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By X. L. Song

In this paper, ZrSiO4-Cd(S1-xSex) inclusion pigments were synthesized by hydrothermal method. Microstructure, morphology and properties of the powder were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), infrared spectroscopy (IR) and CIE chromaticity, respectively. It shows that, precursors obtained at pH is about 6.0 are sol and products with higher crystallinity, red hues (a*=38.23) and inclusion ratio when hydrothermal synthesis temperature is 180? and holding time is 12h. Hydrothermal reaction mechanism was further analyzed as well. In particular, an ideal model of pigment formation was proposed.

Jan 1, 2014

By Hung-wei Liu, Kevin Plucknett

Early attempts to manufacture titanium aluminides using blended elemental powders, through powder metallurgical processes, have been obstructed due to serious swelling during sintering. Although the use of pre-alloyed powder can avoid this undesired expansion problem, there are limited commercial powder sources available. Therefore, in the present research, fundamental studies on the synthesis of dual-phase (? plus a2) Ti48Al intermetallic materials is undertaken, in particular assessing powder manufacture. In order to produce pre-alloyed powders, highly porous Ti48Al pieces are initially sintered from elemental Ti and Al powder blends, and subsequently pulverised into powders. The powder size is then further reduced by use of either dry or wet milling processes (i.e. shatterbox grinding, attrition, or ball milling). Among these methods, shatterbox grinding has shown the highest efficiency, with a slight mechanical alloying effect observed. The manufactured powder morphologies and phases, as well the sintered material, will be discussed.

Jan 1, 2015

By A. Arenas-Flores, Pandiyan Thangarasu, J. P. Hernández-Lara, F. R. Barrientos-Hernández, J. A. Romero-Serrano, A. Hernández-Ramírez, M. Pérez-Labra

BaTiO3 doped with Gd3+, was synthesized from BaCO3, TiO2, and Gd2O3 as powders using the solid state reaction method (Ba1-xGdxTi1-x/4O3). The milling of the precursors was performed in an agate mortar with acetone as control means and compositions x = 0.001, 0.005, 0.05, 0.15, 0.25, 0.35 Gd3+ (wt%). Firstly, the powder mixture was decarbonated at 900 °C for 8 h, after it was sintered at 1400 °C for 5 h. Tetragonality of synthesized BaTiO3 doped with Gd3+ was analyzed by X-ray diffraction (XRD), scanning electron microscopy (SEM) and Raman spectroscopy (RS). Subsequently, the powders sintered were uniaxially compacted cold until to obtain pellets of about 10 mm in diameter; which again were sintered at 1400 °C for 4 h. XRD patterns and Raman spectra results revealed that the crystal phase of the obtained particles was predominately tetragonal BaTiO3.

Mar 1, 2017

By H. Zhong, S. Wang, Q. Lin

To improve the flotation performance of chalcopyrite collector, 2-(tert-butoxy)ethyl xanthate (TBEX) and its derivative O-(2-(tert-butoxy)ethyl)-N-ethyl-thionocarbamate (TBEETC) were designed and prepared by the introduction of a 2-(tert-butoxy) ethyl group into xanthate and thionocarbamate. TBEX and TBEETC were both prepared via the one-pot method with superior efficiency, which has significant commercial implications. The micro-flotation tests demonstrated that compared with sodium isobutyl xanthate (SIBX) and O-isopropyl-N-ethyl-thionocarbamate (Z-200), TBEX and TBEETC both possessed better collecting ability and selectivity for chalcopyrite. DFT calculations and XPS were utilised to investigate the flotation mechanism involving TBEX or TBEETC and chalcopyrite. The results demonstrate that although 2-(tert-butoxy) ethyl group does not interact with minerals directly, its introduction reduces the energy of HOMO, so that they can better accept electrons instead of donating electrons which leads to better interaction with copper atoms rather than iron atoms. Keywords: Chalcopyrite, flotation, thionocarbamate, xanthate, synthesis

Jan 1, 2020

By Z. Yang, X. Bian

"The synthesis of 3-hydroxy-2-naphthyl hydroxamic acid (H2O5) as a collector for bastnaesite is described. The flotation performance of H2O5 with respect to bastnaesite was investigated by flotation tests, measurements of the surface adsorption capacity, and polarizing microscopy. The results indicated that H2O5 exhibits superior collecting performance compared with direct flotation recovery of bastnaesite, with recoveries above 90% at pH 8–9. The adsorption mechanism of H2O5 on bastnaesite was studied by solution chemistry analysis and ?-potential tests. The results showed that the adsorption of H2O5 is associated with the types and concentrations of hydrolysis products of rare earth cations on the bastnaesite surface. At pH 8–9, the hydrolysis-dominant components RE(OH)2+ and RE(OH)2 + of the rare earth cations were adsorbed onto the bastnaesite surfaces, which were considered to be the major positive active points and were beneficial to chemical adsorption of the reagents. The pH range of 7–10 was optimum for bastnaesite floatability, and the adsorption of H205 on bastnaesite was by means of chemical adsorption through formation of a five-membered ring chelate. IntroductionThe rare earth elements (REEs) have long been known as ‘industrial gold’ and are widely used in the petroleum, chemical, ceramic, metallurgical, and permanent magnet material industries because of their special physicochemical properties (Chen, 2011; Krishnamurthy and Guptac, 2002; Esquivel, Bohe, and Pasquevich, 2002; Abrahami, Xiao, and Yang, 2015). Demand for REEs is growing in response to continuous advances in science and technology. Currently, most REEs are extracted from bastnaesite ((Ce,La)CO3F) (Chelgani et al., 2015; Yosry, 1990), which is recovered from rare earth ores by flotation. Typically, hydroxamic acids are used as bastnaesite collectors (Xu, 2015; Ren, 1997; Mousumi and Venugopal, 2016). Research into the mechanism of interaction between hydroxamic acids and bastnaesite is important for improving the recoveries of bastnaesite. However, there have been few studies that examine this mechanism."

Jan 1, 2017

By Binbin Luo, Northeastern University, Chuanyao Sun, Jie Liu, Yimin Zhu, Yanjun Li

"A series of new type collectors a-bromo-saturated fatty acids, CH3(CH2)5CHBrCOOH (a-BHA), CH3(CH2)7CHBrCOOH (a-BDA), CH3(CH2)9CHBrCOOH (a-BLA), CH3(CH2)11CHBrCOOH (a-BMA) were synthesized from saturated fatty acids and bromine by solvent-free method (Hell-Volhard-Zelinski reaction) in laboratory. The micro-flotation tests of quartz mineral were conducted at a relatively low temperature of 15 °C. The adsorption mechanism of such collectors on quartz mineral surface were established by zeta potential measurements, in conjunction with the results of quartz micro-flotation tests. The flotation results showed that the collecting ability is in the order of a-BMA > a-BLA > a-BDA > a-BHA for the flotation of quartz mineral, which also demonstrating that the a-bromo-saturated fatty acids (a-BFAs) are new selective collectors for reverse flotation to remove quartz mineral from iron ores at a relatively low temperature.INTRODUCTIONThe requirement of higher pulp temperature to maintain the activity of fatty acid anionic collectors which have been widely applied in technological process of iron ores reverse flotation lead to a great deal of energy consumption.The purpose of this paper is to synthesize a new modified collector with carbon chains from eight to fourteen atoms, with strong electronegativity bromine atom introduced into a-carbon position to improve the activity and solubility of the reagent so that it can be adopted at a comparatively low pulp temperature. The collecting performances of these new collectors on quartz surface were studied, and the structure - properties were discussed in light of zeta potential measurements and quantum chemistry calculations."

Jan 1, 2016

Al2O3,-WC Composite powder for cutting tools was synthesized by self-propagating high-temperature synthesis using A1 powder as a reducing agent. WC, W2C and Al2O3 were concurrently formed in WO3Al-C system. It was found that the complete reaction was achieved with excessive addition of carbon and appropriate processing parameters such as degree of dilution, particle size of aluminum, compaction pressures of green pellets and carbon source. The final product which was leached by 50% HN03+HF diluted solution was consisted of Al2O3-55wt% WC having 2-3um of mean particle size.

Jan 1, 1999

By S Serp, M Duchateau, P Chevreux

Molten salt reactor (MSR) is a promising advanced reactor system aiming to the transmutation of minor actinides such as americium in order to reduce the inventory of ultimate nuclear waste. The fuel is a molten salt in which actinides are homogeneously dissolved in the liquid phase. A chloride salt may be retained for this concept, as it provides low melting point, high solubility of actinides, harder neutron spectrum. To avoid corrosion and precipitation issues, molten salt composition has to be carefully controlled with impurity content as low as possible. Obtaining pure actinide chlorides without contaminants such as oxide, oxychloride, hydroxide and water is still a challenge. To prepare actinide-bearing salt, the chlorination of actinides oxides was investigated in an unstirred reactor under flowing gas as solid-gas reaction. The carbochlorination of PuO2 were performed in the temperature range of 600 to 800°C with chlorine gas as a chlorinating agent and the presence of solid carbon. PuCl3 was successfully synthesised by this method and characterised by X-ray diffraction measurements but some impurities such as oxide phase remain inside the formed product. Refinements of anhydrous and hydrated PuCl3 phases by Le Bail method were also performed for crystalline materials definition. Conversion mainly depends on the chlorinating temperature and the contact between the oxide and the chlorinating agent. A conversion value of 70–80 per cent was achieved at 700°C from PuO2 with quite high specific surface area. The conversion rate was not improved with increasing the chlorination time. The volatilisation of Pu was observed during the carbochlorination experiments. To avoid a loss of Pu caused by sublimation, the chlorination temperature should be limited to 650°C despite that the conversion of PuO2 to PuCl3 was enhanced by increasing temperature. Both carbochlorination and hydrochlorination of AmO2 were also carried out leading to the formation of AmCl3. These first results suggest that americium oxide was chlorinated more readily than plutonium oxide. The purity of produced PuCl3 and AmCl3 still deserves further investigations.

Jun 19, 2024

By Shigehito Deki

"A new wet process has been developed for the synthesis of various kinds of oxide thin films on various kinds of substrates, even which have complex surface morphology, from aqueous solution. The process was named as the LPD, Liquid Phase Deposition, method, which has some advantages over the conventional dry processes. This process can be applied to an on-site synthesis of advanced materials in the thin film technology. In this paper, some current topics on the synthesis of the composite thin oxide films by the LPD method, are presented.IntroductionGenerally, metal oxide thin films have been made by different preparative processes such as r.f. sputtering, chemical vapor depositon, CVD, laser ablation and sol-gel method, etc [1-3]. Each method has it own advantages and disadvantage. In some cases, the process is not suitable for the preparation of thin film on substrate with large surface area or complex surface morphology, and makes the deposition apparatus complicated and expenisve. By using Liquid Phase Deposition, LPD, method which overcomes some of those problems, metal oxide or hydroxide thin film can be formed on the substrate with large surface area and complex surface morphology, which are immersed into the aqueous solution only at ambient temperature and under atmosphere without any special equipments and high energy. And also, multicomponent oxide thin films can be formed readily by mixing solutions containing the objective metal ions, because it is performed in the aqueous solution which is typically a homogeneous mixing system. This process utilizes ligand-exchange, hydrolysis, equlibrium reaction of metal-fluoro complex species, MF x (x-2n>-, and F consumptive reaction. In the aqueous solution, MFx<x-2n>-is hydrolyzed with water to release F ions by a ligand exchange equilibrium reaction as following;"

Jan 1, 2000

By Hong Ro Lee, Seang Suk Cho, Byung Sun Chun, Chang Whan Won

"The preparation of Al203-SiC-TiC composite powders was studied by SHS process using silica (source of Si02) powder instead of Si which is expensive. And, aluminum powder was used as reducing agent of silica and charcoal activated was used as carbon source. Effects of the molar ratio in raw material mixtures and compaction pressure and initial temperature of reactant on the products and combustion process were studied. The most important variable affecting the synthesis of Al203-SiC-TiC was the molar ratio of carbon. The combustion reaction generated in powder state without preheating. But the unreactants exist in the product on all molar ratio. When the preheating temperature is over 400 °C, the combustion reaction was able to be generated in pellet state. Without preheating, the combustion reaction was possible by Ti02 addition. The optimum condition in this system was the molar ratio of Si02:Ti02:Al:C=2.5:0.5:4:3.1. INTRODUCTIONCeramics have demonstrated a capability as a cutting tool, especially in competition with WC-Co cermets (ceramic-metal composites) as inserts for metal turning and milling operation. The advantage of ceramics compared with carbides is retention of high hardness, strength, and chemical inertness to temperatures in excess of 1000 ·c . This allows use of the ceramics at much higher machining speeds than can be tolerated by carbides. However, the ceramics have lower toughness than the carbide materials, and have only been used successfully in the limited operations of turning and milling. There are several classes of cutting tools. The addition of TiC or PSZ, or both, and reinforcement with SiC overcame the poor fracture toughness and thermal-shock resistance that limited Al203 use in the past [1]."

Jan 1, 1998

By Sutham Niyomwas

Keywords: Al2O3-SiCW, Ceramic Matrix Composite, Carbothermal Reduction, Kaolin The formations of Al2O3-SiCw composite have been obtained in situ by carbothermal reduction of a mixture of kaolin and activated carbon. The reaction temperature was controlled at between 1400°C to 1600°C. The synthesized products were mixtures of alumina and silicon carbide in the form of whiskers. The effects of milling time of precursors and reaction temperature are presented. XRD and SEM analyses indicate complete reaction of precursors to yield Al2O3-SiC as product powders, with the SiC having porous and whisker morphology.

Jan 1, 2005

By Alaina Mallard, Jannette Chorney, David Hutchins, Grant C. Wallace, Jerome P. Downey

Current commercial processes for producing ceramic carbides require temperatures of 1400–2000 °C and often use extensive milling operations to produce a powder product. A process that could reduce the energy requirements of commercial carbide production could allow for these materials to be implemented in a greater number of applications. In this study, tungstate (WO4 2−) and silicate (SiO3 2−) anions were adsorbed onto activated carbon and converted into silicon carbide (SiC) whiskers and a mixture of tungsten and tungsten carbide (W/WC) crystals via carbothermal reduction using inert and reducing gas atmospheres at temperatures much lower than what is required by current commercial processes (950 °C for W/WC/W2C and 1200 °C for SiC). The adsorption process was statistically-optimized via a central composite response surface analysis using DesignExpert 9. Inductive coupled plasma optical emission spectroscopy (ICP-OES) was used to measure, and optimize, adsorption efficiency while the carburization products were characterized using X-ray diffraction and scanning electron microscopy.

Mar 1, 2017

By H. Hahn, B. H. Kear, K. Kan, S. C. Danforth, G. Skandan, W. Chang

"A new chemical synthetic process for the production of non-agglomeratednano structured ceramic (n-ceramic) powders, starting from metalorganic precursors, is described. The process combines rapid thermal decomposition of a precursor/carrier gas stream in a hot tubular reactor with rapid condensation of the product particle species on a cold substrate. Critical to the success of this Chemical Vapor Condensation (CVC) process are (1) a low concentration of precursor compound in the carrier gas, (2) rapid expansion of the gas stream through an uniformly heated tubular reactor under a reduced inert gas pressure of 1-35 mbar, and (3) rapid quenching of the gas phase nucleated clusters or nanoparticles as they exit from the reactor tube. A wide variety of metal organic precursors is available commercially, all of which can be utilized in the CVC process to produce n-ceramic powders, including single phase, multiphase and multicomponent systems.The CVC process has been used to synthesize non-agglomerated n-SiCxNy and n-ZrOxCy powders, with controlled particle size in the range 2-20 nm. Heat treatment of the assynthesized n-powders in various high purity gas streams causes compositional and structural modifications, including particle purification and crystallization, as well as transformation to a whisker-like morphology. Thus, as-synthesized amorphous n-SiCxNy particles transform to (1) cubic n-SiC particles, when heated in flowing argon at temperatures> 1350 °C, (2) hexagonal n-Si3N4 whiskers, when heated in flowing NH3IH2 at 1400 °C, and (3) cubic nSiC whiskers, when heated in flowing H2 at 1400 °C.Non-agglomerated n-ceramic powders form uniformly dense powder compacts by cold pressing, which can be sintered to theoretical density at temperatures as low as 0.5 Tm' For example, full densification ofn-Zr02 powder compacts under free sintering conditions can be achieved at 1125 °C."

Jan 1, 1994

By Leiv Kolbeinsen, Vincent Canaguier, Ingeborg-Helene Svenum

The syntheses of stoichiometric iron chromite and chromites with chosen impurity content have been developed using the induction skull melting technique. The aim for this synthetic material is to obtain pure samples to study the carburization by methane-hydrogen gas mixtures. For each synthesis, the parameters influencing the skull melting experiment have been considered. The product phases have been analyzed using X-Ray Diffraction (XRD), Scanning Electron Microscopy (SEM), Energy-Dispersive X-ray Spectroscopy (EDS) and X-ray Photoelectron Spectroscopy (XPS). The synthetic material was subsequently pelletized and sintered in argon. The use of excess iron was found to improve the quality of the final product as well as to help the melting. The difference in magnesium content between first and last solids formed seem to indicate a segregation phenomenon, while no evidence could support a similar trend for aluminum substitution in chromite.

Mar 1, 2017

By Bhavani Kedika, Venkatagiri Noole, Krishna Thotla, Krishna Reddy Chepyala

Cationic lipids are attractive candidates for transgene delivery and expression and are safer alternatives to viral delivery vehicles. Here, we report the design, synthesis, characterization and transgene expression efficacies of a series of chrysin derived cationic lipids. A series of ten lipids of chrysin was synthesized by treating the 7-hydroxy group with dibromoalkane and further substitution of the bromo derivative with alkyl amines. The synthesized lipids were characterized spectroscopically. Parallel screening of the synthesized lipids for in vitro plasmid delivery expressing luciferase led to identification of several leads that demonstrated higher transgene expression when compared to the standard. Transgene expression efficacy was dependent on the chain length of the lipid. The influence of the various physicochemical properties on transgene expression efficacies was investigated. This study indicates that lipids derived from chrysin results in high levels of transgene expression and may be attractive for gene therapy applications.

Mar 1, 2017

By T. I. Arbuzova

The present work presents the original data concerning using a high pressure torsion method and a shock wave loading technique to produce compact oxide nanomaterials and investigations of the effect of severe plastic deformation on a microstructure, crystal lattice and stability of these compounds. This allowed us to compare two ways of deformation action that can be characterized as quasi-static and dynamic effect, correspondingly. Particular attention was paid to a stoichiometry and surface composition changes upon severe plastic deformations. A procedure for studying chemistry of the oxide nanomaterials by means of nuclear microanalysis and Rutherford back scattering has been worked through. For surface studies the X-ray photoelectron spectroscopy has been used. It was shown that both distortion methods permit to produce massive nano-scale oxide materials from the coarse-grained powder during a single technological cycle. Bulk nanocrystalline materials based on LaMnO3, TiOy and ZrO2:Y2O3 were obtained by the quasi-static deformation technique. Nanoscaled ceramics of CuO, Mn3O4 and LaMnO3 were produced by the dynamic deformations. The density of the nanoceramics comes to 99%. Size effects and specific imperfection of the nanoceramics obtained lead to a set of particularities of physical properties.

Jan 1, 2006

By S. N. Ojha, Gouthama, R. K. Mandal

"Spray deposition processing of liquid immiscible alloys, based on AI-Pb and Cu-Pb systems have been investigated. Process variables have been optimized to generate uniform dispersion of ultrafine second phase particles in· the matrix of the primary phase. Mechanisms governing the microstructural evolution in this synthesis methodology are discussed. Results of the present investigation are used to demonstrate that rapid solidification of atomized droplets initially provides a high nucleation rate of the second phase during the liquid phase separation. The solid matrix phase nucleates at a later stage and grows with a high velocity enabling trapping of the dispersed phase. Subsequent alteration in the size and size distribution of the second phase is suggested to arise further during deposition of high velocity droplets. Possible reasons for this effect are brought out. Microstructural features of atomized powders and spray-deposits of these alloys are presented to support the present approach of synthesizing composites. IntroductionIn recent years, synthesis of advanced materials with metastable microstructures and ultra fine dispersion of second phase particles has led to the development of novel techniques of materials processing. The other requirement of such a processing methodology is to achieve near-net shape geometries in less number of processing steps. The solidification processing method via spray deposition route qualifies these criteria. This process primarily involves atomization of a melt by high energy gas jets into spray of droplets which are subsequently propelled by the kinetic energy of the gas towards a deposition substrate to build-up a thick high density preform. Although the concept of spray deposition was pioneered by Singer [1] in the early seventies, the fundamentals of the deposition process has been understood only recently [2-4]. Several benefits of spray deposition processing are by now well established [5,6]. Rapid solidification effects are inherent in spray deposition processing due to high heat exchange rate at the droplet-gas interface and also on the deposition surface by force convection. Since considerable heat extraction occurs from the atomized spray prior to droplet consolidation, a relatively low processing temperature is ensured in this process. As a result deleterious coarsening phenomenon can be minimized. In addition, controlled maneuvering of the substrate provides the capability of the process in producing disc, sheet or tube shape preforms of difficult to work materials in a single operation. A significant improvement in properties, resulting from microstructural homogeneity and refinement in grain size induced by spray deposition has been reported for several alloy systems [7,8]."

Jan 1, 1994

By L. Lü, M. O. Lai

"Mechanical alloying is a dry, high energy ball milling process which has been used to synthesize metallic powders in the solid state. The present study use this technique to synthesize Cu-base shape memory alloy powder from commercial Cu70Zn30, Cu86Zn14 and element AI powders. The evolution and formation of shape memory alloy powder were monitored using X-ray diffraction and microscopy. It was observed that shape memory alloy powder started to form after 1.8 ks of mechanical alloying. ? phase was clearly detected after 3.6 ks of mechanical alloying. The intensity of X-ray diffraction of the y phase increased when mechanical alloying duration was prolonged indicating an increase in the amount of y phase. Microstructure observation showed different stages of formation of alloyed powders: welding between powders and formation of layered structure, deformation and fracturing of layered structure, and finally the formation of alloyed powders.IntroductionMechanical alloying (MA) is a process used for producing powders with controlled and extremely fine microstructure. It was original developed in 1966 (1) to produce aNi-based superalloy combining oxide dispersion strengthening with gamma prime precipitation hardening. In recent years this technique has been used in producing a wide range of materials including intermetallic compounds (2, 3), amorphous materials (4-6) and other materials (7-9). In MA, a blend of powders is subjected to highly energetic compressive collision. The powder panicles are welded and fractured during ball milling. Therefore, it is essential that at least one of powders should be ductile to act as combiner. It has however been found that brittle components without soft element can also be mechanically alloyed (10), even ceramic powders (11).The present work aims to study the mechanism of formation of shape memory alloy powder during MA."

Jan 1, 1994

By K. Yoo

Cuprous oxide is one of the oldest antifouling agents and also acts as red pigment in these paints. In printed circuit board manufacturing industries, waste etchant contains a substantial amount of copper ion. In the present study, a process was suggested for recovering cuprous oxides from the waste etchant and optimum conditions were investigated to recover the cuprous oxides. The process consists of two steps: in first step, Cu powder is added into wastewater solution, and cupric ions re-duce into cuprous ions (Cu+Cu2+?2Cu+), where cuprous ions precipitate as cuprous chloride; In second step, cuprous oxide is synthesized by adding NaOH into cuprous chloride solution (2CuCl+2NaOH?Cu2O+NaCl+H2O). Optimum conditions were investigated to recover cuprous oxide in the processes. When copper powder was added into wastewater with copper ions, Cu concentration decreased from 15.6% to 2.6% and ORP decreased from 620 mV to -59.9 mV. This result shows that cupric ions reduced into cuprous ions. XRD data indicated that the precipitate was cuprous chloride powder. Using the cuprous chloride recovered and NaOH solution, cuprous oxide was synthesized. To investigate the optimum condition, various NaOH solutions were added into water with CuCl, and then pH, ORP, Cu concentration, Cu contents in precipitates were analysed. XRD data showed that main component of precipitates was cuprous oxide.

Jan 1, 2014

By J. Aguilar-Santillan, H. Balmori-Ramirez, R. C. Bradt, I. Vernet-Patiño, F. Cunha

Kyanite is an alumino-silicate mineral that has been widely used for the production of refractory products for industrial applications. Kyanite provides a high alumina content, it readily produces mullite during firing, good hot strength of products and can be adapted to produce dimensional stability of products during firing. This research addresses the application of kyanite in mixes to produce (0 dense mullite aggregates with the addition of alumina, (ii) dense composite refractory aggregates of forsterite / spinel with additions of magnesia, and (iii) dense cordierite aggregates with the addition of talc. Effects of attrition milling and conventional ceramic processing are addressed as they affect the properties of these unique aggregates.

Jan 1, 2004