Kinetic modelling of nickel powder precipitation by high-pressure hydrogen reduction

The active mechanisms in the precipitation of nickel powder by hydrogen reduction were investigated by means of mathematical models based on the moment form of the population balance equation (PBE). The objective of the work was to establish the mechanisms involved in powder formation and how these are affected by the presence of impurities. The effects of two major impurities were considered namely; iron, inherently present as ferrous sulphate, and a morphology modifier, a polyacrylic acid derivative used as an additive. Experiments were conducted on a laboratory and pilot-plant scale using a 0.5 and 75 L stainless steel autoclave, respectively. Nickel powder samples were collected from the autoclaves after each successive batch reduction (densification) and the particle size distribution (PSD) analysed using a laser diffraction technique. The PSD data was then transformed into moments and the experimental values were compared with those simulated using different models based on the moment form of the PBE. Five models were tested namely: (a) aggregation-only; (b) aggregation and growth; (c) nucleation and aggregation; (d) nucleation and growth and (e) aggregation and breakage. Under standard operating conditions, the process was best simulated by a size-independent aggregation and growth model in the early stages of the cycle, with breakage and growth becoming significant in later stages of the cycle when large particles have been formed. Crystallisation in the presence of Fe was characterised by a size-independent aggregation and growth model with varying degrees of nucleation depending on the Fe concentration and the available surface area. At modifier dosages of 0.25 and 5 vol% the process was best modelled by a size-independent aggregation and growth model coupled with a constant breakage frequency model. Based on the mathematical modelling results and evidence from scanning electron micrographs, the spherically shaped nickel powder particles were proposed to be formed through the formation of a pre-cursor by secondary aggregation followed by spherulitic growth. The degree of compactness of the spherulites was proposed to be determined by the number of active growth sites on the nickel particle surface. The morphology modifier was found to act as a growth inhibitor, decreasing the number of growth sites leading to more open spherulites. Iron was found to induce surface nucleation, thus, creating more growth sites on the particle surface and leading to more compact spherulites.     

Effect of Al2O3 particle size on preparation and properties of ZTA ceramics formed by gelcasting

Zirconia-toughened alumina (ZTA) ceramics were prepared using three different kinds of Al₂O₃ powders (marked PW-A average particle size: 7.53 μm, marked PW-B average particle size: 1.76 μm, marked PW-C average particle size: 0.61 μm) by gelcasting. Effect of Al₂O₃ particle size on zeta potential, dispersant dosage and solid volume fractions of ZTA suspensions as well as the mechanical properties of ZTA green bodies and ceramics were investigated. The optimum dosages of dispersant for ZTA suspensions prepared by PW-A, PW-B and PW-C are 0.4 wt%, 0.5 wt% and 0.7 wt%, respectively. The highest solid volume fractions of ZTA suspensions can reach 62 vol% (SP-A), 60 vol% (SP-B) and 52 vol% (SP-C), respectively. The green bodies show a bending strength as high as 20 MPa, which can meet the requirement of machining. The Al₂O₃ powder with fine particle size is beneficial to the improvement of mechanical properties. The ZTA ceramics prepared by PW-B Al₂O₃ powder show the highest bending strength (680 MPa) and toughness (7.49 MPa m^1/2).     

Lyothermal synthesis of nanocrystalline BaSnO3 powders

The synthesis of BaSnO₃ powders has been investigated at lyothermal conditions (temperature of 250 °C; t = 6 h), starting from SnO₂·xH₂O and Ba(OH)₂ and methanol, ethanol, isopropanol and acetone as solvents. Among them isopropanol was found to be the most suitable medium for preparing BaSnO₃. By addition of the modifier Genapol X-080 during the processing, the BET specific surface area of the end-powder was increased by a factor of 10. The as-prepared powder consisted of BaSn(OH)₆. The thermal behavior, the crystallization behavior and the structure evolution of the powder during heating treatment have been studied with the TG–DTA–MS, XRD and FTIR. The weight loss of the as-prepared powder of about 12 wt% heated up to 1200 °C is mainly attributed to the dehydration around 260 °C which leads to the structure rearrangement and the building of the [SnO₆] octahedra. At this temperature BaSn(OH)₆ converts to an amorphous phase, from which BaSnO₃ nucleates and grows with increasing temperature. The obtained BaSnO₃ powders had a BET specific surface area of 16.56 m²/g and a primary crystallite size of 49 nm.     

Synthesis and characteristics of nanocrystalline 3Y-TZP and CuO powders for ceramic composites

A weakly agglomerated 3Y-TZP powder with 100% tetragonal crystal structure and a primary crystallite diameter of 8 nm was prepared by co-precipitation of metal chlorides in an ammonia solution, followed by extensive washing with ethanol, drying and calcining at 550 °C. Powder characteristics as function of thermal treatment are discussed. A copper oxalate precipitation for the preparation of nanocrystalline CuO powders was optimised in order to minimise aggregation and agglomeration. The influence of calcination procedure and synthesis medium on several powder characteristics of the CuO powders were investigated in detail. Oxalate precipitation in ethanol followed by sequential drying and calcination in air at 250 °C in an open tubular furnace with proper air-powder contact area was found to be the optimal procedure for producing nanocrystalline single-phase CuO powder with small aggregates and weak agglomerates. With this optimal procedure a CuO powder with crystallite diameter and BET equivalent particle diameter of respectively 12 and 20 nm was obtained.     

Fabrication and characterization of WO3 flocky microspheres induced by ethanol

The novel tungsten trioxide flocky microspheres induced by ethanol were successfully obtained via a simple and convenient hydrothermal route. The as-prepared products were characterized by X-ray powder diffraction, scanning electron microscopy, transmission electron microscopy, BET surface area measurement and UV-Vis diffuse reflectance spectroscopy. WO₃ powder prepared with volume ratio (v_ethanol/v_water) of 40% revealed a complete flocky microsphere structure with particle size of 3.0-4.0 μm and exhibited good photochromic property. The possible formation mechanism of the flocky microspheres was proposed and the improved photochromic properties were also investigated.     

Correlation of compaction pressure, green density, pore size distribution and sintering temperature of a nano-crystalline 2Y-TZP-Al2O3 composite

Highly sinter-active nano crystalline composite powder of 2 mol% yttria doped tetragonal zirconia polycrystal (2Y-TZP) with 2 wt% alumina was synthesized by co-precipitation method. Crystallization temperature of the amorphous precursor powder, measured from simultaneous thermogravimetric (TG) and differential thermal analysis (DTA) techniques was found to be ∼470 °C. The powder was calcined at different temperatures in the range of 700-1000 °C. XRD patterns of the calcined powders revealed the presence of a single tetragonal phase. Particle size of the calcined powder measured by different techniques (X-ray line broadening, BET surface area and laser scattering technique) indicated an increase in the average particle size with calcination temperature. The study of compaction behaviour revealed the presence of soft agglomerates in the calcined powder. Pore size distribution of the green compacts obtained from a mercury porosimeter was found to be monomodal above a critical pressure. The onset temperature of sintering was found to increase with calcination temperature. Powders calcined at 800 °C and 900 °C had shown better sinterability at 1200 °C owing to the presence of finer pores with a narrow size distribution in the green compacts. Sintering behaviour of the powder calcined at 700 °C was found to be marginally poorer in comparison to the other samples, whereas the powder calcined at 800 °C had demonstrated best densification behaviour, especially when compacted at 300 MPa.     

Synthesis and characterization of high-purity aluminum nitride nanopowder by RF induction thermal plasma

High-purity aluminum nitride nanopowder was synthesized using the RF induction thermal plasma technique. The nitrogen gas flow rate, plasma power and reactor pressure were controlled to increase the conversion rate of Al powder to AlN nanoparticles. The compositions of the obtained powders were investigated through XRD and EDS analysis. The synthesized aluminum nitride nanoparticles included polygonal and rod-shaped nanoparticles and ultra-fine particles below 10 nm. The particle sizes generally ranged from 20–60 nm in TEM analysis. The specific surface area, band structure and impurities of aluminum nitride nanoparticles were also evaluated by BET, FTIR and ICP-OES analysis.     

SDS/MAP复配表面活性剂改性纳米氢氧化镁作用机理研究

十二烷基硫酸钠（SDS）/磷酸酯（MAP）复配表面活性剂作为改性剂,对纳米氢氧化镁进行改性研究。通过X射线衍射（XRD）、透射电镜（TEM）、红外光谱分析（FT-IR）、BET法比表面积测定和在液体石蜡中的悬浮液体积测定等手段,研究了SDS与MAP以1︰1的质量比复配时其添加量对改性纳米氢氧化镁性能的影响,并初步探讨了改性机理。结果表明：随着SDS/MAP添加量的增加,样品表面的疏水性能呈现先增加后减小的趋势,其用量为样品质量的0.2%时达到最大值;粒径呈现先减小后增大又减小的变化规律,其用量分别在0.2%和0.5%时出现拐点;比表面积的变化规律与粒径一致。说明在水相中随着SDS/MAP添加量的不同,其可能分别以双分子层和单分子层吸附于氢氧化镁颗粒表面。     

Low temperature synthesis of nanocrystalline magnesium aluminate spinel by a soft chemical method

A new simple soft chemical method – synthesizing nanocrystalline MgAl₂O₄ spinel powder with oxalic acid as organic template and nitric acid as an oxidizing agent – is described. The method was developed with the objective of obtaining phase pure nanocrystalline MgAl₂O₄ spinel powder with uniform particle size and morphology at a much lower temperature than that used by conventional methods. The synthesized powders were characterized by X-ray diffractometry (XRD), thermogravimetry (TGA), Fourier transform infrared spectroscopy (FTIR), surface area analysis (BET) and field emission scanning electron microscopy (FE-SEM). The average crystallite size of the single phase material was 30 nm. Through this method, porous MgAl₂O₄ powder with a high surface area of 162.2 m²g⁻¹ and 141 m²g⁻¹ was obtained at 600 °C and 700 °C, respectively.     

Sonochemical synthesis of LaMnO3 nano-powder

We report the preparation of LaMnO₃ nanosized powder by the sonochemical process. Sodium dodecyl sulphate (SDS) was used as surfactant, to prevent agglomeration. The particle size obtained in this method was 19–55 nm. The phase formation temperature of LaMnO₃ was 700 °C which is lower than other conventional processes. So sonochemical process is cost effective and it is more acceptable considering its ease of preparation in comparison to other conventional processes. Powder synthesized was characterized by measuring crystallite size, specific surface area, morphology and by thermal analysis. The particle sizes of the powders were controlled by calcinations schedule. Narrow size distribution and core and shell structure of the prepared powder was revealed by transmission electron microscopy.     

Formation enthalpy and magnetic properties of Bi-YIG powders

The formation enthalpy and magnetic properties of bismuth-doped yttrium iron garnet powders were investigated. The formation enthalpy and the crystallization temperature both decreased with increasing bismuth substitution for Bi_xY_3−xFe₅O₁₂ (0.25 ≦ x ≦ 1.25) powders prepared by the coprecipitation process. Bi substitution for Y can significantly reduce crystallization temperature for bismuth-doped yttrium iron garnet powders, and the magnetic properties (saturation magnetization, remanence, and coercive force) are independent of Bi substitution amounts. The average particle size has been determined by the specific surface area. As Bi substitution for Y increased, the average particle size also increased, while the specific surface area decreased.     

A simple and efficient preparation of LaFeO3 nanopowders by glycine-nitrate process: Effect of glycine concentration

LaFeO₃ perovskites have been prepared by the glycine-nitrate process (GNP) at various glycine-to-nitrate molar ratios. The perovskites have been systematically characterized by X-ray diffraction, BET surface area, scanning electron microscopy, transmission electron microscopy and temperature-programmed reduction to study the effect of glycine concentration on various properties of LaFeO₃. The X-ray diffraction patterns of the as-prepared and calcined samples show the formation of orthorhombic phase without any impurities. The BET specific surface areas of various perovskites increased with an increase in glycine-to-nitrate ratio (GNR) of 2.0 but were nearly constant at higher ratios. The scanning electron microscopy indicates that the prepared material is flake-like at GNRs ≤1.5 and exists as agglomerated particles at GNRs ≥2.0. The particle size of the as-prepared samples was in the range of 30-130 nm depending on the GNR and the calcined samples exhibited particle size in the range of 60-160 nm. The samples that were prepared at GNR < 1.5 did not show any peaks in temperature-programmed reduction, but the samples prepared at a GNR of 2.0 and above showed the reduction of Feⁿ⁺.     

Preparation of porous carbons from thermoplastic precursors and their performance for electric double layer capacitors

Porous carbons with high surface area were successfully prepared from thermoplastic precursors, such as poly(vinyl alcohol) (PVA), hydroxyl propyl cellulose and poly(ethylene terephthalate), by the carbonization of a mixture with MgO at 900 °C in an inert atmosphere. After carbonization the MgO was dissolved out using a diluted sulfuric acid and the carbons formed were isolated. The mixing of the PVA carbon precursor with the MgO precursors (reagent grade MgO, magnesium acetate or citrate) was done either in powder form or in an aqueous solution. The BET surface area of the carbons obtained via solution mixing could reach a very high value, such as 2000 m²/g, without any activation process. The pore structure of the resultant carbons was found to depend strongly on the mixing method; the carbons prepared via solution mixing were rich in mesopores, but those produced via powder mixing were rich in micropores. The size of mesopores was found to be almost the same as that of the MgO particles, suggesting a way of controlling the mesopore size in the resultant carbons. Measurement of capacitance was carried out in 1 mol/L H₂SO₄ electrolyte. The porous carbon with a BET surface area of 1900 m²/g prepared at 900 °C through solution mixing of Mg acetate with PVA showed a fairly high EDLC capacitance, about 250 F/g with a current density of 20 mA/g and 210 F/g with 1000 mA/g. The rate performance was closely related to the mesoporous surface area.     

Yttria stabilized zirconia formed by micro ceramic injection molding: Rheological properties and debinding effects on the sintered part

Micro Ceramic Injection Molding (μCIM) is a near net-shape process to produce smaller and intricate parts at a competitive cost. The application of nano-sized ceramic powder in μCIM has the advantages of fine grain size growth and good surface finish. However, the nano size effect causes agglomeration and low powder loadings, which result in defects during the μCIM process and in the sintered components. This study extensively investigated the debinding and sintering of yttria-stabilized zirconia (YSZ), as well as its rheological properties, using polypropylene (PP) as the primary binder and palm stearin as the secondary binder. 50 nm Yttria stabilized zirconia (YSZ) powders were mixed with palm stearin and PP at a powder loading of 37–43 vol%. The results of rheological studies showed that the feedstock had a dilatant flow characteristic and a viscosity of around 10–40 Pa s. Feedstock with 38 vol% powder loading had the lowest activation energy of 9.48 kJ/mol. The green part of the injected feedstock had flexural strength ranging from 13 to16 MPa, within which the feedstock with 43 vol% powder loading had the highest green density. Solvent debinding was carried out at three temperatures (50, 60, and 70 °C) using heptane. A large porous region was clearly identified at 70 °C compared with 50 °C. A debinding split furnace with argon gas was used to remove PP at 450 °C for 4 h. The debound samples did not shrink when 94%–98% of the binder system was removed. All debound samples sintered at 1350 °C and 41 vol% had the highest mechanical properties with hardness of 900 HV and a flexural strength of 400 MPa.     

A TEM-based method as an alternative to the BET method for measuring off-line the specific surface area of nanoaerosols

At the present time, no stabilised method exists allowing an estimation of the specific surface area for airborne nanostructured particles (nanoaerosols). Recent toxicological studies have, however, revealed biological effects linked to the surface area of these particles. Only the BET method, which can determine the specific mass surface area of a powder, constitutes a reference both in toxicology and in the materials domain. However, this technique is not applicable to nanostructured aerosols given the mass quantities of particles required (between approximately some mg to hundreds of mg taking into account the limit of quantification of existing BET instruments).To characterise the specific surface area of airborne nanostructured particles, a method based on analysing transmission electron microscopy (TEM) images is proposed. This has recourse in particular to previous work carried out in the area of nanoparticles originating from combustion (soot), and takes into account structural parameters of nanostructured particles including the number distribution of primary particles, their overlap coefficient and the fractal dimension of agglomerates and aggregates.The approach proposed in this work was applied to five commercially-available nanostructured powders of differing natures (SiO₂, ZrO₂, Al₂O₃, Fe₂O₃ and Fe₃O₄). This first involved their prior analysis by the BET method and then being placed in suspension in aerosol form using a vortex-type shaker system. The procedure to calculate the specific surface area using image analysis was then applied to the sampled aerosols and compared to the BET measurements. The experimental results obtained on the five nanostructured powders cover a range of specific surface areas from 20 to 200 m²/g, the primary particles having mean diameters varying from 7 to 47 nm. Close agreement was observed between the two approaches which, taking into account measurement uncertainties, are statistically equivalent at significance level α = 0.05.     

Influence of composite LiCl-KCl molten salt on microstructure and electrochemical performance of spinel Li4Ti5O12

A series of spinel Li₄Ti₅O₁₂ samples were synthesized via a composite molten-salt method (CMSM) using the mixtures of LiCl and KCl with different L values (L is defined as the molar ratio of LiCl:KCl) as the reaction media. It is found that the melting point of the composite molten salt can effectively influence the formation of particles, and leads to different electrochemical performances of the as-prepare Li₄Ti₅O₁₂. The investigations of X-ray diffraction (XRD), particle size distribution (PSD), Brunauer-Emmet-Teller (BET) surface area, and scanning electron microscopy (SEM) indicate that the as-prepared Li₄Ti₅O₁₂ with L = 1.5 is a pure phase, and has uniform homogeneous octahedral shape particles, rather narrow PSD, and high BET surface area. Electrochemical tests show that the optimized Li₄Ti₅O₁₂ with L = 1.5 has an initial discharge capacity of 169 mAh g⁻¹ and an initial charge-discharge efficiency of 94% at 0.2 C rate, and achieves good rate performances from 0.2 C to 5 C.     

Electrochemical characterization of a new binary oxide of Mo with Co for O2 evolution in alkaline solution

The α-CoMoO₄ oxide has been obtained by a precipitation method and investigated for the first time for electrocatalysis of the oxygen evolution reaction (oer) in alkaline medium. This method produced the pure crystalline CoMoO4 monoclinic phase with crystallite size ∼46 nm and lattice constants: a = 9.666 Å, b = 8.854 Å, c = 7.755 Å and β = 113.82°. The average particle size (based on area density) and the BET surface area of powders of the oxide were 11.58 μm and 9.4 m² g⁻¹, respectively. Results show that the new oxide is quite active for the oer. Values of the Tafel slope and the reaction order with respect to OH⁻ concentration are observed to be ∼60 mV and ∼1, respectively.     

A review of the control of pore structure in MgO-templated nanoporous carbons

Nanoporous carbons with a high surface area were directly prepared from various carbon precursors without any stabilization and activation processes. Various carbon precursors, including poly(vinyl alcohol), poly(ethylene terephthalate), polyimide, coal tar pitch, were used and MgO itself, Mg acetate, Mg citrate, Mg gluconate and Mg hydroxy-carbonate were employed as MgO precursor. Carbon precursor was mixed with MgO precursor in different ratios either in powder (powder mixing) or in solution (solution mixing), and heat-treated at 900 °C in inert atmosphere. MgO formed in the carbonization products was dissolved out using a diluted acid. BET surface area of the carbons obtained could be reached to high value, as high as 2000 m²/g, even though any activation process was not applied. Most carbons prepared through this method were rich in mesopores. Size of mesopores in the resultant carbons was tunable by selecting MgO precursor and relative volume between mesopores and micropores was controlled by carbon precursor.     

Solid oxide derived from waste shells of Turbonilla striatula as a renewable catalyst for biodiesel production

Biodiesel production via transesterification of mustard oil with methanol using solid oxide catalyst derived from waste shell of Turbonilla striatula was investigated. The shells were calcined at different temperatures for 4 h and catalyst characterizations were carried out by X-ray diffraction (XRD), scanning electron microscope (SEM), energy dispersive spectrometer (EDS), Fourier transform infrared spectrometer (FT-IR), thermogravimetric analysis (TGA)/differential scanning calorimetry (DSC) and Brunauer-Emmett-Teller (BET) surface area measurements . Formation of solid oxide i.e. CaO was confirmed at calcination temperature of 800 °C. The effect of the molar ratio of methanol to oil, the reaction temperature, catalyst calcination temperature and catalyst amount used for transesterification were studied to optimize the reaction conditions. Biodiesel yield of 93.3% was achieved when transesterification was carried out at 65 ± 5 °C by employing 3.0 wt.% catalyst and 9:1 methanol to oil molar ratio. BET surface area indicated that the shells calcined in the temperature range of 700 °C-900 °C exhibited enhanced surface area and higher pore volume than the shells calcined at 600 °C. Reusability of the catalysts prepared in different temperatures was also investigated.     

Agglomeration of α-Al2O3 powders prepared by gel combustion

Ultrafine α-Al₂O₃ powders were prepared by a gel combustion method and the agglomeration characteristic of the resultant powders was studied. A variety of fine crystallite α-Al₂O₃ powders with different agglomeration structures could be obtained by altering the citrate-to-nitrate ratio γ and calcining the precursors at 1050 °C for 2 h. All the powders were of nearly equivalent crystallite size (60–80 nm) except for the P1 powder (113 nm) from the gel with γ = 0.033. The primary crystallites of the obtained α-Al₂O₃ powders were formed into large secondary particles with different degree of agglomeration. Except for the powder P1, the mean particle sizes from specific surface area and particle size distribution measurement increase with increasing citrate-to-nitrate ratio in the fuel-lean condition and decrease in the fuel-rich condition. Densities of alumina ceramics from powders P4 and P5 sintered at different temperatures were relatively low due to the wide particle size distribution.