The Effects of Calcium‐to‐Phosphorus Ratio on the Densification and Mechanical Properties of Hydroxyapatite Ceramic

In this work, hydroxyapatite (HA) powders were synthesized using calcium hydroxide Ca(OH)₂ and orthophosphoric acid H₃PO₄ via wet chemical precipitation method in aqueous medium. Calcium‐to‐phosphorus (Ca/P) ratio was set to 1.57, 1.67, 1.87 that yield calcium‐deficient HA, stoichiometric HA, and calcium‐rich HA, respectively. These synthesized HA powders (having different Ca/P ratio) were characterized in terms of particle size and microstructural examination. Then, the densification and mechanical properties of the calcium‐deficient HA, stoichiometric HA, and calcium‐rich HA were evaluated from 1000 to 1350°C. Experimental results have shown that no decomposition of hydroxyapatite phase was observed for stoichiometric HA (Ca/P = 1.67) and calcium‐deficient HA (Ca/P = 1.57) despite sintered at high temperature of 1300°C. However, calcium oxide (CaO) was detected for calcium‐rich HA (Ca/P = 1.87) when samples sintered at the same temperature. The study revealed that the highest mechanical properties were found in stoichiometric HA samples sintered at 1100–1150°C, having relative density of ~99.8%, Young's modulus of ~120 GPa, Vickers hardness of ~7.23 GPa, and fracture toughness of ~1.22 MPam^1/2.     

Synthesis of ternary ceramics (Cr2AlC) by using biochars

In this paper, we report the synthesis of Cr₂AlC by using biochars derived from lignin, Distiller's dried grains with solubles (DDGS), and hemp fibers. Initially, the powders were pyrolyzed at 1350°C for 4 h in Ar atmosphere to form biochars. The ball-milled and sieved biochar powders were then mixed with Cr and Al powders in different stoichiometric ratios according to the C-content of the biochars. The mixed powders were reacted at 1350°C for 4 h in Ar atmosphere. Detailed scanning electron microscopy and X-ray diffraction analysis showed the powders derived from hemp and DDGS biochars were > 90% pure as compared to powders derived from lignin biochar which was 76% pure. It is expected that ternary ceramics derived from biochars can be an addition avenue for carbon-storage.     

Preparation of Phase‐Pure K0.5Na0.5NbO3 Fine Powders by a Solid‐State Reaction at 625°C from a Precursor Comprising Nb2O5 and K,Na Acetates

Phase‐pure K_0.5Na_0.5NbO₃ (KNN) fine powders were synthesized via a solid‐state route from a homogeneous solid mixture. A colloidal dispersion comprising a mixed ethanol solution of potassium and sodium acetates and Nb₂O₅ fine particles was attrition milled and dried carefully to avoid water absorption. Two‐step calcination in air at 450°C and 625°C, each for 3 h, resulted in the phase‐pure KNN powders. The volume‐based median diameter of the final product was ca. 0.8 μm. Starting from the same precursors without dissolving the acetates, the phase‐pure KNN was never achieved even when the two calcination temperatures were increased to 550°C and 700°C, in spite of the same milling conditions. Key issues of eliminating second phases were (i) starting from a wet‐milled mixture with a single solution containing both of the A‐site species, and (ii) repeated wet milling of the reaction mixture to disintegrate reaction‐induced agglomerates. These enabled rapid nuclei growth from chemically interacted precursor prior to calcination, and short diffusion path due to repeated deagglomeration, excluding formation of off‐stoichiometric second phases. All these items were confirmed by different analytical tools, among others, thermo‐gravimetry and differential thermal analysis (TG‐DTA), particle size analyses, and XPS at various reaction stages. On the heating stage microscope, a shrinkage onset was observed at 850°C, that is, 150 K lower than that of conventionally prepared KNN, that is, via a solid‐state synthesis from carbonates by a two‐step calcination at 800°C and 750°C, for 4 h each. No second phase was observed after sintering up to 1100°C.     

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.     

Low temperature synthesis of Titanium diboride by carbothermal method

Titanium diboride powders have been synthesized by means of carbothermal reduction method utilizing Titanium oxide, Boric acid and Graphite. The effect of mechanical activation of mixed raw materials and the use of additional Boric acid on the final phases have been studied. The resultant powders were characterized by X-ray diffraction (XRD) analyzer and Field Emission Scanning Electron Microscope (FESEM). XRD patterns showed that TiB₂, TiC and C phases after heat treatment at stoichiometric ratio of reactants. By increasing the milling time, the unwanted phases such as C and TiC will be reduced. Pure TiB₂ could be synthesized with mechanical activation of raw materials for 24?h at non-stoichiometric ratio (using additional Boric acid) and heat treatment at low temperature of 1380?°C. In this condition, Titanium diboride could be achieved with residual carbon of 0.92 0.09wt% and mean average particle size of 3.28µm. Thermal analysis (TGA-DTA) was used to determine the reaction progress and mechanism. Results revealed that the intermediate phase, TiBO₃, played an important role in getting to lower temperature synthesis. This phase was identified after mechanical milling of raw materials and heat treatment at temperature of 1250?°C.     

Synthesis of triclinic and hexagonal SmBO3 powders by mechanically activated annealing of Sm2O3 and B2O3 blends

Samarium borate (SmBO₃) powders were fabricated from oxide raw materials by a two-step solid-state synthesis method including mechanical activation and annealing. Blends containing stoichiometric amounts of samarium oxide (Sm₂O₃) and boron oxide (B₂O₃) were mechanically activated in a high-energy ball mill and subsequently annealed in air. Afterwards, mechanically activated and annealed powders were washed with distilled water in order to remove probable unreacted B₂O₃ phase. The effects of mechanical activation duration (15 min, 1 h, 3 h and 9 h) and annealing temperature (700–1250 °C) on the resultant powders were investigated. Compositional, microstructural, physical, thermal and optical properties of the powders obtained throughout the different process steps were characterized by using an X-ray diffractometry (XRD), particle size analysis (PSA), stereomicroscopy (SM), scanning electron microscopy (SEM), transmission electron microscopy (TEM), gas pycnometry, differential scanning calorimetry (DSC), heating stage microscopy (HSM), atomic absorption spectrometry (AAS), Fourier transform infrared (FTIR) spectrometry and ultraviolet-visible spectrophotometry (UV–vis) techniques. Fine-grained and pure SmBO₃ powders were successfully synthesized via a simple, feasible and scalable route, yielding both triclinic and hexagonal crystal structures. Triclinic SmBO₃ powders were synthesized after mechanical activation for 1 h and annealing at 700 °C for 2 h. The polymorphic transformation temperature of SmBO₃ powders from triclinic to hexagonal is about 1080 °C. Due to the effect of mechanical activation, the synthesis of triclinic SmBO₃ phase and its transformation to hexagonal form were found to take place at ∼50–100 °C lower temperatures than those reported in other methods. Mainly hexagonal SmBO₃ powders were obtained after annealing at 1150 °C in the presence of a very small amount of triclinic SmBO₃. The resultant powders showed intense UV absorptions in the range between 1025 and 1150 nm with minimum reflectivity of 0.57% (triclinic SmBO₃ phase) and 0.68% (hexagonal SmBO₃ phase) depending on their crystal structures.     

One-pot synthesis of monoclinic ZrO2 nanocrystals under subcritical hydrothermal conditions

This study reports a one-pot synthesis technique for the preparation of single-phase monoclinic zirconium oxide (ZrO₂) nanocrystals. The products were synthesized from only zirconium oxynitrate (ZrO(NO₃)₂) as the precursor under hydrothermal conditions using subcritical water. The precursor was heat-treated in a batch-type reactor at a reaction temperature of 250 °C for 24 h to obtain pure monoclinic-structured ZrO₂ nanocrystals. The crystallization temperature of the ZrO₂ phase was also greater than 200 °C. However, the products of reactions conducted at 200 °C for 24 h were mixtures of the tetragonal and monoclinic structures. At a reaction temperature of 250 °C, the volume fraction of the monoclinic phase increased; however, the reaction time was also important. The heat-treatment was performed for more than 12 h in order to obtain single-phase monoclinic ZrO₂ nanocrystals. The crystallite size of this product was approximately 20 nm, and water, hydroxide groups, and nitro groups were chemisorbed on its surface.     

Synthesis of ultra-fine hafnium carbide powders combining the methods of liquid precursor conversion and plasma activated sintering

Ultra-fine hafnium carbide (HfC) powders were synthesized using a novel method combining liquid precursor conversion and plasma activated sintering (PAS). Solution-based processing was used to achieve a fine-scale mixing of the reactants, and further treatment by PAS allowed fast formation of HfC. We investigated the effect of the type of acid used during the liquid precursor conversion on the synthesized powders, where mixtures were prepared using salicylic acid, citric acid, or a combination of these. The results show that pure HfC powders (with an average particle sizes of 350 nm) were obtained at a relatively low temperature (1550 °C) using a HfOCl₂·8H₂O precursor with the mixed acids. The oxygen content of the synthesized powders was only 0.97 wt%. The type of acid had a significant effect on the synthesis product. When using only citric acid, the temperature required to produce pure hafnium carbide increased to 1700 °C. In the case of a salicylic acid precursor, pure HfC was not obtained, even at a synthesis temperature of 1700 °C.     

New Method of Synthesizing Aluminum Oxynitride Spinel Powders

Aluminum oxynitride spinel (AlON) powders were synthesized by aluminothermic reaction in a reducing N₂‐CO atmosphere. Low cost and easily available aluminum and γ‐Al₂O₃ alumina micrometer‐sized powders were employed as starting materials. Mixed powders consisting of 75 wt% Al and 25 wt% Al₂O₃ were milled together and pressed into billets with diameter of 20 mm and height of 15 mm. Green‐body billets were then calcined in charcoal‐protected condition (namely in a N₂‐CO atmosphere) at 1600°C. Phase composition and microstructure of final sintered products were analyzed. The results showed that AlON phase with AlN as a minor phase was formed at 1600°C for 3 h. At the same time, grains of AlON were tabular in shape and whiskers can be found in samples after being sintered at 1600°C.     

Synthesis of La0.9Sr0.1Al0.85Mg0.1Co0.05O2.875 using a polymeric method

Nanocrystalline La_0.9Sr_0.1Al_0.85Mg_0.1Co_0.05O_2.875 (LSAMC) powders were synthesized via a polymeric method using poly(vinyl alcohol) (PVA). The effect of PVA content on the synthesized powders was studied. When the ratio of positively charged valences (Mⁿ⁺) to hydroxyl groups (OH) is 1.5:1, crystalline LaAlO₃ could be obtained at such a low calcination temperature as 700 °C. While at 900 °C the ratio is of less importance, since pure LaAlO₃ perovskite could be formed for all powders after calcination at 900 °C. Thermal analysis (TG/DTA) was utilized to characterize the thermal decomposition behaviour of precursor powders. The chemical structure of the calcined powder was studied by Fourier transform infrared (FTIR) spectroscopy. The powder morphology and microstructure were examined by SEM. Dense pellets with well-developed submicron microstructures could be formed after sintering at 1450 °C for 5 h. Compared with the solid-state reaction method, the sintering temperature is substantially lower for powder prepared by the PVA method. This is due to the ultrafine and highly reactive powder produced.     

Effect of synthesis parameters on the size of cobalt ferrite crystallite

Nanoparticles of cobalt ferrite (CoFe₂O₄) were synthesized by the EDTA/Citrate complexing method and hydrothermal method without addition of surfactant. The influence of the pH of the reaction medium (8, 9 or 10), the temperature of the thermal treatment (600 °C, 800 °C or 1000 °C for the EDTA/Citrate method, and 120 °C, 140 °C or 160 °C for the hydrothermal method), and the duration of the thermal treatment (2, 4 or 6 h for the EDTA/Citrate complexing method, and 6, 15 or 24 h for the hydrothermal method) on the average crystallite size was studied by means of an experimental design based on the results obtained by XRD. Statistical analysis led to quantification of the influence of the synthesis parameters on the crystallite size of the powders. Results showed that the pH of the reaction medium is the parameter that shows the greatest influence on the growth of the crystallites of the powders obtained by the hydrothermal method, while calcination temperature is the most significant one for the powders produced by the EDTA/Citrate complexing method.     

Two‐Step Carbothermal Synthesis of AlN–SiC Solid Solution Powder Using Combustion Synthesized Precursor

In the present work, a two‐step carbothermal reduction method is employed to prepare the AlN–SiC solid solution (AlN–SiCss) powders by using a combustion synthesized precursor. The precursor is prepared by low‐temperature combustion synthesis (LCS) method using a mixed solution of aluminum nitrate, silicic acid, polyacrylamide, glucose, and urea. The synthesized LCS precursor exhibits a porous and foamy uniform mixture of Al₂O₃ + SiO₂ + C consisting of flaky particles. The carbothermal reduction in the LCS precursor is carried out in two steps. First, the precursors are calcined at 1600°C in argon for 3 h. Subsequently, the precursors are further calcined at 1600°C–1900°C in nitrogen for 3 h. The results indicate that the precursor calcined at and above 1850°C in nitrogen for 3 h yields the single‐phase AlN–SiCss powders. The synthesized AlN–SiCss powder exhibits near‐spherical particles with diameter of 200–500 nm. The experimental and thermodynamical results reveal that the formation of AlN–SiCss occurs via the diffusion of AlN into SiC by virtue of formation of a highly defective β′ intermediate during the second step reaction.     

Preparation and characterization of LnMgAl11O19 (Ln=La,Nd, Gd) ceramic powders

Lanthanide hexaaluminate powders of LaMgAl₁₁O₁₉ (LMA), NdMgAl₁₁O₁₉ (NMA) and GdMgAl₁₁O₁₉ (GMA) were synthesized via the solid state reaction or sol–gel and calcination method. The LMA and NMA powders synthesized by the sol–gel and calcination method at 1600 °C for 8 h exhibit a single hexaaluminate phase with magnetoplumbite structure; however, the GMA powder synthesized by the sol–gel and calcination method at 1600 °C for 8 h contains both a hexaaluminate phase and a small amount of second phase GdAlO₃ with a perovskite structure. The powders synthesized by the solid state reaction method at 1500 °C for 4 h have a small particle size of 1–3 μm, and a large specific surface area and a good uniformity. The powders synthesized by the sol–gel and calcination method at 1600 °C for 8 h have a particle size of 5–20 μm, and exhibit to a certain extent agglomeration.     

Preparation and characterization of ultrafine ZrB2–SiC composite powders by a combined sol–gel and microwave boro/carbothermal reduction method

A combined sol–gel and microwave boro/carbothermal reduction technique was investigated and used to synthesize ultrafine ZrB₂–SiC composite powders from raw starting materials of zirconium oxychloride, boric acid, tetraethoxysilane and glucose. The effects of reaction temperature, molar ratios of n(B)/n(Zr) and n(C)/n(Zr+Si) on the synthesis of ultrafine ZrB₂–SiC composite powders were studied. The results showed that the optimum molar ratios of n(B)/n(Zr) and n(C)/n(Zr+Si) for the preparation of phase pure ultrafine ZrB₂–SiC composite powders were 2.5 and 8.0, respectively, and the firing temperature required was 1300 °C. This temperature was 200 °C lower than that require by using the conventional boro/carbothermal reduction method. Microstructures and phase morphologies of as-prepared ultrafine ZrB₂–SiC composite powders were examined by field emission-scanning electron microscopy (FE-SEM) and transmission electron microscope (TEM), showing that SiC grains were formed evenly among the ZrB₂ grains, and the grain sizes of ZrB₂ in the samples prepared at 1300 °C for 3 h were about 1–2 μm. The average crystalline sizes of these two phases in the as-prepared samples were calculated by using the Scherrer equation as about 58 and 27 nm, respectively.     

Effects of calcination temperature on structure and magnetic properties of pure FeCo2O4 powders

A series of FeCo₂O₄ powders was initially synthesized using a hydrothermal method and subsequently calcined at various temperatures to produce the final product. Pure phase FeCo₂O₄ powders can only be formed in the temperature range of 950–1050 °C. In this work, we study the cation occupation, cation valence, bond length and bond angle changes of the pure phase FeCo₂O₄ powders formed in such a narrow temperature range. Octahedral lattice distortion in the pure phase FeCo₂O₄ samples has been observed. More tetrahedral Fe³⁺ and octahedral Co²⁺ are excited and exchanged their sites as the calcination temperature increases from 950 °C to 1000 °C, and part of Co³⁺ ions are reduced to Co²⁺ in the sample calcined at 1050 °C. The structure of the sample calcined at 1000 °C is close to that of the ideal FeCo₂O₄ spinel. Magnetic measurements show that ferrimagnetism and anti-ferromagnetism coexist in the pure phase FeCo₂O₄ samples. Interaction changes between ferrimagnetism and antiferromagnetism caused by the structural changes of the samples have been studied. Due to the pinning of the local anti-ferromagnetism to ferrimagnetism in the sample, the sample shows a Barkhausen jump below 150 K. As the measurement temperature increases further, the system enters into a reentrant spin glass state.     

Oxidation behavior of β-SiAlON powders fabricated by combustion synthesis

The present study presents the effect of addition of diluents on the crystal morphologies and the impact on the oxidation resistance of β-SiAlON powders obtained from combustion synthesis method. Pure β-SiAlON were synthesized with diluents. It was observed by SEM that the diluents resulted in the transformation from large hexagonal column-shaped crystals to fine isotropic grains. Oxidation experiments were conducted by thermogravimetric analysis (TGA) in the temperature range from 1200 °C to 1400 °C. The TGA results indicated that oxidation was controlled by mixed chemical reaction and diffusion process. The chemical reaction step was found to be rate-controlling at low oxidation temperatures (1200 °C and 1300 °C), while at high temperature (1400 °C), diffusion was found to control the reaction rate. Oxidation products were investigated by X-ray Diffraction (XRD) analysis and found to be made up of SiO₂, Al₂O₃. This research aims to provide guidance for the fabrication of β-SiAlON by combustion synthesis, thus facilitating its further application in high temperature industry.     

Synthesis and characterization of nanometric gadolinia powders by room temperature solid-state displacement reaction and low temperature calcination

Nanometric-sized gadolinia (Gd₂O₃) powders were obtained by applying solid-state displacement reaction at room temperature and low temperature calcination. The XRD analysis revealed that the room temperature product was gadolinium hydroxide, Gd(OH)₃. In order to induce crystallization of Gd₂O₃, the subsequent calcination at 600 ∼ 1200 °C of the room temperature reaction products was studied. Calculation of average crystallite size (D) as well as separation of the effect of crystallite size and strain of nanocrystals was performed on the basic of Williamson-Hall plots. The morphologies of powders calcined at different temperatures were followed by scanning electron microscopy. The pure cubic Gd₂O₃ phase was made at 600 °C which converted to monoclinic Gd₂O₃ phase between 1400° and 1600 °C. High-density (96% of theoretical density) ceramic pellet free of any additives was obtained after pressureless sintering at 1600 °C for 4 h in air, using calcined powder at 600 °C.     

Synthesis and pyrolysis behavior of a soluble polymer precursor for ultra-fine zirconium carbide powders

A soluble polymer precursor for ultra-fine zirconium carbide (ZrC) was successfully synthesized using phenol and zirconium tetrachloride as carbon and zirconium sources, respectively. The pyrolysis behavior and structural evolution of the precursor were studied by Fourier transform infrared spectra (FTIR), differential scanning calorimetry, and thermal gravimetric analysis (DSC–TG). The microstructure and composition of the pyrolysis products were characterized by X-ray diffraction (XRD), laser Raman spectroscopy, scanning electron microscope (SEM) and element analysis. The results indicate that the obtained precursor for the ultra-fine ZrC could be a Zr–O–C chain polymer with phenol and acetylacetone as ligands. The pyrolysis products of the precursor mainly consist of intimately mixed amorphous carbon and tetragonal ZrO₂ (t-ZrO₂) in the temperature range of 300–1200 °C. When the pyrolysis temperature rises up to 1300 °C, the precursor starts to transform gradually into ZrC, accompanied by the formation of monoclinic ZrO₂ (m-ZrO₂). The carbothermal reduction reaction between ZrO₂ and carbon has been substantially completed at a relatively low temperature (1500 °C). The obtained ultra-fine ZrC powders exhibit as well-distributed near-spherical grains with sizes ranging from 50 to 100 nm. The amount of oxygen in the ZrC powders could be further reduced by increasing the pyrolysis temperature from 1500 to 1600 °C but unfortunately the obvious agglomeration of the ZrC grains will be induced.     

Low‐Temperature Synthesis of Nanocrystalline NbB2 Powders by Borothermal Reduction in Molten Salt

Nanocrystalline NbB₂ powders were successfully prepared by borothermal reduction in molten salt at 800°C–1000°C. Due to the more homogeneous mixing and more rapid diffusion of species in the liquid state than in the solid state, the synthesis temperature of pure NbB₂ phase was greatly decreased by the presence of molten NaCl/KCl salt. The NbB₂ powders synthesized at 1000°C had the largest specific surface area of 27.09 m²/g and the lowest equivalent average particle size of 32 nm, respectively.     

Low‐Temperature Sintering of β‐Spodumene Ceramics Using Li2O–GeO2 as a Sintering Additive

Low‐temperature sintering of β‐spodumene ceramics with low coefficient of thermal expansion (CTE) was attained using Li₂O–GeO₂ sintering additive. Single‐phase β‐spodumene ceramics could be synthesized by heat treatment at 1000°C using highly pure and fine amorphous silica, α‐alumina, and lithium carbonate powders mixture via the solid‐state reaction route. The mixture was calcined at 950°C, finely pulverized, compacted, and finally sintered with or without the sintering additive at 800°C–1400°C for 2 h. The relative density reached 98% for the sample sintered with 3 mass% Li₂O–GeO₂ additive at 1000°C. Its Young's modulus was 167 GPa and flexural strength was 115 MPa. Its CTE (from R.T. to 800°C) was 0.7 × 10^?6 K^?1 and dielectric constant was 6.8 with loss tangent of 0.9% at 5 MHz. These properties were excellent or comparative compared with those previously reported for the samples sintered at around 1300°C–1400°C via melt‐quenching routes. As a result, β‐spodumene ceramics with single phase and sufficient properties were obtained at about 300°C lower sintering temperature by adding Li₂O–GeO₂ sintering additive via the conventional solid‐state reaction route. These results suggest that β‐spodumene ceramics sintered with Li₂O–GeO₂ sintering additive has a potential use as LTCC for multichip modules.