Titanate formation

Taruta, S., Itou, Y., Takusagawa, N., Okada K. and Otsuka, N. Influence of aluminum titanate formation on sintering of bimodal size-distributed alumina powder mixtures , J. Am. Ceram. Soc. 80 (1987) 551-556. 

Freudenberg B., Mocellin A. Aluminium titanate formation by solid state reaction of fine AI2O3 and T1O2 powders. J. Am. Ceram Soc. 1987 70 33-38. 

Another important class of titanates that can be produced by hydrothermal synthesis processes are those in the lead zirconate—lead titanate (PZT) family. These piezoelectric materials are widely used in manufacture of ultrasonic transducers, sensors, and minia ture actuators. The electrical properties of these materials are derived from the formation of a homogeneous soHd solution of the oxide end members. The process consists of preparing a coprecipitated titanium—zirconium hydroxide gel. The gel reacts with lead oxide in water to form crystalline PZT particles having an average size of about 1 ]lni (Eig. 3b). A process has been developed at BatteUe (Columbus, Ohio) to the pilot-scale level (5-kg/h). 

Because lactic acid has both hydroxyl and carboxyl functional groups, it undergoes iatramolecular or self-esterificatioa and forms linear polyesters, lactoyUactic acid (4) and higher poly(lactic acid)s, or the cycUc dimer 3,6-dimethyl-/)-dioxane-2,5-dione [95-96-5] (dilactide) (5). Whereas the linear polyesters, lactoyUactic acid and poly(lactic acid)s, are produced under typical condensation conditions such as by removal of water ia the preseace of acidic catalysts, the formation of dilactide with high yield and selectivity requires the use of special catalysts which are primarily weakly basic. The use of tin and ziac oxides and organostaimates and -titanates has been reported (6,21,22). 

In plasticizer manufacture, eg, of phthalates or sebacates, uskig sulfuric or/ -toluenesulfonic acid catalysts, the temperature (140—150°C) requked for rapid reaction and high conversion may dehydrate or oxidize the alcohol and may yield a dark or foul-smelling product. Neutral titanates do not cause such side reactions. Although a temperature of 200°C is requked, esterifications can easily be forced to over 99% conversion without the formation of odors or... 

The addition of an alkanolamine, such as diethanolamine, to TYZOR TBT, as well as the use of a less moisture-sensitive alkanolamine titanate complex such as TYZOR TE, has been reported to prolong catalyst life and minimi2e ha2e formation in the polymer (475—476). Several excellent papers are available that discuss the kinetics and mechanism of titanate-cataly2ed esterification and polycondensation reactions (477—484). 

The type of catalyst influences the rate and reaction mechanism. Reactions catalyzed with both monovalent and divalent metal hydroxides, KOH, NaOH, LiOH and Ba(OH)2, Ca(OH)2, and Mg(OH)2, showed that both valence and ionic radius of hydrated cations affect the formation rate and final concentrations of various reaction intermediates and products.61 For the same valence, a linear relationship was observed between the formaldehyde disappearance rate and ionic radius of hydrated cations where larger cation radii gave rise to higher rate constants. In addition, irrespective of the ionic radii, divalent cations lead to faster formaldehyde disappearance rates titan monovalent cations. For the proposed mechanism where an intermediate chelate participates in the reaction (Fig. 7.30), an increase in positive charge density in smaller cations was suggested to improve the stability of the chelate complex and, therefore, decrease the rate of the reaction. The radii and valence also affect the formation and disappearance of various hydrox-ymethylated phenolic compounds which dictate the composition of final products. 

Studies carried out on Earth, for example, by the NASA infrared telescope on Mauna Kea (Hawaii), showed albedo variations which indicated the presence of holes in the Titanian cloud formations (Griffith, 1993). It is, however, still unclear as to whether these inhomogeneities result from differences in the surface composition. Lorenz et al. (1997) reported large variations in Titan s atmosphere due to photochemical processes. The methane contained in the dense nitrogen atmosphere is decomposed by solar and thermal radiation, and its content may be replenished from methane lakes or from clathrates. 

The photochemistry of Titan s atmosphere can be summarized as follows the unsaturated compounds are formed from HCN and C2H2, which is derived from CH4. Methane decomposition leads to further ethane formation. 

The structures of the thick layers of haze which surround Titan, and which are in some ways comparable to the smog we know so well on Earth, are a mystery to scientists. It is possible that a numeric simulation model has solved the problem (Rannou et al., 2002) their results suggest that winds are responsible for the seasonal variations of the haze structures. The tiny particles which form the haze move from one pole to the other during a Titanian year (which corresponds to 4 years on Earth). This new model also explains the formation of a second separate haze layer above the main layer this is formed from small particles which are blown to the poles and separate from the main haze layer before later returning to it. 

Of the alkenes (Figure 5.5) only ethene has been detected and of the aromatics only benzene has been seen unambiguously surprisingly propene has not been seen despite its well-understood microwave spectrum. Of interest to the origins of life is the onset of polymerisation in HCN to produce cyanopolyynes. These molecules could provide a backbone for the formation of information-propagating molecules required for self-replication. The survival of these species in a planetary atmosphere depends on the planet oxidation would be rapid in the atmosphere of today s Earth but what of the early Earth or somewhere altogether more alkane-based such as Titan ... 

The next most likely possibility is cometary delivery of the atmosphere but again there are some problems with the isotope ratios, this time with D/H. The cometary D/H ratios measured in methane from Halley are 31 3 x 10-5 and 29 10 x 10-5 in Hayuatake and 33 8 x 10-5 in Hale-Bopp, whereas methane measurements from Earth of the Titan atmosphere suggest a methane D/H ratio of 10 5 x 10-5, which is considerably smaller than the ratio in the comets. The methane at least in Titan s atmosphere is not exclusively from cometary sources. Degassing of the rocks from which Titan was formed could be a useful source of methane, especially as the subnebula temperature around Saturn (100 K) is somewhat cooler than that around Jupiter. This would allow volatiles to be more easily trapped on Titan and contribute to the formation of a denser atmosphere. This mechanism would, however, apply to all of Saturn s moons equally and this is not the case. 

Essentially, all reactions that require the formation of a chemical bond with an activation energy of around 100 kJ mol-1 are frozen out at the surface of Titan but are considerably faster in the stratosphere, although still rather slow compared with the rates of reaction at 298 K. Chemistry in the atmosphere of Titan will proceed slowly for neutral reactions but faster for ion-molecule reactions and radical-neutral reactions, both of which have low activation barriers. The Arrhenius equation provides the temperature dependence of rates of reactions but we also need to consider the effect of cold temperatures on thermodynamics and in particular equilibrium. 

The formation of the 1,3CH2 methylene radial in either the triplet or singlet electronic states depends on collisions with other molecules such as N2 in the Titan... 

It is clear that a complex hydrocarbon polymer chemistry must exist in the atmosphere of Titan involving polyyne species, polynitrile species and mixtures of the two, and additional routes to polyaromatic hydrocarbon formation. This presents a significant problem for the gas chromatography/mass spectrometry instruments on the Huygens probe. There should be hydrocarbon fragments, producing perhaps... 

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