Synthesis,Characterization, and Microstructure of Hafnium Boride‐Based Composite Ceramics Via Preceramic Method

The ceramic precursor for HfB₂/HfC/SiC/C was prepared via solution‐based processing of polyhafnoxanesal, linear phenolic resin, boric acid and poly[(methylsilylene)acetylene)]. The obtained precursor could be cured at 250°C and subsequently heat treated at relative lower temperature (1500°C) to form HfB₂/HfC/SiC/C ceramic powders. The ceramic powders were characterized by element analysis, thermal gravimetric analysis, X‐ray diffraction, Raman spectroscopy, and Scanning electron microscopy. The results indicated that the ceramic powders with particle size of 200~500 nm were consisted of pure phase HfB₂, HfC, and SiC along with free carbon as fourth phase with low crystallinity.     

Magnetoelectric Response in (1−x)PbZr0.65Ti0.35O3–xBaFe12O19 Multiferroic Ceramic Composites

The magnetoelectric (ME) properties of PbZr_0.65Ti_0.35O₃–BaFe₁₂O₁₉ (PZT–BaM) multiferroic ceramic composites have been investigated in this work. These materials, containing both the ferroelectric PZT and ferrimagnetic BaM phases, were prepared from the conventional solid‐state reaction method, and their main (micro)structural characteristics are provided. The ME measurements were performed over wide frequency and temperature ranges, and the influence of the BaM content was appraised. An enhanced ME coefficient (α) was obtained for the applied magnetic field of 0.8 kOe, at 97 kHz. In addition, the results reveal a high thermal stability of α in the whole analyzed temperature range, showing that the studied PZT‐based ceramic composites have great potential for practical applications.     

Influences of Liquid‐Phase Sintering on Structure,Grain Growth,and Dielectric Behavior of PbZr0.52Ti0.48O3 Ceramics

In this work, to formulate piezoceramic systems such as PbZr_0.52Ti_0.48O₃ (PZT) for low‐temperature co‐fired ceramic (LTCC)‐based devices, liquid‐phase sintering approach is demonstrated. ZnO–B₂O₃ (ZB) binary glass system is used as sintering aid. X‐ray diffraction (XRD) study confirms the formation of morphotropic phase boundary (MPB; tetragonal + rhombohedral) in PZT prepared by hydrothermal route. ZB is found to induce change in tetragonal/rhombohedral ratio in MPB of PZT. 1%ZB in PZT is found to raise the tetragonality from 71% to 92% in MPB region of PZT. ZB addition in PZT has reduced the sintering temperature from 1250 to 825°C for relative density about 91% with sustaining MPB phase. 1% ZB content is optimal percentage to enhance sinterability and relative density. Uniform dispersion of glass in PZT matrix is confirmed by SEM images. ZB content in PZT is found to controlling grain growth during sintering. Highest dielectric constant and lowest dielectric loss with low sintering temperature (825°C) of 1%ZB among all glass added in PZT exhibit technical suitability of 1%ZB + PZT to use as LTCC‐based energy storage devices.     

Effect of flake size on thermal properties of graphene oxide/poly(methyl methacrylate) composites prepared via in situ polymerization

The effect of graphene oxide (GO) flake size on thermal properties of GO/poly(methyl methacrylate) (GO/PMMA) composites prepared via in situ polymerization was investigated. Two styles of GO sheets were synthesized from different sizes of graphite powders by modified Hummers' method and GO/PMMA composites with GO of different sizes were prepared via in situ polymerization. Transmission electron microscopy verified that GO sheets produced from large graphite powders was obviously larger than that from small graphite powders. The similar number of layers and disorder degree of two types of GO sheets were proved by X‐ray diffraction and Raman, respectively. X‐ray diffraction and scanning electron microscopy results of GO/composites proved the homogenous dispersion of both two types of GO sheets in polymer matrix. Dynamic mechanical analysis and thermogravimetric analysis results showed that large GO sheets exhibit better improvement than small GO sheets in thermal properties of the composites. Compared with neat PMMA, the glass transition temperature and decomposition temperature of the composites with large GO sheets (0.20 wt %) were increased by 15.9 and 25.9 °C, respectively. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46290.     

Intergranular Stress Induced Phase Transition in CaZrO3 Modified KNN‐Based Lead‐Free Piezoelectrics

The phase transition temperatures of CaZrO₃‐doped (Na_0.49K_0.49Li_0.02)(Nb_0.8Ta_0.2)O₃ lead‐free piezoelectrics (LKNNT‐CZ5) have been studied with X‐ray diffraction and Raman scattering. It is found that LKNNT‐CZ5 ceramics and powders with the same crystallite size (~2–5 μm) exhibit distinctly different phase transition behaviors versus temperature. The ceramic bulk changes its orthorhombic phase to tetragonal structure abruptly after being pulverized to powders at room temperature(RT), and follows a phase transition sequence with increasing temperature: orthorhombic (RT–65°C), orthorhombic and tetragonal (65°C–105°C), and tetragonal phase (105°C to ~220°C). Contrastively, the powders hold a tetragonal structure without any phase transition within the whole temperature region (RT–220°C). These differences might be induced by the existing internal stress or residual strain, which could be released during the grinding process.     

Dense nanocrystalline UO2+x fuel pellets synthesized by high pressure spark plasma sintering

Nanocrystalline UO_2+x powders are prepared by high‐energy ball milling and subsequently consolidated into dense fuel pellets (>95% of theoretical density) under high pressure (750 MPa) by spark plasma sintering at low sintering temperatures (600°C‐700°C). The grain size achieved in the dense nano‐ceramic pellets varies within 60‐160 nm as controlled by sintering temperature and duration. The sintered fuel pellets are single phase UO_2+x with hyper‐stoichiometric compositions as derived by X‐ray diffraction, and micro‐Raman measurements indicate that random oxygen interstitials and Willis clusters dominate the single phase nano‐sized oxide pellets of UO_2.03 and UO_2.11, respectively. The thermal conductivities of the densified nano‐sized oxide fuel pellets are measured by laser flash, and the fuel stoichiometry displays a dominant effect in controlling thermal transport properties. A reduction in thermal conductivity is also observed for the dense nano‐sized pellets as compared with micron‐sized counterparts reported in the literature. The correlation among the SPS sintering parameters—microstructure control—properties is established, and the nano‐sized UO_2+x pellets with controlled microstructure can serve as the model systems for fundamental understandings of fuel behaviors and obtaining critical experimental data for multi‐physics MARMOT model validation.     

Nanoscaled Interface Between Microgold Particles and Biphase Glass‐Ceramic Matrix

This article presents a detailed study on the nanoscaled interface between microelongated gold particles (GP) and biphase leucite/feldspar glass‐ceramic matrix. The glass‐ceramic composite with a nonuniform GP distribution was processed through hot‐pressing under vacuum using a commercial dental ceramic furnace for glass‐ceramic dental crown manufacturing. Heat treatments at 900°C, 1100°C, and 1300°C were conducted, and microstructural features along the interface were used to verify the chemical reactions between GP and glass‐ceramic matrix. It was observed that the amorphous glass‐ceramic matrix had nanoscaled biphase structures, and the distributed nanoscaled amorphous leucite phase was attracted to GP during hot‐pressing, and was more reactive with GP than the feldspar phase. The thickness of the interfacial phase formed through chemical reactions between GP and glass‐ceramic matrix is around 30 nm. The chemically bonded interface has contributed significantly toward the substantial improvements in both strength and toughness of the GP‐reinforced glass‐ceramic matrix composite. Characterization techniques, including X‐ray diffraction and field‐emission scanning electron Microscopy, incorporating X‐ray microanalysis using energy dispersive spectrometry, have been employed in this study.     

Photocatalytic degradation of dyestuff wastewater under visible light irradiation using micron‐sized mixed crystal TiO2 powders

A phase transformation of micron‐sized TiO₂ powder from anatase to rutile was attempted by heat‐treatment in order to generate a new mixed crystal TiO₂ with high associated photocatalytic activity. Heat‐treated micron‐sized TiO₂ powders at different transition stages were characterized by X‐ray diffraction analysis (XRD), Fourier transform infrared spectroscopy (FT‐IR) and transmission electron microscopy (TEM) methods. The tests of photocatalytic activity of the heat‐treated micron‐sized TiO₂ powders were conducted by the photocatalytic degradation of Rhodamine B and Acid Red B under visible light irradiation. The results indicate that mixed crystal TiO₂ photocatalyst heat‐treated at 400 °C for 60 min shows the highest photocatalytic activity. It can effectively decompose the Rhodamine B and Acid Red B in aqueous solution after 6 h visible light irradiation. A remarkable improvement in photocatalytic activity of TiO₂ is caused by the formation of combined rutile–anatase phases and separation of photogenerated electron–hole pairs. Copyright © 2007 Society of Chemical Industry     

Sinterability of Forsterite Prepared via Solid‐State Reaction

In this work, the sinterability of forsterite powder synthesized via solid‐state reaction was investigated. X‐ray diffraction (XRD) analyses indicate that the synthesized powder possessed peaks that correspond to stoichiometric forsterite. Scanning electron micrographs revealed that the powders were formed agglomerates, which were made up of loosely packed fine particles. Subsequently, the forsterite powders were cold isostatically pressed into a disk shape under 200 MPa and sintered in air at temperature ranging from 1200°C to 1500°C (interval of 50°C) with ramp rate of 10°C/min and dwelling time of 2 h. The sinterability of each sintered samples was examined in terms of phase stability, relative density, Vickers hardness, fracture toughness, and microstructural examination. XRD examination on all the sintered samples exhibited pure forsterite, in which the generated peaks were found to be in a good agreement with JCPDS card no. 34‐0189. The densification of forsterite progressed to reach a maximum relative density of ~91% at 1500°C. This study also revealed that high‐strength forsterite ceramic can be synthesized via solid‐state reaction as forsterite attained favorable mechanical properties, having fracture toughness of 4.88 MPam^1/2 and hardness of 7.11 GPa at 1400°C.     

Thermal and dynamic mechanical properties of organic–inorganic hybrid composites of itaconate‐containing poly(butylene succinate) and methacrylate‐substituted polysilsesquioxane

Itaconate‐unit‐containing poly(butylene succinate) (PBSI) was synthesized by the reaction of 1,4‐butanediol, succinic acid, and itaconic acid in a molar ratio of 2.0 : 1.0 : 1.0, and the obtained PBSI was reacted with methacryl‐group‐substituted polysilsesquioxane (ME‐PSQ) in the presence of benzoyl peroxide (BPO) at 130°C to produce PBSI/ME‐PSQ hybrid composites. The thermal and dynamic mechanical properties of the PBSI/ME‐PSQ hybrid composites were investigated in comparison with those of PBSI cured at 130°C in the presence of BPO. As a result, the hybrid composites showed a much higher thermal degradation temperature and storage modulus in the rubbery state than the cured PBSI (C‐PBSI). The thermal degradation temperature and storage modulus of the hybrid composites increased with increasing ME‐PSQ content. The glass‐transition temperature, measured by dynamic mechanical analysis of the hybrid composites, somewhat increased with increasing ME‐PSQ content. However, the glass‐transition temperatures of all the hybrid composites were lower than that of C‐PBSI. Although the IR absorption peak related to C?C groups was not detected for C‐PBSI, some olefinic absorption peaks remained for all the hybrid composites. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Piezo and dielectric properties of PHB–PZT composite

Flexible piezoelectric composite films made of poly(3‐hydroxybutyrate) (PHB) in powder form and lead zirconate titanate (PZT) ceramic powder were obtained by mixing both powders and pressing at 180°C. The effect of PZT on PHB crystallization was investigated using differential scanning calorimetry (DSC). The relative dielectric constant and dielectric loss factor were analyzed by dielectric spectroscopy and the α‐relaxation of amorphous phase of PHB was observed. After suitable polarization, the composite film displayed piezoelectric activity indicating the possibility of using that material as a sensor. POLYM. COMPOS., 2009. © 2008 Society of Plastics Engineers     

Sintering and Piezoelectric Properties of Co-Fired Lead Zirconate Titanate/Ag Composites

Lead zirconate titanate (PZT) ceramics were co-fired with pure Ag powders at 1200°C for 1 h, and the ferroelectric and piezoelectric properties of the resultant PZT/Ag composites were evaluated, aimed at potential applications in functionally graded piezoelectric actuators with enhanced mechanical reliabilities. In the range of 1–15 vol% Ag concentration, pure Ag powder remained as the second phase in the composites, and a small quantity of Ag entered into the crystal lattice of PZT and slightly increased the lattice constants of a and c . The Ag powders were found to aggregate together and grow to larger particles in the composites. The ceramic grains grew from an initial size of 1.5 μm for monolithic PZT to 2.5 μm for the PZT/Ag composites, and the grain size was almost the same for various Ag concentrations. It was found that the ferroelectric and piezoelectric properties decreased when Ag was added to PZT. In the range of 1–15 vol% Ag concentration, the remanent polarization P _r decreased from 38 to 27 μC/cm², the piezoelectric constant d ₃₃ decreased from 394 to 105 pC/N, and the planar electromechanical coupling factor k _p decreased from 0.69 to 0.15, respectively. These piezoelectric properties of the present PZT/Ag composites were compared with the results reported for PZT/Pt composites, and discussed in relation to microstructural features.     

Nano‐sized silica supported Me2Si(Ind)2ZrCl2/MAO catalyst for ethylene polymerization

Nano‐sized and micro‐sized silica particles were used to support a zirconocene catalyst [racemic‐dimethylsilbis(1‐indenyl)zirconium dichloride], with methylaluminoxane as a cocatalyst. The resulting catalyst was used to catalyze the polymerization of ethylene in the temperature range of 40–70°C. Polyethylene samples produced were characterized with scanning electron microscopy (SEM), X‐ray diffraction (XRD), differential scanning calorimetry (DSC), and gel permeation chromatography (GPC). Nano‐sized catalyst exhibited better ethylene polymerization activity than micro‐sized catalyst. At the optimum temperature of 60°C, nano‐sized catalyst's activity was two times the micro‐sized catalyst's activity. Polymers obtained with nano‐sized catalyst had higher molecular weight (based on GPC measurements) and higher crystallinity (based on XRD and DSC measurements) than those obtained with micro‐sized catalyst. The better performances of nano‐sized catalyst were attributed to its large external surface area and its absence of internal diffusion resistance. SEM indicated that polymer morphology contained discrete tiny particles with thin long fiberous interlamellar links. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

ZrB2–SiC–G Composite Prepared by Spark Plasma Sintering of In‐Situ Synthesized ZrB2–SiC–C Composite Powders

To avoid introduction of milling media during ball‐milling process and ensure uniform distribution of SiC and graphite in ZrB₂ matrix, ultrafine ZrB₂–SiC–C composite powders were in‐situ synthesized using inorganic–organic hybrid precursors of Zr(OPr)₄, Si(OC₂H₅)₄, H₃BO₃, and excessive C₆H₁₄O₆ as source of zirconium, silicon, boron, and carbon, respectively. To inhabit grain growth, the ZrB₂–SiC–C composite powders were densified by spark plasma sintering (SPS) at 1950°C for 10 min with the heating rate of 100°C/min. The precursor powders were investigated by thermogravimetric analysis–differential scanning calorimetry and Fourier transform infrared spectroscopy. The ceramic powders were analyzed by X‐ray diffraction, X‐ray photoelectron spectroscopy, and scanning electron microscopy. The lamellar substance was found and determined as graphite nanosheet by scanning electron microscopy, Raman spectrum, and X‐ray diffraction. The SiC grains and graphite nanosheets distributed in ZrB₂ matrix uniformly and the grain sizes of ZrB₂ and SiC were about 5 μm and 2 μm, respectively. The carbon converted into graphite nanosheets under high temperature during the process of SPS. The presence of graphite nanosheets alters the load‐displacement curves in the fracture process of ZrB₂–SiC–G composite. A novel way was explored to prepare ZrB₂–SiC–G composite by SPS of in‐situ synthesized ZrB₂–SiC–C composite powders.     

Role of Nano‐ and Micron‐Sized Particles of TiO2 Additive on Microwave Dielectric Properties of Li2ZnTi3O8 – 4 wt% TiO2 Ceramics

Microwave dielectric ceramics with the composition of Li₂ZnTi₃O₈ – 4 wt% TiO₂ were synthesized by the conventional solid‐state reaction. 4 wt% TiO₂ powders with different particles size were added to the Li₂ZnTi₃O₈ ceramic. Then the ceramic samples were sintered at temperatures 1075°C, 1050°C, 1000°C, and 950°C for 4 h. The effect of the particles size of TiO₂ additive on the microwave dielectric properties of the ceramics has been investigated. In the study two categories of particles size of TiO₂ additive have been used; (i) Nanoparticle (50 nm), (ii) Micron sized (40, 5, 1 μm) powder. X‐ray showed that the TiO₂ additive has not solved in the LZT structure and has not almost undergone chemical reaction with the LZT ceramic. The results showed that the addition of TiO₂ nanoparticles to the LZT ceramics significantly improved the density and a dense and uniform microstructure and also abnormal grain growth were observed by SEM. The use of TiO₂ nanoparticle reduces porosity and leads to an increase in green density. The maximum density was found to be 98.5% of the theoretical density and the best relative permittivity of 28, quality factor of 68000 GHz and τ_f value of ?2 ppm/°C were obtained for the samples added with 4 wt% of the TiO₂ nanoparticles, sintered at 1050°C for 4 h.     

Preparation and characterization of high permittivity and low loss PTFE/CaTiO3 microwave laminates

This article discusses the preparation and characterization of CaTiO₃ filled PTFE flexible laminates for microwave substrate applications. Single phase CaTiO₃ filler composition was prepared through solid‐state ceramic route. Phase formation was confirmed by powder X‐ray diffraction studies. Morphology and filler distribution of the composites were studied using scanning electron microscopic technique. Permittivity and loss tangent of the composite substrates were measured at X‐band frequency region (8.2–12.4 GHz) using waveguide cavity perturbation technique. Effective permittivity of the composites was compared with theoretically predicted values. Temperature coefficient of permittivity (τ_εr) of the composites was also measured in the 0–100°C temperature range. PTFE/CaTiO₃ composite has an effective permittivity of 11.8 and a loss tangent of 0.0036 at optimum filler loading. POLYM. COMPOS., 2009. © 2008 Society of Plastics Engineers     

Solvothermal Conversion of Nanofiber to Nanorod‐Like Mesoporous γ‐Al2O3 Powders,and Study Their Adsorption Efficiency for Congo Red

Mesoporous γ‐Al₂O₃ powders with nanofiber and nanorod‐like structures were synthesized using boehmite sols in the presence of triblock copolymer, P123 in ethanol by solvothermal process at different temparatures (100°C–165°C) followed by calcination at 400°C–1000°C. The powders were characterized by low‐ and wide‐angle X‐ray diffraction (XRD), N₂ adsorption–desorption, and transmission electron microscopy (TEM). The adsorption efficiency of the powders with Congo red (CR) was studied by UV–vis spectroscopy. The γ‐Al₂O₃ phase became stable up to 1000°C. The nanorods obtained at 165°C had narrower pore size distribution (PSD) than nanofibers synthesized at 100°C, the former showed higher CR adsorption efficiency. The stepwise growth mechanism of nanofibers to nanorods conversion with increase in solvothermal temperatures was illustrated.     

Combining Soft Chemistry and Spark Plasma Sintering to Produce Highly Dense and Finely Grained Soft Ferrimagnetic Y3Fe5O12 (YIG) Ceramics

We report the synthesis of yttrium iron garnet (YIG) combining soft chemistry route, namely the polyol process, and spark plasma sintering (SPS) technique. The polyol process produced an intermediary amorphous phase containing both iron and yttrium cations in the desired ratio. They were annealed at 400°C in air to decompose the organic content of the reaction (polyol and acetate). To achieve the garnet phase, the polyol‐obtained precursor was subjected to reactive SPS treatment at a temperature of 750°C, far below the typical temperatures (1350°C) used in the classic solid‐state reaction process. In 15 min pure and high‐density Y₃Fe₅O₁₂ ceramic, with about 100 nm sized crystalline grains, was obtained. We report as well the characterization of the initial amorphous phase and the obtained YIG by X‐ray diffraction, scanning electron microscopy, Fourier‐transform infrared spectroscopy, ⁵⁷Fe Mössbauer spectrometry, and magnetization measurements.     

Preceramic polymer as precursor for near‐stoichiometric silicon carbon with high ceramic yield

Precursor polycarbosilane containing acetylenic and Si? H group (PCAS) has been successfully prepared by the reaction of dilithioacetylene with methyl dichlorosilane, and characterized by gel permeation chromatography, Fourier transform infrared spectroscopy, ¹H‐NMR, ¹³C‐NMR, and ²⁹Si‐NMR. Thermogravimetric analysis curve in nitrogen showed the temperature of 5 wt % weight losses (T_d5) was 613°C, while the ceramic yield of PCAS was 88% at 1000°C. Pyrolysis behavior and structure evolution of the cured PCAS were studied by means of X‐ray diffraction, Raman, scanning electron microscope‐energy dispersive X‐ray spectrometer, transmission electron microscope (selected area electron diffraction and high resolution transmission electron microscope), and elemental analysis. The polymer to ceramic conversion was completed at 1600°C and the results revealed that the ceramic consisted of β‐SiC and α‐SiC. The composition of the ceramic was near‐stoichiometric with molar ratio of Si/C (1.02 : 1) except rare and localized free carbon inclusions. The SiC ceramics exhibited high thermo‐oxidation resistance at elevated temperatures in air atmosphere. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41335.     

Magnetoelectric composites of nickel ferrite and lead zirconnate titanate prepared by spark plasma sintering

Magnetoelectric (ME) bulk composites of ferrite and lead zirconnate titanate (PZT) were prepared by spark plasma sintering (SPS) of mechanically mixed ferrites, BaFe₂O₄ or NiFe₂O₄ and a soft lead zirconnate titanate, PZT-5A, powders. The feasibility of retarding possible reactions occurring between the ferrite and lead zirconnate titanate was approved by applying such a dynamic process as SPS. It was further revealed that nickel ferrite and PZT-5A is a more favorable combination that underwent no obvious reactions up to 1050 °C. Efforts were made to optimize the SPS processing parameters in order to produce immiscible composites with high electrical resistivity, low dielectric loss and better magnetoelectric response.