Characteristics of powder and sintered bodies of hydrothermally synthesized Mn-Zn ferrites

To improve the sinterability of powders fabricated by the conventional mixed-oxides method, ultrafine Mn-Zn ferrite powders were hydrothermally synthesized from metal nitrates solution using ammonia as a precipitant. The R value (alkalinity) was introduced to adjust the amount of added OH^– in the reaction suspension. The characteristics of the powders synthesized at different hydrothermal conditions and the properties of the sintered bodies were investigated. The results show that the R value and hydrothermal time have a great effect on the compositions and phases of hydrothermally synthesized Mn-Zn ferrite powders. Powders synthesized from a starting suspension with a higher content of Zn ions (or lower content of Mn²⁺) may approach to a stable spinel structure with a lower Mn/Zn ratio as the hydrothermal time is longer. Factors affecting the position of the diffraction angle (2) of the spinel Mn-Zn ferrite (311) of powders may include both the compositions of spinel ferrite structure and crystallite sizes (or particle sizes) of powders. Some possible reasons were suggested to explain the dependence of composition and phase of hydrothermally synthesized Mn-Zn ferrite powders on the R value and hydrothermal time. The temperature that the green compact begins to shrink at increases with increasing R value, and ranges from 510°C (R = 2) to 650°C (R = 6). After being sintered at 950°C for 2 h in N₂ atmosphere, the relative sintered density of each specimen reaches a value of 94.5–99.8%.     

Low temperature synthesis of nanocrystalline lithium ferrite by a modified citrate gel precursor method

Single phase nanocrystalline lithium ferrite is synthesized by a modified citrate gel precursor technique. Ferrite nanoparticles of average size of 8 nm, obtained after calcination of the citrate gel made by the usual method at 450 °C, show superparamagnetic behavior. However, small amounts of -Fe₂O₃ is formed as an impurity phase due to the initial formation of some -Fe₂O₃ phase. On the other hand, when the pH of the mixed solution is increased to 7 after the addition of ammonia solution, a lower calcination temperature of 200 °C is sufficient for the formation of single phase lithium ferrite nanoparticles of size 30 nm. No impurity phases are detected when the nanocrystalline powders are calcined at higher temperatures. The magnetic properties of the ferrite nanoparticles of different sizes obtained by calcining the powders at different temperatures are studied.     

Preparation of composite Al2O3-TiO2 particles from organometallic precursors and transformations during heating

Equimolar Al₂O₃-TiO₂ composite powders were prepared via controlled hydrolysis of organometallic precursors, sometimes in the presence of submicrometre commercial-Al₂O₃ or anatase-TiO₂ particles. Variations in the chemical procedures were used aimed at different submicrostructures within the resulting powders. Heating such powders in air shows that structural behaviour is influenced by the micromorphology of the composite particle. Transformation temperatures of the titania phases seem to depend upon some size parameter which would represent their morphology within the powders. Studies performed on a series of non-equimolar Al₂O₃-TiO₂ composite powders showed that the temperature of -Al₂O₃ formation may be decreased by 210° C possibly due to a seeding effect of rutile. Pseudobrookite Al₂TiO₅ was never detected at 1300° C in air.     

Effects of doping with La and Mn on the crystallite growth and phase transition of BaTiO3 powders

The effects of La and Mn dopants on the crystallite growth and the phase transformation of BaTiO₃ powders were studied. The barium titanate powders were obtained by calcining barium titanyl oxalate tetrahydrate in the temperature range 800 to 1200 °C. Crystallite growth of BaTiO₃ powders was promoted by the use of Mn dopant due to the increase of oxygen vacancies. The dissolution of La dopant into BaTiO₃ structure may decrease the oxygen vacancies so that the growth of BaTiO₃ crystallites is inhibited at high temperature ( 900 °C). When the crystallite size is small, the barium titanate can exist as a cubic phase due to the manifestation of the surface energy. Undoped cubic BaTiO₃ powders can be stable at a size < 30 nm. Doping with La and Mn would bring the crystallite size for the cubic-to-tetragonal phase transformation to 100 nm, resulting from the presence of cation or oxygen vacancies.     

Decomposition of Ca : Cu = 1 : 1 nitrate powder: thermal analysis and structural studies

Thermal decomposition processes in mixtures of Ca : Cu = 1 : 1 nitrate powders produced by a conventional technique and by freeze drying method have been investigated by thermal analysis and X-ray diffraction. Results have been compared with literature values and data obtained by our investigations of individual calcium and copper nitrates. Temperatures at which decomposition processes occur change with by ±30°C and depend also on the level of mixing of the nitrates. An exemption is the temperature for CuO phase formation, which was determined for the Cu-nitrate and for both 1 : 1-nitrate powders to be at 266°C. The domains of stability for different phases are shown to be variable. Also, for 1 : 1-powders, -type and -type Ca(NO₃)₂ · 2H₂O phases coexist, while in Ca-nitrate only the -type phase was observed.     

Preparation of silicon carbide powders by chemical vapour deposition of the (CH3)2SiCl2-H2 system

Silicon carbide (SiC) powders were prepared by chemical vapour deposition (CVD) using (CH₃)₂SiCl₂ and H₂ as source gases at temperatures of 1273 to 1673 K. Various kinds of SiC powders such as amorphous powder, -type single-phase powder and composite powder were obtained. The composite powders contained free silicon and/or free carbon phases of about a few nanometres in diameter. All the particles observed were spherical in shape and uniform in size. The particle size increased from 45 to 130 nm with decreasing reaction temperature and gas flow rate, as well as with increasing reactant concentration. The lattice parameter of the -SiC particles decreased with increasing reaction temperature. All the lattice parameters were larger than those of bulk -SiC.     

RF plasma synthesis of YBa2Cu3O7?x powders

Fine powders of YBa₂Cu₃O_7–x have been synthesized by injecting mixed nitrate solutions of yttrium, barium, and copper into an argon rf thermal plasma. In general, the as-produced powders were dark brown and nonconducting. To obtain superconductivity, the as-produced powders were annealed either in a flowing oxygen tube furnace (at 900C) or in a lowpressure oxygen rf plasma. X-ray powder diffraction, scanning electron microscopy, and centrifugal sedimentation were used for powder characterization. For resistance measurements, bulk samples were prepared by isostatic pressing and tube furnace sintering of the annealed powders. The superconducting transition temperature (at 50% drop of resistivity) was 86 K.     

Chemical reactivities of hafnium and its derived boride, carbide and nitride compounds at relatively mild temperature

MB₂/SiC composites are materials of choice for ultra-high-temperature structural applications, primarily in the aerospace arena. These composites are processed in a hot-press operation at a temperature range of 1900 to 2200°C. This article assesses potential mild-temperature (below 1500°C) chemical reactions that may lead to structures and coatings made of HfB₂/SiC under pressureless or mild-pressure conditions. The reactions are anticipated to be involved in reactive and shape-forming processes, where ceramic precursors and/or reactive powders are incorporated. This article pays special attention to exothermic reactions as well as to formers of a liquid phase; both can aid the desired phase formation, microstructure development, and sintering of the composite under milder conditions than currently practiced. Reactions between loosely mixed powders with melting points significantly above 1500°C were detected by X-ray diffraction (XRD) analyses. Significant solid-phase reactions of the loose powder mixtures were observed at this mild temperature in powder form. Preliminary microstructural studies using scanning electron microscopy (SEM), transmission electron microscopy (TEM), and energy-dispersive X-ray Spectroscopy (EDX) techniques have confirmed the presence of unique reaction mechanisms between the loosely connected particles.Good examples are the reactions between Hf powder and powders of BN or B₄C, all having melting points above 2200°C, which form at 1500°C, or below HfB₂/HfN and HfB₂/HfC crystalline domains, respectively. These reactions are less intuitive than the reaction with B₂O₃, which forms HfB₂/HfO₂, potentially via molten or gaseous phases of boron oxide.     

Microstructures and their stability in rapidly solidified Al-Fe-(V, Si) alloy powders

Microstructures and their stability in as-atomised Al-6.5Fe-1.5V and Al-6.5Fe-1.5V-1.7Si powders have been investigated using transmission electron microscopy (TEM) equipped with energy dispersive X-ray spectroscopy (EDXS), scanning electron microscopy (SEM), X-ray diffraction (XRD) and differential scanning calorimetry (DSC) techniques. It was observed that microstructures of the as-atomised powder particles showed a close relationship with powder particle sizes. The as-atomised powders exhibited three types of microstructures, namely 'zone A', 'zone B' and 'zone C'. The 'zone A' type microstructure consisted of very fine and homogeneous distributed precipitates in the -Al matrix. The 'zone B' microstructure represented the regions consisting of microcellular structures whereas the 'zone C' microstructure represented the regions consisting of coarse cellular structures and globular quasi-crystalline phase particles. Fine powder particles exhibited both 'zone A' and 'zone B' microstructures. The size of 'zone A' decreased with increasing powder particle sizes. The intercellular phases in 'zone B' of both Al-Fe-V and Al-Fe-V-Si were very fine, randomly oriented microquasi-crystalline icosahedral particles. Microstructures of coarse powder particles exhibited both 'zone B' and 'zone C'. The intercellular phases in 'zone C' of Al-Fe-V powders could be Al₆Fe, whereas in Al-Fe-V-Si powders they were probably silicide phase. Formation of powder microstructures may be explained by the interactions between the growing -Al fronts with the freely dispersed, primary phase particles or the solute micro-segregation. Studies using DSC techniques have revealed the microstructural stability of as-atomised powders. There were three DSC exotherms observed in the as-atomised Al-Fe-V powders. The 'zone A' was stable at elevated temperatures and the exotherm peak corresponding to the transformation reactions occurring in 'zone A' was at 360°C. The exotherm peak, which might correspond to the transformation of the globular clusters of microquasi-crystalline icosahedral phase to single-phase icosahedral particles, was at 450°C. The exotherm peak, which may correspond to the formation of Al₁₃Fe₄ and Al₄₅(V, Fe)₇ phases, was at 500°C. In the as-atomised Al-Fe-V-Si powders, only one exotherm was observed with a peak at 400°C. This exotherm may correspond to precipitation of silicide phase particles.     

Nanosized hydroxyapatite powders derived from coprecipitation process

Nanosized hydoxyapatite (Ca₁₀(PO₄)₆(OH)₂ or HA) powders were prepared by a coprecipitation process using calcium nitrate and phosphoric acid as starting materials. The synthesized powders were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and Brunauer-Emmett-Teller (BET) specific area measurment techniques. Single phase HA, with an average grain size of about 60 nm and a BET surface area of 62 m²/g, was obtained. No grain coarsening was observed when the HA powders were heated at 600°C for 4 hours. HA ceramics were obtained by sintering the powders at temperatures from 1000°C to 1200°C. Dense HA ceramics with a theoretical density of 98% and grain size of 6.5 m were achieved after sintering the HA powders at 1200°C for 2 hours. HA phase was observed to decompose into tricalcium phosphate when sintered at 1300°C. The microstructure development of the sintered HA ceramics with sintering temperature was also characterized and discussed.     

Parametric study of the plasma synthesis of ultrafine silicon nitride powders

The high-temperature plasma synthesis of ultrafine silicon nitride (Si₃N₄) powders through the vapour-phase reaction between SiCl₄ and NH₃ in an Ar/H₂ radio frequency (r.f.) inductively coupled plasma was investigated. The experiments were carried out at a 25–39 kW plate power level and at atmospheric pressure. Special attention was paid to the influence of the reactor wall temperature and plasma operating conditions on the quality of the powder. With a cold-wall reactor, the powders obtained were white to light brown in colour and were composed of crystalline, amorphous and Si₃N₄ whisker phases. Both and -Si₃N₄ were present in these products. The NH₄Cl, formed as a by-product of the reaction, could be eliminated from the Si₃N₄ by thermal treatment. The BET specific surface area of the powder after thermal treatment was about 60 m²g^–1. The use of the hot-wall reactor resulted in a considerable reduction in the amount of NH₄Cl remaining in the powder (less than 1 wt%) and a considerable increase in the fraction of the powder obtained in crystalline form. These powders were composed of a mixture of amorphous phase and 30 wt% or more of the and -Si₃N₄ crystalline phases. The BET specific surface area of the powder after thermal treatment was found to be 40 m²g^–1. The experimental results are discussed in relation to their use for optimizing reactor design for the vapour-phase synthesis of ultrafine ceramic powders.     

Solution combustion synthesis of CeO2-CeAlO3 nano-composites by mixture-of-fuels approach

Nano-composites of CeO₂-CeAlO₃ are synthesised by solution combustion method employing (a) urea and (b) a mixture of urea and glycine as fuels with corresponding metal nitrates. The as-prepared powders are all nano-sized (5-30 nm) and the same is confirmed by broadening of the X-ray diffraction peaks and transmission electron microscopy. A starting composition of Ce:Al in the atomic ratio 4:6 gives rise to different phases depending on the fuel being used for combustion. When urea alone is used as fuel, nano-crystalline CeO₂ phase is formed with Al₂O₃ being in the amorphous state. When the mixture of fuels is used, a mixture of nano-sized CeO₂ and CeAlO₃ phases is obtained. However, upon sintering at 1400 ° C in air, the stable phases CeO₂ and -Al₂O₃ are formed in both the cases. Combustion synthesis using mixture-of-fuels is proposed to be a route to stabilise low oxidation compounds such as CeAlO₃.     

Hydrothermal precipitation and characterization of nanocrystalline BaTiO3 particles

Crystalline BaTiO₃ powders were precipitated by reacting fine TiO₂ particles with a strongly alkaline solution of Ba(OH)₂ under hydrothermal conditions at 80°C to 240°C. The characteristics of the powders were investigated by X-ray diffraction, transmission electron microscopy, thermal analysis and atomic emission spectroscopy. For a fixed reaction time of 24 hours, the average particle size of BaTiO₃ increased from 50 nm at 90°C to 100 nm at 240°C. At synthesis temperatures below 150°C, the BaTiO₃ particles had a narrow size distribution and were predominantly cubic in structure. Higher synthesis temperatures produced a mixture of the cubic and tetragonal phases in which the concentration of the tetragonal phase increased with increasing temperature. A bimodal distribution of sizes developed for long reaction times (96 h) at the highest synthesis temperature (240°C). Thermal analysis revealed little weight loss on heating the powders to temperatures up to 700°C. The influence of particle size and processing-related hydroxyl defects on the crystal structure of the BaTiO₃ powder is discussed.     

Characterization and electrical properties of sol-gel synthesized (Sr, Pb)TiO3 powders

Y-doped (Sr, Pb)TiO₃ powders were prepared by a sol-gel route as well as the calcination of gel precursors. The results of DTA/TG showed that the thermal decomposition of dry precursors mainly occurred below 600°C. Meanwhile, infrared ray (IR) spectrum meter, X-ray diffraction (XRD) meter and transmission electron microscope (TEM) were used to characterize the synthesized powders, respectively. Using the synthesized powders as starting materials, Sr_0.5Pb_0.5TiO₃ semiconducting ceramics were fabricated at 1050°C. Sample's room temperature resistivity is 1.51 × 10² · cm, its resistivity jumps more than 5 orders of magnitude above the Curie temperature (T _c). With increasing the soaking time, the room temperature resistivity and the negative temperature coefficient of resistance (NTCR) effect below T _c increased, showing the electrical properties of (Sr, Pb)TiO₃ thermistors are obviously affected by PbO loss.     

Preparation of ceramic composite powders from waste colliery minestones

An investigation was carried out to examine the potential for producing ceramic composites from waste colliery minestones. The nature of the raw materials had a marked influence on the kinetics and the product morphology. The product phases and product composition were dependent on the reaction temperature. Mullite-SiC composite powders could be formed at temperatures below 1300C while Al₂O₂-SiC was the final product of reduction at higher temperatures.Visiting scientist from Changsha Research Institute of Mining and Metallurgy, China.     

Processing and characterisation of sol-gel glasses and powders in the system TeO2-TiO2

Sol-gel processing routes have been developed for the production of thin films and powders in the system TeO₂-TiO₂ from tellurium and titanium alkoxides. The structure and properties of the resultant materials have been characterised as a function of heat treatment temperature. Pure sol-gel derived TeO₂ thin films are difficult to prepare with good optical transparency due to the presence of organic impurities and/or a highly dispersed metallic tellurium phase when heated at temperatures up to approximately 340°C, with crystallisation to -TeO₂ occurring when the heat treatment temperature is further increased. Additions of TiO₂ were found to retard the crystallisation of the -TeO₂ but promote the formation of other TiO₂ or TiTe₃O₈ phases. However, an optimum composition in the range 0.9TeO₂ 0.1TiO₂ was identified, which allows optically transparent thin films to be prepared with high refractive index and offers the potential for practical device manufacture.     

Sapphire matrix composites reinforced with single crystal YAG phases

An investigation of fabrication technology on eutectic composites consisting of Al₂O₃ phases and YAG (Y₃Al₅O₁₂) phases was carried out by applying the unidirectional solidification process. Unidirectionally solidified eutectic composites consisting of 110 sapphire phases and 420 single crystal YAG phases could be fabricated successfully by lowering a Mo crucible at a speed of 5 mm h^–1 under a pressure of 10^–5 mmHg of argon. These eutectic composites have excellent high-temperature properties up to 1973 K. For example, the flexural strength is 360–500 MPa independent of testing temperature from room temperature to 1973 K. Oxidation resistance at 1973 K in an air atmosphere is superior to SiC and Si₃N₄ and the microstructure of these eutectic composites is stable even after heat treatment at 1773 K for 50 h in an air atmosphere.     

Microstructure and Magnetic Properties of Bulk FeCo Alloys Fabricated from Mechanically Alloying and Chemically Synthesized Powders

Three different methods of fabrication of FeCo soft magnetic material using ferromagnetic powders are compared: (i) simple sintering of elemental powders of Fe and Co, (ii) sintering of mechanically alloying FeCo powder, and (iii) sintering of chemically synthesized FeCo powder. The microstructure of ferromagnetic powders and bulk sintered alloys is characterized using scanning electron microscopy and energy-dispersive X-ray spectroscopy analysis. The best magnetic properties with high saturation magnetization, M _s = 211.3 emu/g, are obtained for bulk FeCo alloy sintered from chemically synthesized powder. It consists of nearly spherical FeCo particles with diameters from 5 to 15 μ m. The mean particle size of chemically synthesized FeCo powder can be controlled by changing the melt composition, temperature, and process duration. The relatively large size of FeCo particles reduces the influence of surface oxidation on the particle magnetic properties. The low-cost chemical technology developed is promising for a large-scale production of small FeCo magnetic components of arbitrary shapes with high-dimensional precision.     

Preparation of Y-TZP/AI2O3 whisker preform by an in situ method

In situ growth of AI₂O₃ whiskers into the matrix of Y-TZP (yttria-doped tetragonal zirconia polycrystals) was examined in order to prepare Y-TZP/AI₂O₃ whisker preform for the composites. Various shapes of AI₂O₃ particles were grown by the reaction of AI₂O₃ and AIF₃ powders with moist nitrogen or oxygen gases at high temperature. They showed a trend to change the particle shapes from massive rhombohedron whisker platelet as the processing temperature was increased. These particles, however, grew only on the surface and not inside the pellets It was found necessary to introduce the carrier gas inside the pellets for particle growth to occur internally. AI₂O₃ whiskers can be synthesized inside the pellets by mixing with an organic space-forming agent having a relatively large particle size.     

Phase formation in yttrium aluminum garnet powders synthesized by chemical methods

Yttrium aluminum garnet (YAG) powders were synthesized by precipitation of hydroxides using three types of precursors: nitrates (nitrate process), isopropoxides (alkoxide process), and isopropoxides chelated with ethyl acetoacetate (modified alkoxide process). The phase development in the powders during heat treatments was investigated with DTA and XRD. An intermediate hexagonal YAlO₃ (YAH) phase was formed at 800°C in all powders regardless of the synthesis processes, but its complete transformation to YAG at higher temperatures (1000°C) occurred only in the powders prepared by the nitrate and modified alkoxide processes. The alkoxide process led to the largest deviation from the bulk composition, producing a single phase of YAH that transformed into YAG plus a stable YAM (Y₄Al₂O₉) phase. The modified alkoxide process led to the most homogeneous bulk composition, resulting in the least amount of YAH in the powder. The poor chemical homogeneity in the powders prepared by the nitrate and alkoxide processes was attributed to the segregation of the hydroxides and to the presence of the double alkoxide, respectively.