Alpha phase alumina

Fig. 7.13. The conversion of theta- to alpha-phase alumina was found to be strongly affected by shock modification in work of Beauchamp and co-workers [90B01]. Whereas the unshocked powder showed evidence for an incubation period of 60 min, the shock-modified materials show immediate conversion typical of the presence of shock-formed nuclei.

Support-phase changes or loss of surface area are, of course, irreversible, and replacement of the catalyst may be appropriate. Catalyst damage may take the form of phase changes to the alumina support from gamma to theta or alpha phase. The last is catalyticaky inert because of insignificant surface area. Theta alumina has a low surface area (< 100 /g) relative to gamma alumina (180 m /g) and has poor halogen retention. 

Thermal treatment of shock-modified theta-phase alumina, which initially contained about 30% alpha phase, showed a dramatic change in the rate of transformation to the alpha phase [90B01]. As shown in Fig. 7.13, the shocked sample showed no evidence for an incubation period and displayed a rapid conversion to the alpha phase, in sharp contrast to the unshocked sample. Such behavior clearly indicates that the shock process resulted in formation of larger concentrations of alpha-phase nuclei. 

Alumina, present in the gamma modification, is the most suitable high surface area support for noble metals. The y-Al203 in washcoats typically has a surface area of 150-175 m g However, at high temperatures y-alumina transforms into the alpha phase, and stabilization to prevent this is essential. Another concern is the diffusion of rhodium into alumina, which calls for the application of diffusion barriers. 

Perhaps even more noteworthy is the effect of crystallographic phase. While one phase of a specific composition may readily incorporate from a particular bath composition, another phase of the same composition may incorporate to a much lower extent or not at all. For instance, in the alumina particle system, the alpha phase has been found to readily incorporate from an acidic copper bath while the gamma phase incorporates at less than one tenth the amount of alpha, if at all, as shown in Table 1 [2, 11, 27, 31, 33],... 

X-ray diffraction conducted on the codeposited powder revealed that the deposit obtained from a suspension of gamma alumina, which had been partially converted to the alpha phase, contained both phases of alumina. Whereas, the powder codeposited from a suspension having a 50 50 mixture of alpha to gamma alumina powder, consisted only of the alpha phase. Using a parallel plate electrode configuration, Chen et al. [31] concluded that only alpha alumina can be codeposited. Chen also observed a difference in codeposition with copper when using two different phases of the titanium oxide particle system rutile readily codeposited but anatase titania did not... 

The work by Chen et al. also resulted in no measurable incorporation with particle diameters of 0.05 and 0.02 pm gamma alumina in copper [31]. When the 0.02 pm gamma particles were calcined to obtain a mix of gamma and alpha alumina, codeposition increased to 2.9 vol.%, under the same codeposition conditions. Furthermore, when the 0.02 pm gamma powders were completely converted to the alpha phase of alumina, incorporation rose to 3.3 vol.% [31]-... 

X-ray diffraction of the Buehler-supplied gamma alumina powder used in a RCE study showed the powder to be actually a combination of alpha and gamma phase alumina [28], However, the relatively high particle incorporation obtained with this alpha-gamma alumina cannot be attributed to the partial alpha crystallographic character of the powder, since the pure alpha alumina codeposited to a lesser extent. 

The preparation of precious metal supported catalysts by the HTAD process is illustrated by the synthesis of a wide range of silver on alumina materials, and Pt-, Pt-Ir, Ir-alumina catalysts. It is interesting to note that the aerosol synthesis of alumina without any metal loading results in a material showing only broad reflections by XRD. When the alumina sample was calcined to 900°C, only reflections for a-alumina were evident. The low temperature required for calcination to the alpha-phase along with TEM results suggest that this material was formed as nano-phase, a-alumina. Furthermore, the use of this material for hexane conversions at 450°C indicated that it has an exceptionally low surface acidity as evidenced by the lack of any detectable cracking or isomerization. 

Another form of alkali metal attack on the hot faces of refractory linings involves their high temperature reaction with various components of the brick to form expansive crystalline phases which cause brick to bloat on their hot faces and, subsequently, erode or spall. An example Is the case of alumina brick exposed to sodium at temperatures from about 1700°F to 3000°F. Although sodium does not form a low temperature melt with alumina, it reacts with the alpha phase of alumina, corundum, to form beta alumina, sodium aluminate. Beta alumina has a much greater volume than the very dense corundum and, therefore, disrupts the brick bonding matrix, causing eventual bond failure. 

XRD patterns of Ni -AI2O3 membranes calcined at 900 are shown in Fig. 1 (a). The composite membrane composed of alumina (alpha-phase, corundum (AI2O3, JCPDS 10-0173)) and nickel aluminum oxide (NiAb04, JCPDS 10-0339) as an intermediate phase, which results from the interaction between Ni salt and alumina support disk. However, after reduction in H2, the peaks associated with the NiAb04 phase disappeared. The only phases present were alumina and nickel... 

Alumina is hexagonal close-packed with a corundum structure. Several metastable structures exist, but they all ultimately irreversibly transform to the hexagonal alpha phase. 

Fig. 7 Creep-resistance of the eutectic fiber consisting of interpenetrating phases of alpha-alumina and yttrium-aluminum-garnet (YAG) up to very high temperatures compared with other types of oxide fibers... 

Vapor Phase Hydrogenation of Acetic Anhydride Acetic anhydride was pumped into an evaporator where it was mixed with hydrogen. The temperature of anhydride-hydrogen mixture was raised to the reaction temperature in a preheater zone, made of a 2 feet bed packed with 2 mm glass beads. The reaction took place in a 2 feet catalyst bed packed with 1 m.m. alpha-alumina coated with 0.5% Pd. The effluent was condensed and analyzed by G.C. 

Vanadyl phosphates (VPO) and multiple component molybdate (MCM) are good examples of catalysts, and alpha alumina, amorphous silica and alumino-silicates are good examples of catalyst supports that can be fabricated in the form of 45 to 150 im diameter spray dried porous spheres with attrition resistance improved by a relatively thin peripheral layer rich in amorphous silica, amorphous alumina, or phosphorus oxides. The hard phase component or precursor is selected in each case so that it will not interfere with the catalytic performance of the catalyst. 

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