Gamma phase alumina

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. 

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],... 

Alumina membranes. It has been established that several phases of alumina exist and a particular phase of alumina is determined not only by the temperature it has experienced but also by the chemical path it has taken. For commercial membrane applications, the alpha- and gamma-phases of alumina are the most common. Alpha-alumina membranes are well known for their thermal and hydrothermal stabilities beyond 1,000 C. In fact, other transitional forms of alumina will undergo transformation towards the thermodynamically stable alpha-alumina at elevated tcmjxratures beyond 900 C. On the contrary, commercial gamma-alumina membranes are typically calcined at 400-600 C during production and are, therefore, subject to potential structural changes beyond 600°C. Moreover, alumina chemistry reveals that phase transition also occurs beyond that temperature [Wefers and Misra, 1987]. 

Despite the above-mentioned advantages of cerium oxide and a-alumina especially for the conversion of alcohols, a wide variety of investigations have dealt with alkene conversion on y-alumina-supported active species [16, 28, 41]. For sol-gel layers, which can also be used as a support for CPO [8], the determination of the aluminum phase is often not reported (e.g. [42]) as calcination temperatures between 300 and 700 °C could result in a considerable contribution of amorphous phases to gamma phases and at 800-1000 °C there is an additional transition to a delta phase [43]. 

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. 

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. 

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]-... 

The catalysts, both fresh and used, were characterized as to BET surface area, pore size distribution, elemental analysis, x-ray diffraction and XPS. Some BET and pore volume data are given in Table 1. The diffraction pattern of Catalyst B gave some indication of a gamma-alumina phase, not well resolved All other peaks were well-resolved, suggesting the absence of amorphous or highly-dispersed phases. 

Gas/vapor phase modifications. Many inorganic membrane materials display functional groups that have chemical affinity to selected chemical agents. A well known example is a gamma-alumina membrane which has hydroxyl groups on the surfaces of the alumina crystallites. These hydroxyl groups present on the pore walls and the macroscopic surface of the membrane can act as the reactive sites for modifications of the pore structure with a chemical agent such as the diversified family of silane compounds (chloro- or alkoxy>silanes). 

The presence of water at elevated temperatures is also a critical factor in the performance of gamma-alumina membranes. Water has been known to promote the aforementioned phase transition of alumina at a lower tempeiauire. 

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