at a room temperature under the oxygen pressure of 1-10 Pa by pulsed laser deposition. Bi₂Zn_2/3Nb_4/3O₇ thin films were then post-annealed below 200 °C in a rapid thermal process furnace in air for 20 min. The dielectric and leakage current properties of Bi₂Zn_2/3Nb_4/3O₇ thin films are strongly influenced by the oxygen pressure during deposition and the post-annealing temperature. Bi₂Zn_2/3Nb_4/3O₇ thin films deposited under 1 Pa oxygen pressure and then post-annealed at a temperature of 150 °C show uniform surface morphologies. Dielectric constant and loss tangent are 57 and 0.005 at 10 kHz, respectively. The high resolution TEM image and the electron diffraction pattern show that nano crystallites exist in the amorphous thin film, which may be the origin of high dielectric constant in the Bi₂Zn_2/3Nb_4/3O₇ thin films deposited at low temperatures. Moreover, Bi₂Zn_2/3Nb_4/3O₇ thin film exhibits the excellent leakage current characteristics with a high breakdown strength and the leakage current density is approximately 1 × 10⁻⁷ A/cm² at an applied bias field of 300 kV/cm. Bi₂Zn_2/3Nb_4/3O₇ thin films are potential materials for embedded capacitor applications.     

Synthesis and phosphorescence properties of Mn, La and Ho in MgAl2Si2O8

Mn⁴⁺, La³⁺ and Ho³⁺ doped MgAl₂Si₂O₈-based phosphors were first synthesized by solid state reaction. They were characterized by thermogravimetry (TG), differential thermal analysis (DTA), X-ray powder diffraction (XRD), photoluminescence (PL) and scanning electron microscopy (SEM). The phosphors were obtained at about 1300 °C. They showed broad red and fuchsia-pink emission bands in the range of 610-715 nm and had a different maximum intensity when activated by UV illumination. Such a fuchsia-pink emission can be attributed to the intrinsic d-d transitions of Mn⁴⁺.     

Oxidation performance of Mo3Si with Al additions

The Mo₃Si alloys with different aluminum contents were fabricated by the arc-melting and drop-casting technique, heat treated and then exposed to air at 700, 800, 900 and 1000 °C in order to assess their oxidation behavior. Line scan studies led to the assumption that the oxide scale thermally grown at 1000 °C was composed of SiO₂ which was located closer to the alloy matrix and Al₂O₃ around the outer surface of the oxidized sample, while the Mo oxide volatilized at this oxidation temperature. The results also showed that the unalloyed sample (Mo₃Si) underwent a pest reaction in a short time of exposure, while the sample with 16 at.% Al exhibited the best oxidation behavior, which could be attributed to the formation of SiO₂ and Al₂O₃ in the oxide scale.     

Phase transformations in face centered cubic (Al0.32Cr0.68)2O3 thin films

Face centered cubic (Al_0.32Cr_0.68)₂O₃ thin films have been annealed in the temperature range of 500–1000 °C during 2–8 h. The fcc structure of the film remains intact when annealed at temperatures up to 700 °C for 8 h. X-ray diffraction and transmission electron microscopy show the onset of phase transformation to corundum phase alloys in the sample annealed at 900 °C for 2 h, where annealing at 1000 °C for 2 h results in complete phase transformation to α-(Al_0.32Cr_0.68)₂O₃. In-plane and out-of-plane line scans performed in EDX TEM and θ/2θ XRD patterns did not show any phase separation into α-Cr₂O₃ and Al₂O₃ prior and after the annealing. The apparent activation energy of this process is 380–480 kJ/mol as determined by the Johnson–Mehl–Avrami model.     

Perpendicular magnetic anisotropy in 70 nm CoFe2O4 thin films fabricated on SiO2/Si(1 0 0) by the sol-gel method

Cobalt ferrite CoFe₂O₄ films were fabricated on SiO₂/Si(1 0 0) by the sol-gel method. Films crystallized at/above 600 °C are stoichiometric as expected. With increase of the annealing temperature from 600 °C to 750 °C, the columnar grain size of CoFe₂O₄ film increases from 13 nm to 50 nm, resulting in surface roughness increasing from 0.46 nm to 2.55 nm. Magnetic hysteresis loops in both in-plane and out-of-plane directions, at different annealing temperatures, indicate that the films annealed at 750 °C exhibit obvious perpendicular magnetic anisotropy. Simultaneously, with the annealing temperature increasing from 600 °C to 750 °C, the out of plane coercivity increases from 1 kOe to 2.4 kOe and the corresponding saturation magnetization increases from 200 emu/cm³ to 283 emu/cm³. In addition, all crystallized films exhibit cluster-like structured magnetic domains.     

Development and oxidation resistance of air plasma sprayed Mo-Si-Al coating on an Nbss/Nb5Si3 in situ composite

A Mo-Si-Al coating, which is mainly composed of Mo(Si,Al)₂ and Mo₅(Si,Al)₃, was developed to protect a Nb_ss/Nb₅Si₃ in situ composite by air plasma spraying. After oxidation at 1250 °C, the oxidation curve followed parabolic law and even after oxidation for 100 h, the weight gain of Mo-Si-Al coating was 8.24 mg/cm². The surface of the oxidized samples became flatter and smoother as time increased due to the formation of SiO₂ glass. Moreover, the microstructure of Mo-Si-Al coating changed and a layer structured interdiffusion zone was formed at the substrate-coating interface after oxidation.     

Oxidation of Cr2AlC at 1300 °C in air

High purity, dense Cr₂AlC compounds were synthesized via a powder metallurgical route, and their oxidation behavior was investigated at 1300 °C in air for up to 336 h. A thin external oxide layer formed, which consisted primarily of not Cr₂O₃ but Al₂O₃. Since Al was consumed to produce the Al₂O₃, Al-depletion and Cr-enrichment occurred underneath the Al₂O₃ layer. This led to the formation of a Cr₇C₃ layer containing voids. These grew during oxidation, eventually destroying the Cr₇C₃ layer formed on the unoxidized Cr₂AlC matrix.