Cryochemical processes

FIGURE 4.17 Samples of ceramics with oriented porosity obtained using cryochemical processing (A) Ti02 cross-sections of AljOj ceramics perpendicular (B) and parallel (C) to the macroscopic ice growth direction. ... 

Metal vapor techniques provide unique means for cryochemical solid-phase synthesis of metal-containing systems. In this way, metastable compounds, whose existence earlier was only supposed, have been obtained [7]. Besides, cryochemical processes produce stabilized small metal clusters of quantum type, which are the intermediate form of matter between isolated atoms and bulk metal [8, 9]. However, known methods of cryochemical solid-phase synthesis used low-molecular-weight matrices, in which the initial products of such a synthesis can be conserved only at low temperatures, when the matrix is enough rigid to hinder transformation or loss of these products. 

Simultaneous evaporation of metal with organic and inorganic substances followed by vapor deposition on a substrate allows the production of composite films containing M nanoparticles stabilized in various dielectric matrices [2, 28]. The use of monomer molecules in this process polymerizing during deposition or as a result of the subsequent reactions yields polymeric nanocomposite films with metal inclusions [2, 3, 28, 37]. The new low-temperature synthesis of polymeric nanocomposite films has been elaborated recently. This synthesis is based on the deposition of M/SC and monomers vapors at temperature 80 K followed by low-temperature solid-state polymerization of obtained films in conditions of frozen thermal movement of molecules (cryochemical synthesis) [2], This synthesis has important features, which will be considered further. 

VI. Theoretical Treatment of Autowave Processes in Solid-State Cryochemical Conversions (The Simplest Model)... 

VI. THEORETICAL TREATMENT OF AUTOWAVE PROCESSES IN SOLID-STATE CRYOCHEMICAL CONVERSIONS (THE SIMPLEST MODEL)... 

The next important step in the study of the regularities of the autowave modes of cryochemical conversion was to perform a series of experiments with thin-film samples of reactants. The changeover to such objects, characterized by the most intense heat absorption, allowed the realization of quasi-isothermal conditions of the process development and thus favored the manifestation of the abovementioned isothermal mechanism of wave excitation, which involves autodispersing the sample layer by layer due to the density difference between the initial and final reaction products. The new conditions not only not suppressed the phenomenon, but made it possible to reveal some details of the traveling-wave-front structure, which will be discussed here and also in Section X. 

The extensively studied (especially during the recent years) transitions of solids from the metastable amorphous state to the polycrystalline state (see ref. 58 and the references therein) are of autowave character and resemble very much the above regimes of solid-state cryochemical reactions. The action of autodispersion, which facilitates phase transition by allowing it to proceed on the surface of a fracture instead of in the glass volume, cannot be excluded in the case of those processes either. Actually, the two classes of processes are similar in their physical nature both are connected with rearrangement of the solid matrix and are of exothermic character, differing only in the extent of the thermal effect. It should be added that fracturing and autodispersion of the sample are very typical of the autowave destruction of amorphous states and can be seen even by the unaided eye. 

Various kinds of low-temperature processing have been used in materials science and technology. Among these, the cryochemical method is believed to be the first from the work of Landsberg and Campbell who dealt with the synthesis of nanocrystalline powders of W and W-Re alloys. This new synthesis technique attracted the attention of several groups who used this new method for the... 

In this coimection, a cryochemical solid-phase synthesis of metal-polymer systems is of special importance. As a result of such a synthesis, metal clusters and organometallic assemblies formed at low temperatures are buried in a polymer environment, which offers possibilities to stabilize and study these products over a large temperature range. This method was first offered and described in reference 10. The thermal rearrangement of the initial low-temperature system is governed by relaxation processes in polymer matrix. In particular, the aggregation of metal atom clusters to form metal nanocrystals in cryochemically produced metal-polymer systems yields new nanocomposite materials with valuable properties. The study of the mechanism of cluster aggregation, which depends on the characteristics of the polymer matrix, will allow the nanocomposite structure to proceed in the needed direction. Thus, it becomes possible to determine the methods of cryochemical synthesis of metal-polymer materials with predetermined properties. 

Metal-polymer systems obtained as a result of vapor deposition cryochemical synthesis contain stabilized small nonmetallic clusters of metal atoms and metal nanocrystals, but only metal nanocrystals participate in conductivity processes. The data on Ag-containing PPX composites [44] testify to the fact that the relative part of metal stabilized in cluster form at ambient temperature sharply decreases with increasing total metal content even in the range 0-2 vol. %. Therefore, at measurements of conductivity, which were carried out at considerably higher metal concentrations, it was accepted that as a first approximation, all metal is as nanocrystals. 

When metal particles are isolated in a polymer so that the interaction between them can be neglected, the conductivity of a composite is determined by that of a polymer matrix. In such composites, metal nanoparticles can only inject carriers into a polymer but do not influence substantially the conductivity process [59], This is the case of metal-PPX films prepared by the cryochemical vapor deposition teclmique if such films contain metal or semiconductor nanocrystals in amounts less than 4—5 vol. % [30]. The conductivity of such composites follows classical olmfic current-voltage relationship [30] and Arrheiuus dependence on temperature [57]. At higher metal contents the mechaiusm of conductivity in synthesized composite films changes under influence of the interparficle interaction. In PPX films containing Pb nanoparficles in amounts from 5 to 10 vol. %, the dependence of current I on voltage U looks like In / [30]. This dependence is characteristic for a... 

Most of these features of cryochemical reactions are also of great significance for cryotropic gelation processes [8]. Moreover, if the system contains polymeric solutes, the stiU-liquid fraction can exist even at rather low temperatures and such... 

Shlyakhtin OA, Oleinikov NN, Tretyakov YD (2005) Cryochemical synthesis of materials. In Komameni S, Lee B (eds) Chemical processing of ceramics (2nd edn), vol 28, Materials engineering series. CRC, Boca Raton, p 77... 

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