Glass-free LTCC microwave dielectric ceramics

The sintering behavior, microstructure and microwave dielectric properties of complex pyrophosphate compounds AMP₂O₇ (A = Ca, Sr; M = Zn, Cu) were investigated in this paper. All compounds could be densified below the temperature of 950 °C without any glass addition, and exhibit low permittivity (_r < 8), high Q × f value and negative temperature coefficient of resonant frequency. The Q × f value was discussed from the point of view of bond strength. The chemical compatibility with silver and copper was also investigated. All compounds seriously react with silver at 700 °C. However SrZnP₂O₇ could be co-fired with copper in reduced atmosphere. The microwave dielectric properties of SrZnP₂O₇ sintered at 950 °C in reducing atmosphere are: _r = 7.06, Q × f = 52781 GHz, τ_f = −70 ppm/°C. In terms of its lower sintering temperature, chemical compatibility with copper and good microwave dielectric properties, SrZnP₂O₇ ceramic is very promising for low temperature co-fired ceramic (LTCC) applications.     

On the Synthesis of In Situ Ni-SiO2 Nanocomposites by Isothermal and Non Isothermal Reduction Technique

In situ Ni-SiO₂ nanocomposites were prepared from silica gels containing NiCl₂ and dextrose by isothermal and non isothermal reduction treatment. Analysis of the isothermal kinetic data indicates that contracting geometry and nucleation and growth type of mechanism remain operative in the 600-750°C and 800-950°C temperature range respectively. However, analysis of non isothermal kinetic data reveals that contracting geometry type of mechanism solely remains operative over the entire temperature range of 600-950°C. Transmission electron microscopic (TEM) studies reveals that the microstructural features of the nanocomposites are sensitive to reduction conditions.     

Kinetics of Carbon Multi-wall Nanotube Synthesis by Catalytic Pyrolysis of Methane

By method of isothermal gravimetry at 600-700°C, CH₄ concentration 32-100% in Ar and 91-100% in H₂ under atmospheric pressure the kinetics of CH₄ pyrolysis under Ni/La₂O₃ catalysts is studied. Estimated apparent activation energy of reaction is 73 kJ/mol for fresh catalyst and 71 kJ/mol for aged one. The reaction order on CH₄ changes from 1.05 at 600°C to 1.3 at 700°C. The influence of H₂ concentration on the reaction rate is more complicated. On the basis of kinetics measurements continuously working laboratory-scale reactor with gas and catalyst counter-flow is constructed and tested.     

Preparation of cobalt oxide nanoparticles and cobalt powders by solvothermal process and their characterization

Co₃O₄ nanoparticles and cobalt (fcc-Co) powders were successfully synthesized by solvothermal process from a single precursor. The reaction of Co(Ac)₂ with sodium dodecylbenzenesulfonate (SDBS) shows evident-dependent temperature effect. At 180 °C, Co(Ac)₂ reacts with SDBS to produce precursor CoCO₃ plate structures, which are assembled by small nanoparticles. At the temperature of 250 °C, the precursor CoCO₃ can be gradually decomposed to form Co₃O₄ nanoparticles with diameter of ca. 70 nm. While, at 250 °C, the reaction of Co(Ac)₂ with SDBS also produce precursor CoCO₃ nanoparticles/plates, but the CoCO₃ nanoparticles/plates would only decompose to give metal Co. In this process, SDBS acts as not only a surfactant but also a reagent. Magnetic measurements reveal that the as-prepared Co₃O₄ nanoparticles exhibit weak ferromagnetic properties and Co powders show ferromagnetic properties. In addition, a possible formation mechanism was elaborately discussed.     

Effect of β-spodumene on the phase development in an alumina/aluminium-titanate system

The effect of β-spodumene additions on the in situ phase formation and abundances in an Al₂O₃–Al₂TiO₅ system in the temperature range 1000–1400 °C has been studied by neutron diffraction and differential thermal analysis. Results show that β-spodumene began to decompose by phase separation and partial melting at 1290 °C, followed by complete melting at 1330 °C. Formation of Al₂TiO₅ was observed to occur at 1310 °C and its abundance increased with temperature. The addition of β-spodumene as a sintering aid did not cause its reaction with alumina or rutile to form additional phases. Addition of β-spodumene in excess of 5 wt% resulted in pronounced vitrification, which partly recrystallised when cooled to room temperature. The temperatures of Al₂TiO₅ formation and melting of β-spodumene are consistent with the results of differential thermal analysis.     

Microwave dielectric properties and microstructures of MgTa2O6 ceramics with CuO addition

The effect of CuO addition on the microstructures and the microwave dielectric properties of MgTa₂O₆ ceramics has been investigated. It is found that low level-doping of CuO (up to 1 wt.%) can significantly improve the density of the specimens and their microwave dielectric properties. Tremendous sintering temperature reduction can be achieved due to the liquid phase effect of CuO addition observed by scanning electronic microscopy (SEM). The sintered samples exhibit excellent microwave dielectric properties, which depend upon the liquid phase and the sintering temperature. With 0.5 wt.% CuO addition, MgTa₂O₆ ceramic can be sintered at 1400 °C and possesses a dielectric constant (_r) of 28, a Q × f value of 58000 GHz and a temperature coefficient of resonant frequency (τ_f) of 18 ppm/°C.     

Destruction of carbon disulfide in aqueous solutions by sonochemical oxidation

Carbon disulfide (CS₂) is toxic to animals and aquatic organisms, and can also decompose to carbonyl sulfide (OCS) and hydrogen sulfide (H₂S) in aqueous environment. The kinetics of the sonochemical degradation of aqueous CS₂ was studied in a batch reactor at 20 kHz and 20 °C, and the effects of process parameters (e.g. concentration, ultrasonic intensity, irradiating gas) investigated. The concentrations of unbuffered CS₂ solutions used were (6.4–7.0)×10⁻⁴, 10.5×10⁻⁴ and (13.2–13.6)×10⁻⁴ M and the intensities were varied from 14 to 50 W. The reaction rate was found to be zero-order and the rate constant for the degradation at 20 °C and 14W in air was 21.1 μM/min using the largest initial concentration range studied. At the same initial concentration range but at 50 W (39.47 W/m²) the degradation rate of CS₂ was 46.7 μM/min, more than two times that at 14 W (11.04 W/m²). The rate of CS₂ sonochemical degradation in the presence of the different gases was in the order of He>air≥N₂O>Ar; the rate with helium was found to be about three times that of argon. The formation of sulfate (SO₄²⁻) as reaction product with air as the irradiating gas was enhanced in the presence of hydrogen peroxide (H₂O₂) and inhibited in the presence of 1-butanol. The sonochemical oxidation of CS₂ may prove to be an efficient and environmentally benign way for the removal of this hazardous pollutant from natural water and wastewater.     

SO2 SCRUBBING BY ULTRAFINE CA(OH)2 AEROSOL

The objective of the present study was to generate submicrometer calcium hydroxide aerosols and to investigate the effectiveness of such aerosols in sulfur capture. The effectiveness of SO₂ removal by Ca(OH)₂ aerosol has been investigated in an isothermal reactor. Ca(OH) ₂ aerosol was generated by a novel fluidizer system in which submicrometer-sized powders were entrained in gases. SO₂ was added to this aerosol to a concentration of 2000 ppm. The aerosol-SO₂ mixture was heated to 550°C-750°C in an isothermal tube reactor. The SO₂ removal efficiency, which varied from 20% to 70%, was determined to be a function of the aerosol concentration, reactor temperature and residence time. The fraction of aerosol reacted was not affected strongly by the aerosol concentration. The reaction kinetics were determined from the experimental data using a simple analytical model in which the rate is first order in both SO₂ and calcium hydroxide aerosol concentrations.     

Formation, characterization and magnetic properties of carbon-encapsulated iron carbide nanoparticles

Fe₃C nanoparticles encapsulated in carbon shell with a size range of 20–50 nm were obtained in large scale by reacting anhydrous FeCl₃, hexamethylenetetramine and metal Na in an autoclave at 650 °C. Magnetization measurements show that the as-obtained materials display superparamagnetic properties at room temperature. A possible formation mechanism of the core–shell nano-structures was discussed.     

Sorption and degradation of bisphenol A by aerobic activated sludge

Laboratory-scale batch experiments were conducted to investigate the sorption and degradation of bisphenol A (BPA) at μg/L range in an aerobic activated sludge system. The sorption isotherms and thermodynamics indicated that the sorption of BPA on sludge was mainly a physical process in which partitioning played a dominating role. The values of sorption coefficient K_oc were between 621 and 736 L/kg in the temperature range of 10–30 °C. Both mixed liquor suspended solid (MLSS) and temperature influenced BPA sorption on sludge. The degradation of BPA by acclimated activated sludge could be described by first-order reaction equation with the first-order degradation rate constant of 0.80 h⁻¹ at 20 °C. The decrease of initial COD concentration and the increase of MLSS concentration and temperature enhanced BPA degradation rate. The removal of BPA in the activated sludge system was characterized by a quick sorption on the activated sludge and subsequent biodegradation.     

Solution-phase synthesis of smaller cuprous oxide nanocubes

Smaller cuprous oxides (Cu₂O) nanocubes were synthesized by solution-phase method at 160 °C, using ethylene glycol reducing Cu(NO₃)₂·3H₂O with poly(vinylypyrrolidone) (pvp) as capping agent. The Cu₂O nanocubes were characterized by field-emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), selected area electron diffraction (SAED) and X-ray powder diffraction (XRD). SEM showed that most of Cu₂O nanocubes were uniform and monodisperse, with the average edge length about 130 nm. The TEM results were consistent with the SEM results. Selected area electron diffraction (SAED) suggested that as-prepared Cu₂O nanocubes were single crystalline. The geometric shape and size of Cu₂O nanoparticles were greatly affected by the presence of PVP and its molar ratio (in repeating unit) relative to copper nitrate, temperature and the concentration of Cu(NO₃)₂·3H₂O. The mechanism of Cu₂O nanocubes formation was also discussed.     

Removal of NO from flue gas by aqueous chlorine-dioxide scrubbing solution in a lab-scale bubbling reactor

The present study attempts to clean up nitric oxide from the simulated flue gas using aqueous chlorine-dioxide solution in the bubbling reactor. Chlorine-dioxide is generated by chloride–chlorate process. Experiments are carried out to examine the effect of various operating variables like input NO concentration, presence of SO₂, pH of the solution and NaCl feeding rate on the NO_x removal efficiency at 45 °C. Complete oxidation of nitric oxide into nitrogen dioxide occurred on passing sufficient ClO₂ gas into the scrubbing solution. NO is finally converted into nitrate and ClO₂ is reduced into chloride ions. A plausible reaction mechanism concerning NO_x removal by ClO₂ is suggested. DeNO_x efficiency increased slightly with the increasing input NO concentration. The presence of SO₂ improved the NO₂ absorption but pH of solution showed marginal effect on NO₂ absorption. NO_x removal mechanism changed when medium of solution changed from acidic to alkaline. A constant NO_x removal efficiency of about 60% has been achieved in the wide pH range of 3–11 under optimized conditions.     

Piezoelectric and dielectric properties of PZT–PZN–PMS ceramics prepared by molten salt synthesis method

Piezoelectric powders and ceramics with the composition of Pb_0.95Sr_0.05(Zr_0.52Ti_0.48)O₃–Pb(Zn_1/3Nb_2/3)O₃–Pb(Mn_1/3Sb_2/3)O₃ (PZT–PZN–PMS) were prepared by molten salt synthesis (MSS) and conventional mixed-oxide (CMO) methods, respectively. The influence of synthesis process on the properties of powders and ceramics were investigated in detail. The results show that the MSS method significantly improved the sinterability of PZT–PZN–PMS ceramics, resulting in an improvement of dielectric and piezoelectric properties compared to the CMO method. The optimum values of MSS samples are as follows: _r = 1773; tan δ = 0.0040; T_c = 280 °C; d₃₃ = 455 pC/N; k_p = 0.70; Q_m = 888; E_c = 10.3 kV/cm; and P_r = 28.2 μC/cm², at calcination of 800 °C and sintering of 1120 °C temperature.     

Characterization of the thorium phosphate-hydrogenphosphate hydrate (TPHPH) and study of its transformation into the thorium phosphate-diphosphate (β-TPD)

The preparation of thorium phosphate-diphosphate (Th₄(PO₄)₄P₂O₇, TPD) was developed through the precipitation of thorium phosphate-hydrogenphosphate hydrate (Th₂(PO₄)₂(HPO₄)·H₂O, TPHPH) at 150–160 °C in closed PTFE container or in autoclaves. From EPMA analyses and SEM observations, the initial precipitate was single phase and multilayered. The behaviour of TPHPH (orthorhombic system with a = 21.368(2) Å, b = 6.695(1) Å and c = 7.023(1) Å) was followed when heating up to 1250 °C. It was first dehydrated leading to the anhydrous thorium phosphate-hydrogenphosphate (TPHP, orthorhombic system with a = 21.229(2) Å, b = 6.661(1) Å and c = 7.031(1) Å at 220 °C) after heating between 180 and 200 °C. This one turned progressively into the new low-temperature variety of TPD (called -TPD, orthorhombic system with a = 21.206(2) Å, b = 6.657(1) Å and c = 7.057(1) Å at 300 °C) correlatively to the condensation of hydrogenphosphate groups into diphosphate entities. These three phases (TPHPH, TPHP and -TPD) exhibit closely related 2D layered structures, therefore different from the 3D structure of the thorium phosphate-diphosphate (high-temperature variety). This latter compound, now called β-TPD, was obtained by heating -TPD above 950 °C. All the techniques involved in this study (XRD, Raman and IR spectroscopy, ¹H and ³¹P NMR) confirmed the successive chemical reactions proposed.     

Tribological behavior of PTFE nanocomposite films reinforced with carbon nanoparticles

Carbon-based nanoparticles synthesized by heat treatment of nanodiamond in the temperature range of 1000–1900 °C were added to PTFE film to investigate the structural effect of the carbon particles on the tribological properties of PTFE composite film. Carbon-based nanoparticles were prepared by milling with micron sized beads in chemically treated water before their addition to PTFE film. The wear and frictional properties of PTFE nanocomposite film were measured by the ball on plate type wear test. The wear resistance of PTFE film was found to be enhanced by the addition of 2 wt% of carbon nanoparticles. The wear coefficient of PTFE film was decreased from 16.2 to 3.5 × 10⁻⁶ mm³/N m by the addition of carbon-based nanoparticles heat-treated at 1000 °C. Increasing the heating temperature of the nanodiamonds caused the extent of aggregation and particle size to increase. The wear resistance of PTFE nanocomposite film was enhanced by the addition of nanodiamonds heat-treated at 1000 °C, but decreased when the heat treatment temperature of carbon nanoparticles was further increased. Tribological behavior of PTFE nanocomposite films depending on the types of carbon nanoparticles were explained based on the structural, physical and chemical modification of carbon nanoparticles.     

Application of response surface method for predicting electroless nickel plating

Electroless nickel plating process has been studied considering pure copper (99.99%) as a substrate material. Deposition per unit area has been considered as a response variable and individual as well as combined effects of process parameters on deposited mass have been studied. Regression analysis and Student’s t test have been used to identify the significant influencing process parameters. It has been observed that reducing agent (NaBH₄), source of metal (NiCl₂ · 6H₂O) and temperature significantly affect the deposition. The interactions among various process parameters have also been observed to be significant. Mathematical modeling has been carried out by a second-order response surface model with central composite design (CCD) to take into account the effect of curvature in the predicted response. Equations for response surfaces have been determined for various deposition times using MATLAB software package. Most of the response surfaces show that deposition thickness increases with increased values of process parameters within the adopted range but with different rates. The test for reliability for predicting response surface equations shows that these equations give an excellent fitting to the observed values.     

Growth kinetics of Mo3Si layer in the Mo5Si3/Mo diffusion couple

The diffusion processes and growth kinetics of the Mo₃Si silicide layer occurring at annealing the Mo₅Si₃/Mo diffusion couple between 1180 and 1800 °C were studied by electrothermography. The experimental results are supplemented with calculations on the behaviour of the initial Mo₅Si₃/Mo diffusion couple on the basis of the reaction diffusion model describing the transformation of the Mo₅Si₃ layer into a Mo₃Si one. The values of the parabolic growth constant for Mo₃Si layer were determined and the silicon diffusion coefficient in the Mo₃Si phase was calculated: D = 0.165 exp[(− 247 ± 10) / RT], cm²/s, where the activation energy is expressed in terms of kJ/mol.     

Low temperature metal oxide film deposition and reaction kinetics in supercritical carbon dioxide

An effective method is developed for low temperature metal oxide deposition through thermal decomposition of metal diketonates in supercritical carbon dioxide (scCO₂) solvent. The rates of Al(acac)₃ (Aluminum acetyl acetonate) and Ga(acac)₃ (Gallium acetyl acetonate) thermal decomposition in scCO₂ to form conformal Al₂O₃ and Ga₂O₃ thin films on planar surfaces were investigated. The thermal decomposition reaction of Al(acac)₃ and Ga(acac)₃ was found to be initialized at  150 °C and 160 °C respectively in scCO₂ solvent, compared to  250 °C and 360 °C in analogous vacuum-based processes. By measuring the temperature dependence of the growth rates of metal oxide thin films, the apparent activation energy for the thermal decomposition of Al(acac)₃ in scCO₂ is found to be 68 ± 6 kJ/mol, in comparison with 80–100 kJ/mol observed for the corresponding vacuum-based thermal decomposition reaction. The enhanced thermal decomposition rate in scCO₂ is ascribed to the high density solvent which effectively reduces the energy of the polar transition states in the reaction pathway. Preliminary results of thin film deposition of other metal oxides including ZrO_x, FeO_x, Co₂O₃, Cr₂O₃, HfO_x from thermal decomposition of metal diketonates or fluorinated diketonates in scCO₂ are also presented.     

A simple and an effective method for the fabrication of densified glass-ceramics of low temperature co-fired ceramics

This study reports a new, simple and effective pre-calcined method for fabrication BaO–TiO₂–B₂O₃–SiO₂ low temperature co-fired ceramics (LTCC) at a sintering temperature below 900 °C, and with dielectric losses (tan δ) lower than 2 × 10⁻³. The research results have shown that the addition of 2–5 wt% Al₂O₃ could easily eliminate the porosity of the glass-ceramics because of the excellent wetting behavior between alumina and the BaO–B₂O₃–SiO₂ glass liquid phase in the low temperature co-fired ceramic system.     

Consolidation behavior of L12 phase (Al + 12.5 at.% Cu)3Zr powder with nanocrystalline structure during CIP and subsequent sintering

The mechanically alloyed (Al + 12.5 at.% Cu)₃Zr powders were consolidated by cold isostatic pressing (CIP) and subsequent sintering. Effects of CIP pressure and sintering temperature on the stability of metastable L1₂ phase and nanocrystalline structure were investigated. Before sintering, the powders were CIPed at 138, 207, 276, and 414 MPa. The relative densities of the CIP compacts were not greatly affected by the CIP pressure. However, the L1₂ phase of the specimen CIPed at pressures greater than 276 MPa was partially transformed into D0₂₃. The optimum consolidation conditions for maintaining L1₂ phase and nanocrystalline microstructure were determined to be CIP at 207 MPa and sintering at 800 °C for 1 h for which the grain size was 34.2 nm and the relative density was 93.8%. Full density specimens could be prepared by sintering above 900 °C, however, these specimens consisted of L1₂ and D0₂₃ phases. The grain sizes of all the specimens were confirmed by TEM and XRD, and were found to be less than 40 nm. This is one of the smallest grain sizes ever reported in trialuminide intermetallic compounds.