Mg-substituted ZnNb2O6-TiO2 composite ceramics for RF/microwaves ceramic capacitors

Microstructure and microwave dielectric properties of Mg-substituted ZnNb₂O₆-TiO₂ microwave ceramics were investigated. Mg acted as a grain refining reagent and columbite phase stabilization reagent. With an increasing Mg content, the amount of ixiolite (Zn, Mg) TiNb₂O₈ decreased, and the amount of (Zn_0.9Mg_0.1)_0.17Nb_0.33Ti_0.5O₂ and columbite increased. ZnO-Nb₂O₅-1.75TiO₂-5 mol.%MgO exhibited excellent dielectric properties (at 950 °C): ?_r = 35.6, Q × f = 16,000 GHz (at 5.6 GHz) and τ_f = −10 ppm/°C. The material was applied successfully to make RF/microwaves ceramic capacitor, whose self-resonance frequency was 19 GHz at low capacitance of 0.13 pF.     

Mechanochemical synthesis of Al2O3-TiB2 nanocomposite powder from Al-TiO2-H3BO3 mixture

Alumina-titanium diboride nanocomposite (Al₂O₃-TiB₂) was produced using mixtures of titanium dioxide, acid boric and pure aluminum as raw materials via mechanochemical process. The phase transformation and structural characterization during mechanochemical process were utilized by X-ray diffractometry (XRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM), and thermogravimetric analyses (TG-DTA) techniques. A thermodynamic appraisal showed that the reaction between TiO₂, B₂O₃ and Al is highly exothermic and should be self-sustaining. XRD analyses exhibited that the Al₂O₃-TiB₂ nanocomposite was formed after 1.5 h milling time. The results indicate that increasing milling time up to 40 h had no significant effect other than refining the crystallite size.     

Combustion synthesis of Ti3Si1−xAlxC2 solid solutions from TiC-, SiC-, and Al4C3-containing powder compacts

Preparation of the Ti₃Si_1−xAl_xC₂ solid solution with x = 0.2-0.8 was investigated by self-propagating high-temperature synthesis (SHS) using TiC-, SiC-, and Al₄C₃-containing powder compacts. Due to the variation of reaction exothermicity with sample stoichiometry, the combustion temperature and reaction front velocity decreased with increasing Al content of Ti₃Si_1−xAl_xC₂ for the TiC- and Al₄C₃-added samples, but increased for the samples with SiC. In contrast to the formation of Ti₃(Si,Al)C₂ as the dominant phase for the TiC- and SiC-added samples, TiC was identified as the major constituent in the final products of samples adopting Al₄C₃. In addition, the evolution of Ti₃(Si,Al)C₂ was improved by increasing the Al content of the TiC- and SiC-added powder compacts, but deteriorated considerably upon the increase of Al₄C₃ in the Al₄C₃-containing sample.     

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.     

Sol-gel synthesis of Bi3.25La0.75Ti3O12 nanotubes

Ferroelectric Bi_3.25La_0.75Ti₃O₁₂ (BLT) nanotubes were synthesized by sol-gel technique using nanochannel porous anodic aluminum oxide (AAO) templates, and were characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM) and high resolution transmission electron microscopy (HRTEM). BLT nanotubes with diameter of around 240 nm and the wall thickness of about 25 nm exhibited a single orthorhombic perovskite structure and highly preferential crystal growth along the [1 1 7] orientation, which have smooth wall morphologies and well-defined diameters corresponding to the diameter of the applied template. The formation mechanism of BLT nanotubes was discussed.     

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.     

Oxidation resistance of TiAl3-Al composite coating on orthorhombic Ti2AlNb based alloy

The TiAl₃-Al composite coating on orthorhombic Ti₂AlNb based alloy was prepared by cold spray. Oxidation in air at 950 °C indicated that the bare alloy exhibited poor oxidation resistance due to the formation of TiO₂/AlNbO₄ mixture and intended to scale off at the TiO₂ rich zone. A nitride layer about 2 µm was formed under the oxide layer. The oxygen invaded deeply into the alloy and caused severe microhardness enhancement in the near surface region. The TiAl₃-Al composite coating exhibited parabolic oxidation kinetics and showed no sign of degradation after oxidized up to 1098 h at 950 °C in air under quasi-isothermal condition. No scaling of the coating was observed after oxidized at 950 °C up to the tested 150 cycles. The major oxide in the oxidized coating was Al₂O₃. The AlTi₂N, TiAl and small amount of TiO₂ were also observed in the oxidized coating. The EPMA and microhardness tests showed that inward oxygen diffusion was prevented by the interlayer, which was formed between the composite coating and the substrate during heat-treatment. Microstructure analyses demonstrated that the interlayer play a major role in protecting the substrate alloy from high temperature oxidation and interstitial embrittlement.     

Improving the Na2SO4-induced corrosion resistance of Ti3AlC2 by pre-oxidation in air

Ti₃AlC₂ suffers severe Na₂SO₄-induced corrosion attacks at temperatures higher than 800 °C in air. A convenient and efficient pre-oxidation method is proposed to enhance the corrosion resistance of Ti₃AlC₂. The corrosion weight-changes of the pre-oxidized samples were decreased by about four orders of magnitude compared with those of the untreated specimens. The mechanism on improvement of corrosion resistance was investigated by means of thermogravimetric analysis, X-ray diffraction and scanning electron microscopy/energy-dispersive spectroscopy. A continuous and adherent α-Al₂O₃ scale was prepared by high-temperature pre-oxidation treatment in air. The preformed dense Al₂O₃ scale has good compatibility with the Ti₃AlC₂ substrate, and consequently, can act as an efficient barrier against corrosion. Long-time corrosion tests demonstrate that the Al₂O₃ scale conserves after corrosion attack and is capable of long-term stability.     

Dependence of lattice distortion of monoclinic phase on film thickness in Pb(Zr0.58Ti0.42)O3 thin films

In this paper, the chosen composition of PZT film falls in rhombohedral phase region and the dependence of lattice distortion on film thickness in sol-gel derived Pb(Zr_0.58Ti_0.42)O₃ thin films was systematically investigated. The results confirm that the Pb(Zr_0.58Ti_0.42)O₃ films have monoclinic phase even though the composition falls in the rhombohedral phase region. The mixed textures of (1 0 0) and (1 1 1) occur in the PZT films. In the case of mixed textures, a method using ψ-scan XRD to characterize the phase type of Pb(Zr_0.58Ti_0.42)O₃ film is presented. It is found that the phase type of (1 0 0)-oriented grains is M_A phase, and that of (1 1 1)-oriented grains is M_B phase. Moreover, the lattice constants of both M_A and M_B phases are sensitive to the film thickness. The lattice distortion of monoclinic phase becomes smaller as film thickness increases.     

The corrosion behavior of plasma sprayed Fe2Al5 coating in molten Zn

Aluminum coating was plasma sprayed on Fe-0.14-0.22 wt.% C steel substrate, and heat diffusion treatment at 923 °C for 4 h was preformed to the aluminum coating to form Fe₂Al₅ inter-metallic compound coating. The corrosion mechanism of the Fe₂Al₅ coating in molten zinc was investigated. SEM and EDS analysis results show that the corrosion process of the Fe₂Al₅ layer in molten zinc is as follows: Fe₂Al₅ → Fe₂Al₅Zn_x (η) → η + L(liquid phase) → L + η + δ(FeZn₇) → L + δ → L. The η phase and the eutectic structure (η + δ) prevent the diffusion of zinc atoms efficiently. Therefore the Fe₂Al₅ coating delays the reaction between the substrate and molten zinc, promoting the corrosion resistance of the substrate.     

Thermal stability of bulk Zr2Al4C5 ceramic at elevated temperatures

Thermal expansion analysis is applied to the study of phase segregation of Zr₂Al₄C₅ at elevated temperatures (20-2000 °C) under flowing argon. Such information would be useful for the detection of phase decomposition temperature and thermal stability of materials. The detected phase-decomposition temperature of Zr₂Al₄C₅ is approximately 1900 °C. The presented thermal expansion analysis results are in good agreement with the X-ray diffraction (XRD) and SEM results. The results indicate that Zr₂Al₄C₅ is susceptible to decomposition through sublimation of high vapor pressure of Al and weaker covalent bonds between ZrC slabs and Al₄C₃ layers. Thus, minimal amounts of Al, Zr₂Al₃C₅, Al₄C₃ and ZrC form on the surface layer. Zr₂Al₃C₅ further decomposes to ZrC_1 − x and Al₄C₃ at 2000 °C. However, the amount of decomposing phase slowly increases, and the structural shape of bulk Zr₂Al₄C₅ ceramic is always kept stable during heat treatment.     

Synthesis, structural and magnetic characterization of nanocrystalline nickel ferrite—NiFe2O4 obtained by reactive milling

Nanocrystalline nickel ferrite (NiFe₂O₄) has been synthesized from a stoichiometric mixture of oxides NiO and α-Fe₂O₃ in a high energy planetary mill. An annealing at 350 °C, after milling, was used to improve the solid state reaction. The obtained powders were investigated by X-ray diffraction, magnetic measurements, scanning electron microscopy, X-ray microanalysis and differential scanning calorimetry. The particles size distribution was analyzed using a laser particle size analyser. The nickel ferrite begins to form after 4 h of milling and continuously form up to 16 h of milling. The obtained nickel ferrite has many inhomogeneities and a distorted spinel structure. The mean crystallites size at the final time of milling is 9 ± 2 nm and the lattice parameter increases with increase the milling time. DSC measurements revealed a large exothermic peak associated with cations reordering in the crystalline structure. The magnetization of the obtained powder depends on the milling time and annealing. After the complete reaction between the starting oxides the milling reduces the magnetization of the samples. The magnetization increases after annealing, due to the reorganization of the cations into the spinel structure.     

Influence of pre-oxidation on the hot corrosion of Ti3SiC2 in the mixture of Na2SO4-NaCl melts

Polycrystalline Ti₃SiC₂ suffered from serious hot corrosion attack in the mixture of 75wt.%Na₂SO₄ + 25wt.%NaCl melts at 850 °C. In order to improve the hot corrosion resistance of this material, pre-oxidation treatment was conducted at 1200 °C in air for 2 h. A duplex oxide scale with an outer layer of TiO₂ and an inner layer of a mixture of TiO₂ and SiO₂ was formed during the pre-oxidation. Because the outer oxide layer of the pre-oxidation treated specimens could inhibit hot corrosion process, they exhibited good hot corrosion resistance in the mixture of 75wt.%Na₂SO₄ + 25wt.%NaCl melts at 850 °C for 50 h. However, during the hot corrosion the outer layer of TiO₂ would degrade gradually. Once the outer layer damaged, the hot corrosion rate increased sharply, the corrosion behavior was similar to Ti₃SiC₂ corroded under the same conditions. The microstructure and phase compositions of the hot corrosion samples were investigated by SEM/EDS and XRD.     

High dielectric constant of (Ba0.96Ca0.04)(Ti0.85Zr0.15)O3 multilayer ceramic capacitors with Cu doped Ni electrodes

A nickel paste with Cu dopant was used as the internal electrodes in multi-layer ceramic capacitors (MLCCs) using barium titanate (Ba_0.96Ca_0.04)(Ti_0.85Zr_0.15)O₃ ceramic (BCTZ) with copper endtermination. The sintering behaviors of the MLCC and the interfacial structure between the Ni/Cu electrodes and the BCTZ dielectrics have been investigated. The thermal shrinkage and sheet resistance of the Ni/Cu alloys sintered at 1220 °C for 2 h in a reducing atmosphere were measured using thermal analysis techniques (TMA) and four-point probe equipment. The composition distributions, microstructures and line defects were examined using microstructural analysis techniques (SEM/HRTEM) coupled with energy-dispersive spectroscopy (EDS). The Cu alloyed with Ni significantly improves the continuity of the electrode in the MLCC; this is due to there being no mutual trigger reaction between Ni and BCTZ dielectrics. In terms of the electrical properties, the results showed that Ni paste with Cu dopant improves the dielectric constant of the MLCC, but the dielectric loss (tan δ) is a slightly when higher compared to standard MLCC.     

Effects of oxygen content and heating rate on phase transition behavior in Bi2(V0.95Ti0.05)O5.475−x

The phase transition behavior of oxide-ion conductor Bi₂(V_0.95Ti_0.05)O_5.475−x, which has various thermal histories and sample forms, has been studied by means of differential scanning calorimetry. Thermogravimetric analysis revealed that the oxygen content per compositional formula varied with the applied thermal treatment, although no significant structural difference was observed by X-ray diffraction (XRD) analysis. The phase transition behavior from α_f to β_f and from β_f to γ_f, observed at a heating rate of 10 K min⁻¹, are markedly affected by the sample preparation. For example, the endothermic peak of the transition from α_f to β_f appeared at around 400 °C for quenched powder and at around 320 °C for powder cooled at 0.5 K min⁻¹. The trend of the transition temperatures can be qualitatively explained in terms of oxygen content, i.e., Bi₂(V_0.95Ti_0.05)O_5.475−x with less oxygen content exhibits the transition from α_f to β_f at a higher temperature and the transition from β_f to γ_f at a lower temperature. We confirmed the two types of transition behavior from α_f to β_f depending on heating rate of DSC and high-temperature X-ray diffraction (HT-XRD) analysis. At rapid heating rates of 10 and 40 K min⁻¹, α_f transformed to β_f directly. Meanwhile, at a slow heating rate of 2 K min⁻¹, the β_f precipitated from α_f because slow heating allowed the diffusion of Ti and oxygen vacancies induced by the aliovalent doping. This suggests that the small differences of atomic arrangement also affect the phase transition behavior because additional elements have preferable crystallographic sites in α_f and β_f.     

Al2O3-nanodiamond composite coatings with high durability and hydrophobicity prepared by aerosol deposition

We attempted the room-temperature fabrication of Al₂O₃-based nanodiamond (ND) composite coating films on glass substrates by an aerosol deposition (AD) process to improve the anti-scratch and anti-smudge properties of the films. Submicron Al₂O₃ powder capable of fabricating transparent hard coating films was used as a base material for the starting powders, and ND treated by 1H,1H,2H,2H-perfluorooctyltriethoxysilane (PFOTES) was added to the Al₂O₃ to increase the hydrophobicity and anti-wear properties. The ND powder treated by PFOTES was mixed with the Al₂O₃ powder by ball milling to ratios of 0.01 wt.%, 0.03 wt.%, and 0.05 wt.% ND. The water contact angle (CA) of the Al₂O₃-ND composite coating films was increased as the ND ratio increased, and the maximum water CA among all the films was 110°. In contrast to the water CA, the Al₂O₃-ND composite coating films showed low transmittance values of below 50% at a wavelength of 550 nm due to the strong agglomeration of ND. To prevent the agglomeration of ND, the starting powders were mixed by attrition milling. As a result, Al₂O₃-ND composite coating films were produced that showed high transmittance values of close to 80%, even though the starting powder included 1.0 wt.% ND. In addition, the Al₂O₃-ND composite coating films had a high water CA of 109° and superior anti-wear properties compared to those of glass substrates.     

Improved dielectric and non-ohmic properties of Ca2Cu2Ti4O12 ceramics prepared by a polymer pyrolysis method

Non-ohmic and dielectric properties of Ca₂Cu₂Ti₄O₁₂ (CaCu₃Ti₄O₁₂/CaTiO₃ composite) ceramics prepared by a polymer pyrolysis method (PP-ceramic samples) are investigated. The PP-ceramics show a highly dense structure and improved non-ohmic and dielectric properties compared to the ceramics obtained by a solid state reaction method (SSR-ceramic samples). ?′ (tan δ) of the PP-ceramic samples is found to be higher (lower) than that of the SSR-ceramic samples. Interestingly, the PP-ceramic sintered at 1050 °C for 10 h exhibits the high ?′ of 2530 with weak frequency dependence below 1 MHz, the low tan δ less than 0.05 in the frequency range of 160 Hz-177 kHz, and the little temperature coefficient, i.e., |Δ?′| ≤ 15 % in the temperature range from −55 to 85 °C. These results indicate that the CaCu₃Ti₄O₁₂/CaTiO₃ composite system prepared by PP method is a promising high-?′ material for practical capacitor application.     

Phase, structural, and magnetocaloric properties of high temperature annealed LaFe11.6Si1.4BX

The phase relation, microstructural, hysteresis, Curie temperature, and magnetocaloric effects of LaFe_11.6Si_1.4B_x (x = 0.1, 0.2, 0.3, 0.4, and 0.5) prepared by arc-melting and then annealed at 1373 K (1.5 h) + 1523 K (5 h) were investigated. It was found that the main phase is NaZn₁₃-type phase, the impurity phases include α-Fe, Fe₂B, and small amount of La₅Si₃. The boron atom can dissolve into the crystal lattice of LaFe_11.6Si_1.4B_x to form interstitial solid solution, but the content of solid solution is not up to x = 0.5. For LaFe_11.6Si_1.4B_x (x = 0.1, 0.3, and 0.5) compounds, the Curie temperature T_C increases from 190.6 to 198.3 K with the increasing of B content from x = 0.1 to 0.5. The first order magnetic transition behavior becomes weaker and magnetic entropy change ΔS_M (T, H) drops with the increasing of B content, respectively. However, ΔS_M (T, H) still remains a large value, 11.18 J/kg K, when x reaches to 0.5 at 0-2 T. An attractive feature is that both thermal and magnetic hysteresis can be reduced remarkably by introducing B. The maximum magnetic hysteresis loss near T_C drops from 22.52 to 4.95 J/kg when the content of B increases from x = 0.1 to 0.5.     

Mechanochemical synthesis of nanocrystalline ZnWO4 at room temperature

Single nanocrystalline ZnWO₄ powders were successfully synthesized by ball milling at room temperature. A stoichiometric mixture of ZnO and WO₃ in a 1:1 molar ratio was subjected to intense mechanical treatment in air using a planetary ball mill (Fritsch - Premium line - Pulversette No. 7) for a period varying from 5 to 300 min. The influence of the four different milling conditions was investigated on the formation of ZnWO₄. The products obtained were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), Brunauer-Emmer-Teller (BET) surface area, infrared (IR) spectroscopy and X-ray photoelectron spectroscopy (XPS). The synthesis of ZnWO₄ powder started after 5 min milling time and finished after 30 min milling time at a higher speed (1000 rpm). The mechanical treatment up to 300 min did not lead to phase and structure change of ZnWO₄. The product obtained contained nanoparticles with a size of about 50 nm. The photocatalytic activity of the ZnWO₄ powders obtained was investigated by degradation of a model aqueous solution of Malachite Green (MG) upon UV-light irradiation.     

A mild biomolecule-assisted route for preparation of flower-like AgBiS2 crystals

A mild biomolecule-assisted route for preparation of flower-like AgBiS₂ crystals was developed via reactions among AgNO₃, BiCl₃, and l-cystine in N,N-dimethylformamide (DMF) at 200 °C for 12 h. l-cystine was used as both the sulfide source and complexing agent. The as-synthesized AgBiS₂ crystals were characterized by XRD, EDS, XPS, PL, FESEM, TEM, HRTEM, and SAED. Results showed that the synthesized AgBiS₂ crystals had stoichiometric composition, good crystallinity, and flower-like morphology. A possible formation mechanism for flower-like AgBiS₂ crystals was also discussed based on the experiment.