Supercritical deposition

Erkey and co-workers [59-61] prepared Pt- and Ru-doped carbon aerogels using a supercritical deposition method. This involved dissolution of an organometallic precursor in a supercritical fluid and the exposure of a solid substrate to this solution. After impregnation of the support with the metal precursor, it was converted to the metal form by different methods. Dimethyl(l,5-cyclooctadiene) platinum(ll) was used as a precursor for Pt [59,60], and two different Ru complexes, trisacetylacetonate Ru(lll) and Ru(cod)(tmhd)2, were used for Ru [61], Monolithic organic and carbon aerogels... 

A. O. Sezer and J. I. Brand, Electrokinetic effects in supercritical depositions... 

Zhang Y, Kang DF, Saquing C, Aindow M, Erkey, C (2005) Supported platinum nanoparticles by supercritical deposition. Ind Eng Chem Res 44 4161-4164... 

Saquing, C.D., Cheng, T.T., Aindow, M., Erkey, C., 2004. Preparation of platinum/carbon aerogel nanocomposites using a supercritical deposition method. Journal of Physical Chemistry B 108 (23), 7716-7722. 

Supercritial boilers use all-volatile treatments, generally consisting of ammonia and hydrazine. Because of the extreme potential for deposit formation and steam contamination, no soHds can be tolerated in supercritical once-through boiler water, including treatment soHds. 

A method which uses supercritical fluid/solid phase extraction/supercritical fluid chromatography (SE/SPE/SEC) has been developed for the analysis of trace constituents in complex matrices (67). By using this technique, extraction and clean-up are accomplished in one step using unmodified SC CO2. This step is monitored by a photodiode-array detector which allows fractionation. Eigure 10.14 shows a schematic representation of the SE/SPE/SEC set-up. This system allowed selective retention of the sample matrices while eluting and depositing the analytes of interest in the cryogenic trap. Application to the analysis of pesticides from lipid sample matrices have been reported. In this case, the lipids were completely separated from the pesticides. 

Barne.s, H.L. and Czamanske, G.K. (1967) Solubilities and transport of ore minerals. In Barnes, H.L. (ed.). Geochemistry of Hydrothermal Ore Deposits. New York Holt, Rinehart and Win.ston, pp. 334-381. Berndt, M.E., Seyfried, W.E. Jr. and Janeckey, D.R. (1989) Plagiocla.se and epidote buffering of cation ratios in midocean ridge hydrothermal fluids Experimental results in and near the supercritical region. Geochim. Cosmochim. Acta, 53, 2283-2300. 

Crystallization by reaction to form metals, semiconductors (e.g.. Si), and metal oxides including nanocrystals Supercritical fluid deposition... 

The solvent elimination appro2K h is quite straightforward for supercritical fluids lAich are often gases at atmospheric pressure. Each chromatographic peedc is deposited fron the end of a restrictor, connected to the end of the column by a heated transfer line, onto a small area of infrared-transparent support [110,128,129,134]. The support can be moved manually to collect each peak at a n osition or stetq>ed continuously to record the... 

The number of reports on on-line TLC analysis of extracts is quite limited. Stahl [16,29] described a device for supercritical extraction with deposition of the fluid extract on to a moving TLC plate. On-line SFE-TLC provides rapid and simple insight into the extraction performance. Its strength is that the extract is deposited on a plate, which means that detection is a static process. Limitations of SFE-TLC are that quantification is difficult, and that the stability of components on the support material or in the presence of oxygen may be a problem. For additives in beverages (such as benzoic... 

Figure 7.16 Schematic representation of off-line SFC-FTIR. After deposition of the eluites on to a moving ZnSe substrate the window is moved to the focus of a stand-alone FTIR microscope, where the spectmm of each spot is measured with the plate stationary. After Griffiths et al. [374]. Reprinted from P.R. Griffiths et al., in Hyphenated Techniques in Supercritical Fluid Chromatography and Extraction (K. Jinno, ed.), pp. 83-101, Copyright (1992), with permission from Elsevier...

SFC-TLC is largely unexplored. Stahl [927] developed a device for supercritical fluid extraction with deposition of the fluid extracts on a moving TLC plate. Wunsche et al. [928] have described an automated apparatus for direct pSFC-TLC coupling. Compared to collecting the effluent from the SFC in decompression vessels, the direct deposition of the effluent on the TLC plate leads to significant losses of analytes. Multidimensional SFC has been reviewed [929]. 

Blackburn, J.M., Long, D.P., Cabanas, A. and Watkins, J.J. (2001) Deposition of conformal copper and nickel films from supercritical carbon dioxide. Science,... 

RESS [Rapid Expansion of Supercritical Solutions] A process for depositing a film of solid material on a surface. The substance is dissolved in supercritical carbon dioxide. When the pressure is suddenly reduced, the fluid reverts to the gaseous state and the solute is deposited on the walls of the vessel. Used for size-reduction, coating, and microencapsulation. First described in 1879. Developed in 1983 by R. D. Smith at the Battelle Pacific Northwest Laboratory. 

The catalyst can be treated with a solvent to extract hydrocarbon deposits. The most straightforward solvent to use is isobutane, which has been shown to restore catalytic activity only partially. Supercritical solvents have been tested, but they also lead to only partial restoration of the activity. Supercritical alkylation to remove the deposits in situ has been shown in Section III.D.l to be less effective. It is unlikely that this method of operation will lead to a competitive process. 

Petkovic, L.M. and Ginosar, D.M. (2004) The efiect of supercritical isobutane regeneration on the nature of hydrocarbons deposited on a USY zeolite catalyst utilized for isobutane/butene alkylation. Appl. Catal. A, 275, 235-245. 

Power plant boilers are either of the once-through or dmm-type design. Once-through boilers operate under supercritical conditions and have no wastewater streams directly associated with their operation. Drum-type boilers operate under subcritical conditions where steam generated in the drum-type units is in equilibrium with the boiler water. Boiler water impurities are concentrated in the liquid phase. Boiler blowdown serves to maintain concentrations of dissolved and suspended solids at acceptable levels for boiler operation. The sources of impurities in the blowdown are the intake water, internal corrosion of the boiler, and chemicals added to the boiler. Phosphate is added to the boiler to control solids deposition. 

The Rose Run Sandstone is the best characterized of the Cambrian sandstones because it is also an oil and gas reservoir (Fig. 3). It is also the only one of the Cambrian sandstones that is known to retain its sandstone composition in the eastern part of the state rather than passing laterally into carbonate. The Rose Run Sandstone is a sandy layer in the middle of the Knox Dolomite (Fig. 4), which across much of eastern Ohio lies at depths suitable for injection of supercritical C02 (Fig. 3). The Rose Run Sandstone was deposited in a passive margin phase of the Appalachian Basin and consists of interbedded layers of carbonate, primarily dolos-tone, and sandstone (Fig. 5). The sandstone is compositionally mature, consisting largely of quartz. Subordinate reactive minerals are the alkali feldspars and locally abundant glauconite (Fig. 5). Dolomite and quartz are the dominant cements (Janssens 1973 Riley et al. 1993). 

Adhesives. Supercritical fluids might also be used to deposit adhesive films without the use of solvents. They have even been suggested for ungluing at the time of final disposal/recycling of the bonded product. 

Conformal coatings. Deposition of a thin film that nniformly coats all exposed parts of a three-dimensional strnctnre is known as conformal film growth. Conformality is a common requirement for dielectric films. Penetration and uniform coverage of all topography and interstices are vital and depend upon low viscosity, as well as low surface and interfacial energies. Fluoropolymer in supercritical solution might provide die required characteristics. 

Microemulsions. Systems comprising microwater droplets suspended in an scCO T oil phase can be achieved with the use of appropriate surfactants, of which the best appear to be fluorinated. Microemulsions in supercritical hydrofluoro carbons are also possible. Potential may also exist for speciality coatings via low concentration solutions of fluorinated products in supercritical fluid for, e.g., thin-fitm deposition, conformal coatings, and release coatings. Supercritical CO2 will dissolve in formulated systems to improve flow and plasticize melt-processable materials to improve melt-flow characteristics and lower the glass transition temperature. 

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