Compositions: ceramic – Ceramic compositions – Fluorine containing
Reexamination Certificate
1999-09-10
2001-11-13
Group, Karl (Department: 1755)
Compositions: ceramic
Ceramic compositions
Fluorine containing
C501S095100, C501S095300, C501S152000, C502S231000, C502S439000, C423S021100, C423S489000
Reexamination Certificate
active
06316377
ABSTRACT:
FIELD OF THE INVENTION
The present invention relates to nanoparticles containing oxygen, fluorine and a rare earth element or yttrium or scandium. The invention also relates to a hydrothermal method for forming nanoparticles.
BACKGROUND OF THE INVENTION
Hydrothermal reactions, i.e., reactions that take place in hot water at high pressures, have industrial and scientific importance in forming materials such as zeolites and large single crystals. A difficulty with hydrothermal reactions is the high rate of corrosion caused by the conditions necessary to conduct hydrothermal reactions. For example, corrosion of the material lining the walls of a hydrothermal reactor can cause contamination of the product and may even cause a catastrophic failure and explosion of the reactor vessel. Another difficulty is that catalyst support materials that are used in hydrothermal reactions can dissolve or change morphology in a sustained hydrothermal environment. Although ceramic materials have many desirable features for use in reactors, such as linings for reactor chambers and catalyst supports for aqueous phase reactions, ceramic materials are especially sensitive to the corrosive effects of hydrothermal conditions. See, for example, Wendlandt, et al., “The Reactions of Oxides with Water at High Pressures and Temperatures,” Angew. Chem. Int'l. Ed., vol. 3, p47 (1964).
Great efforts have been devoted to the development of new refractory materials. For example, Brown in U.S. Pat. No. 4,057,433 describes a mold having a facing portion comprising finely divided particles of the oxyfluorides of the lanthanide and actinide series. Brown states that the finely divided particles have a particle size of from below 400 mesh to 5 mesh, i.e. having a particle size of from 0.1 to 4000 microns. In the examples section of U.S. Pat. No. 4,057,433 a particle size of 325 mesh (44 micron) is used. Preparations of rare earth oxyfluorides are known (see, e.g., Niihara et al, Bull. Chem. Soc. Jap., 44, 643 (1971) and deKozak, et al., Rev. de Chimie Miner., 17, 440 (1980); however, particles are obtained by pulverizing, and it is known that particle sizes of 1 micron and less are generally not obtainable by conventional grinding processes. Brown does not discuss grinding processes and does not discuss the morphology of the oxyfluorides nor their stability in hydrothermal conditions. In general, morphology and hydrothermal stability cannot be predicted based on a chemical formula since factors such as crystal growing conditions and crystal structure can have a strong influence on a material's properties. Moreover, there is no known correlation between a ceramic material's refractory properties and its performance in hydrothermal conditions.
Dugger in WO 93/17959 discloses that various oxyhalide complexes are useful precursors for making refractory oxides. Dugger does not disclose particle sizes of the oxyhalide precursors (other than passing through a screen size such as 200 mesh) and does not discuss the morphology of the oxyfluorides nor their stability in hydrothermal conditions.
In making ceramic articles it is frequently desirable to use small particles because, relative to larger particles, smaller particles are more reactive and sinter at lower temperatures. However, under hydrothermal conditions, small particles tend to dissolve and (in saturated solutions) deposit on a large crystal, such as a seed crystal, to form large crystalline materials. In other words, in a static cell, or equilibrium, hydrothermal conditions favor the dissolution of small particles and the formation of large particles.
Indeed, nanometer-sized particles have so far only been obtained from a supercritical aqueous environment by two types of non-equilibrium processes. The first approach has been to limit crystal growth by inducing an abrupt homogeneous nucleation of a dissolved solute in the region of an expanding jet (see, e.g., Smith, U.S. Pat. No. 4,734,451, Matson et al., J. Mat. Sci. 22, 1919 (1987) or the rapid thermal decomposition of precursors in solution. The second widely used non-equilibrium approach for production of nanoparticles employs a solid component as one of the reacting starting materials whereby the rate of dissolution limits the precipitation. Examples of the second approach are described in references such as Oota, et al., J. Cryst. Growth 46, 331 (1979) and Fedoseev, et al., Kristall und Technik 3, 95 (1968. Finally, at subcritical temperatures (200° C.), whiskers of hydroxyapatite with widths of 0.1 to 1 micrometer (&mgr;m) were obtained from a dilute solution of beta-Ca
3
(PO
4
)
2
near the vapor pressure of the solution. See Yoshimura, et al., J. Mater. Sci., 29 3399 (1994).
There remains a need for hydrothermal processes for forming nanoparticles under equilibrium conditions and/or from a single phase solution. There is a further need for rare earth oxygen-containing fluoride nanoparticles. There is also a need for nanoparticles materials that are hydrothermally stable and/or have a fiber morphology.
SUMMARY OF THE INVENTION
The present invention provides a method of making a nanoparticle material. In this method, an aqueous precursor composition is prepared that contains (a) a rare earth element or yttrium or scandium and (b) fluorine. The aqueous precursor composition is heated to a temperature of at least about 200° C. under increased pressure for a time sufficient to obtain the nanoparticle material.
In a second aspect, the invention provides a rare earth element oxygen-containing fluoride material. This material comprises nanoparticles that have a diameter smaller than one micrometer and are composed of, at least: (a) a rare earth element or yttrium or scandium, (b) oxygen, and (c) fluoride.
One object of the invention is to provide a method for making nanoparticles under hydrothermal conditions. It is another object of the invention to provide nanofibers of a rare earth, yttrium or scandium oxygen-containing fluoride. Another object of the invention is to provide a nanoparticle material that is stable to high temperature and high pressure conditions.
The subject matter of the present invention is particularly pointed out and distinctly claimed in the concluding portion of this specification. However, both the organization and method of operation, together with further advantages and objects thereof, may best be understood by reference to the following drawings and description.
REFERENCES:
patent: 3607770 (1971-09-01), Rabatin
patent: 3615169 (1971-10-01), Thom
patent: 4057433 (1977-11-01), Brown
patent: 4734451 (1988-03-01), Smith
patent: 4845056 (1989-07-01), Yamanis
patent: 5652192 (1997-07-01), Matson et al.
patent: 6066305 (2000-05-01), Dugger
patent: 2165963 (1999-06-01), None
patent: 241 083 (1987-03-01), None
patent: WO 93/17959 (1993-09-01), None
patent: WO 98/54607 (1998-12-01), None
“Continuous Hydrothermal Processing of Nano-Crystalline Particulates for Chemical-Mechanical Planarization,” Darab et al., J. Elec. Mat., 27)10), 1068-72, 1998, No Month.
“Hydrothermal Processing of Nano Ceramic Powder,” Wang et al., Rare Metal Materials and Engineering, 24(4), 1-6, (Abstract in English) Aug. 1995.
“Hydrothermal Synthesis of Advanced Ceramic Powders,” Dawson, Cer. Bull., 67(10), 1673-78, 1988, No Month.
“Rapid Expansion of Supercritical Fluid Solutions: Solute Formation of Powders, Thin Films, and Fibers,” Matson et al., Ind. Eng. Chem. Res., 26, 2298-2306, 1987, No Month.
“Le Systeme DyF3-Dy2O3, ” deKozak et al., Rev. Chim. Miner., 17, 440-443, 1980.
“Synthesis of Potassium Hexatitanate Fibers by the Hydrothermal Dehydration Method,” Oota et al., J. Cryst. Gro., 46, 331-338, 1979, No Month.
“Studies of Rare Earth Oxyfluorides in the High Temperature Region,” Niihara et al., Bull. Chem. Soc. Jap., 45, 20-23, 1972, No Month.
“The crystal Structure and Nonstiochiometry of Rare Earth Oxyfluoride,” Niihara et al., Bull. Chem. Soc. Jap., 44, 643-48, Mar. 1971.
“The Reaction of Oxides with Water at High Pressure and Temperatures,” Wendlandt et al., Angew. Chem. Intl. Ed., 3, 47-53,
Fulton John L.
Hoffmann Markus M.
Battelle (Memorial Institute)
Group Karl
Rosenberg Frank S.
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