Surface powder synthesis

In general, carbides, nitrides, and borides are manufactured in the vapor phase in order to form high-purity powders. This procedure is fundamentally different than a strict CVD process, since in powder synthesis reactors, deposition on seed particles may be desirable, but deposition on the reactor walls represents a loss of product material. As we will see, in CVD, heterogeneous deposition on a surface will be sought. Aside from this issue of deposition, many of the thermodynamic and kinetic considerations regarding gas phase reactions are similar. 

This chapter discusses the fluid-solid and solid-solid reactions used to produce ceramic powders. The first aspect of this discussion is the spontaneity of a particular reaction for a given temperature and atmosphere. Thermodynamics is used to determine whether a reaction is spontaneous. The thermod3mamics of the thermal decomposition of minerals and metal salts, oxidation reactions, reduction reactions, and nitridation reactions is discussed because these are often used for ceramic powder synthesis. After a discussion of thermodynamics, the kinetics of reaction is given to determine the time necessary to complete the reaction. Reaction kinetics are discussed in terms of the various rate determining steps of mass and heat transfer, as well as surface reaction. After this discussion of reaction kinetics, a brief discussion of the types of equipment used for the synthesis of ceramic powders is presented. Finally, the kinetics of solid—solid interdiffusion is discussed. 

A classic example of a solid—fluid ceramic powder synthesis reaction is that of calcination and dehydration of natural or synthetic raw materials. Calcination reactions are common for the production of many oxides from carbonates, hydrates, sulfates, nitrates, acetates, oxalates, citrates, and so forth. In general, the reactions produce an oxide and a volatile gaseous reaction product, such as CO2, SOg, or HgO. The most extensively studied reactions of this type are the decompositions of magnesium hydroxide, magnesium carbonate, and calcium carbonate. Depending on the particular conditions of time, temperature, ambient pressure of CO2, relative humidity, particle size, and so on, the process may be controlled by a surface reaction, gas diffusion to the reacting... 

As is the case with ceramic sintering, joining, and powder synthesis, microwave-assisted fabrication of ceramic coatings can offer unique benefits. To expose the material surfaces for reaction with a gas phase, fibers or powder particles may be suspended by the flow of gas in the fluidized bed. In addition to the flow of the fluidizing gas, low frequency mechanical vibrations (for example, 10-15 Hz) may be applied to the container to reduce the tendency for the powders or fibers to sinter together to form clumps. As the powder size decreases, the powder s sinterability increases. While vibration may not be necessary for particles as large as, say, 50 pm, it may be beneficial for powder particles that are a few microns in diameter. 

Hexairidium clusters supported on 7-AI2O3 were also examined for catalytic activity for toluene hydrogenation. [Ir6(CO)i5]2- was formed by surface-mediated synthesis on 7-AI2O3 powder by treatment of adsorbed Ir(CO)2(acac) in CO at 373 K and 1 atm. Treatment in He at 573 K caused decarbonylation without fragmentation of the cluster frame, giving as indicated by EXAFS analysis. The supported Ir clusters were catalytically active for... 

In contrast to conventional phosphor powders, ceramic powder synthesis aims at the generation of powders with highly sinteractive surfaces with particle sizes down to the submicron range and specific surface areas of up to 50 mVg. In addition, homogeneous doping on a molecular. scale is of substantial importance. 

Since then, HP became a widely used technique to prepare transparent spinel ceramics. For example, HP process was used to fabricate MgAl204 transparent ceramics, with a nearly 100 % densification [44]. Spinel powders for the production of transparent polyciystalline ceramic windows were produced by using both the traditional ceramic solid-state reaction and solgel methods. Among them, the powders produced from the reaction of organomagnesium compounds with surface modified boehmite precursors were best to produce high-quality transparent spinel ceramics. The powder synthesis method allowed fine control over the particle size. 

In most cases, the fabrication process starts from a mass of powder obtained from commercial sources. Nevertheless, knowledge of powder synthesis methods is very important. Equally important are methods that can be used to determine the physical, chemical, and surface characteristics of the powder. The characteristics of the powder depend strongly on the method used to synthesize it, and these, in turn, influence the subsequent processing of the ceramic. The powder character-... 

The ideal control on the structural and textural properties of perovskite-type oxides can be better achieved by exploiting aerosol spray synthesis methods to prepare highly dispersed and nanostructured materials from metal salt precursors. High-specific-surface-area (above 20m /g) crystalline perovskite-type oxides can be then obtained, which are suitable for a variety of applications. A major advantage of spray methods is that the material is directiy processed from the precursor solution with a reduced number of processing steps during powder synthesis (one-step approach), thus making them ideally suited for... 

Mechanochemical processing (MCP) represents a compelling method for the production of nanostructured HA, during which the reaction is activated by mechanical milling. Mechanochemical powder synthesis is a solid-state synthesis method that takes advantage of the perturbation of surface-bonded species by pressure or mechanical forces to enhance the thermodynamic and kinetic reactions between solids [77]. Pressure can be applied via conventional milling... 

Apphcations of ultrasound to electrochemistry have also seen substantial recent progress. Beneficial effects of ultrasound on electroplating and on organic synthetic apphcations of organic electrochemistry (71) have been known for quite some time. More recent studies have focused on the underlying physical theory of enhanced mass transport near electrode surfaces (72,73). Another important appHcation for sonoelectrochemistry has been developed by J. Reisse and co-workers for the electroreductive synthesis of submicrometer powders of transition metals (74). 

In 1954 the surface fluorination of polyethylene sheets by using a soHd CO2 cooled heat sink was patented (44). Later patents covered the fluorination of PVC (45) and polyethylene bottles (46). Studies of surface fluorination of polymer films have been reported (47). The fluorination of polyethylene powder was described (48) as a fiery intense reaction, which was finally controlled by dilution with an inert gas at reduced pressures. Direct fluorination of polymers was achieved in 1970 (8,49). More recently, surface fluorinations of poly(vinyl fluoride), polycarbonates, polystyrene, and poly(methyl methacrylate), and the surface fluorination of containers have been described (50,51). Partially fluorinated poly(ethylene terephthalate) and polyamides such as nylon have excellent soil release properties as well as high wettabiUty (52,53). The most advanced direct fluorination technology in the area of single-compound synthesis and synthesis of high performance fluids is currently practiced by 3M Co. of St. Paul, Minnesota, and by Exfluor Research Corp. of Austin, Texas. 

Porous samples would appear on the surface to provide such a complex and uncontrolled local environment for deformation of solids that they would be of little interest in scientific investigations. Indeed, the principal interest in their responses is technologically driven they are very effective attenuators of wave profiles and much of materials synthesis and processing is carried out on powders. Duvall [86D01] has summarized the difficulty of work with porous powder samples as follows ... 

Apart from manifold structures, carbons can have various shapes, forms, and textures, including powders with different particle size distributions, foams, whiskers, foils, felts, papers, fibers [76, 77], spherical particles [76] such as mesocarbon microbeads (MCMB s) [78], etc. Comprehensive overviews are given, for example in [67, 71, 72], Further information on the synthesis and structures of carbonaceous materials can be found in [67, 70, 72, 75, 79]. Details of the surface composition and surface chemistry of carbons are reviewed in Chapter II, Sec. 8, and in Chapter III, Sec. 6, of this handbook. Some aspects of surface chemistry of lithiated carbons will also be discussed in Sec. 5.2.2.3. 

After reduction and surface characterization, the iron sample was moved to the reactor and brought to the reaction conditions (7 atm, 3 1 H2 C0, 540 K). Once the reactor temperature, gas flow and pressure were stabilized ( 10 min.) the catalytic activity and selectivity were monitored by on-line gas chromatography. As previously reported, the iron powder exhibited an induction period in which the catalytic activity increased with time. The catalyst reached steady state activity after approximately 4 hours on line. This induction period is believed to be the result of a competition for surface carbon between bulk carbide formation and hydrocarbon synthesis.(6,9) Steady state synthesis is reached only after the surface region of the catalyst is fully carbided. 

The steady state rates of hydrocarbon synthesis over the carbided iron surface are given in Table I. The reaction rates have been normalized to the physical surface area of the starting iron powder [18 M /g] and are reported in molecules/cm sec. A turnover... 

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