Method of making glass-ceramic and articles made therefrom

Abstract

A method of making a glass-ceramic from at least two different metal oxides is disclosed. The method includes providing the two different metal oxides as a glass, heating the glass above the glass transition temperature of the glass to form a coalesced shape; and heating the coalesced shape to a temperature above the crystallization onset temperature of the glass, thereby forming a glass-ceramic comprising at least 1% by volume crystallites, wherein the crystallites have an average size of less than 1 micrometer. The difference between the glass transition temperature and the crystallization onset temperature is at least 25K.

Description

CROSS-REFERENCE TO RELATED APPLICATIONS[0001]This application is a continuation of U.S. Ser. No. 10 / 211,491, filed Aug. 2, 2002, which is a continuation-in-part of U.S. Ser. No. 09 / 922,526, filed Aug. 2, 2001, now abandoned. This application is related to U.S. 2007 / 0135290 A1 filed Jan. 15, 2007. This application is also related to U.S. Ser. No. ______ (Attorney Docket No. 56938US017) and U.S. Ser. No. ______ (Attorney Docket No. 56938US018) filed on even date herewith.FIELD OF THE INVENTION[0002]The present invention relates to a method of making an article by coalescing a plurality of the glass particles. Examples of articles include kitchenware (e.g., plates), dental brackets, and reinforcing fibers, cutting tool inserts, abrasives, and structural components of gas engines, (e.g., valves and bearings).DESCRIPTION OF RELATED ART[0003]A large number of glass and glass-ceramic compositions are known. The majority of oxide glass systems utilize well-known glass-formers such as SiO2, ...

AI Technical Summary

Benefits of technology

[0065]In some embodiments, it may be advantageous for at least a portion of a metal oxide source (in some embodiments, preferably, 10 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, or even at least 95 percent by weight) to be obtained by adding particulate, metallic material comprising at least one of a metal (e.g., Al, Ca, Cu, Cr, Fe, Li, Mg, Ni, Ag, Ti, Zr, and combinations thereof), M, that has a negative enthalpy of oxide formation or an alloy thereof to the melt, or otherwise metal them with the other raw materials. Although not wanting to be bound by theory, it is believed that the heat resulting from the exothermic reaction associated with the oxidation of the metal is beneficial in the formation of a homogeneous melt and resulting amorphous material. For example, it is believed that the additional heat generated by the oxidation reaction within the raw material eliminates or minimizes insufficient heat transfer, and hence facilitates formation and homogeneity of the melt, particularly when forming amorphous particles with x, y, and z dimensions over 150 micrometers. It is also believed that the availability of the additional heat aids in driving various chemical reactions and physical processes (e.g., densification, and spherodization) to completion. Further, it is believed for some embodiments, the presence of the additional heat generated by the oxidation reaction actually enables the formation of a melt, which otherwise is difficult or otherwise not practical due to high melting point of the materials. Further, the presence of the additional heat generated by the oxidation reaction actually enables the formation of amorphous material that otherwise could not be made, or could not be made in the desired size range. Another advantage of the invention include, in forming the amorphous materials, that many of the chemical and physical processes such as melting, densification and spherodizing can be achieved in a short time, so that very high quench rates be can achieved. For additional details, see U.S. Pat. No. 7,168,267 (Rosenflanz et al.), the disclosure of which is incorporated herein by reference.

[0066]The particular selection of metal oxide sources and other additives for making ceramics according to the present invention typically takes into account, for example, the desired composition and microstructure of the resulting ceramics, the desired degree of crystallinity, if any, the desired physical properties (e.g., hardness or toughness) of the resulting ceramics, avoiding or minimizing the presence of undesirable impurities, the desired characteristics of the resulting ceramics, and / or the particular process (including equipment and any purification of the raw materials before and / or during fusion and / or solidification) being used to prepare the ceramics.

[0067]The metal oxide sources and other additives can be in any form suitable to the process and equipment utilized for the present invention. The raw materials can be melted and quenched using techniques and equipment known in the art for making oxide glasses and amorphous metals. Desirable cooling rates include those of 50K / s and greater. Cooling techniques known in the art include roll-chilling. Roll-chilling can be carried out, for example, by melting the metal oxide sources at a temperature typically 20-200° C. higher than the melting point, and cooling / quenching the melt by spraying it under high pressure (e.g., using a gas such as air, argon, nitrogen or the like) onto a high-speed rotary roll(s). Typically, the rolls are made of metal and are water cooled. Metal book molds may also be useful for cooling / quenching the melt.

[0068]Other techniques for forming melts, cooling / quenching melts, and / or otherwise forming glass include vapor phase quenching, plasma spraying, melt-extraction, and gas atomization. Vapor phase quenching can be carried out, for example, by sputtering,

[0069]wherein the metal alloys or metal oxide sources are formed into a sputtering target(s) which are used. The target is fixed at a predetermined position in a sputtering apparatus, and a substrate(s) to be coated is placed at a position opposing the target(s). Typical pressures of 10−3 torr of oxygen gas and Ar gas, discharge is generated between the target(s) and a substrate(s), and Ar or oxygen ions collide against the target to start reaction sputtering, thereby depositing a film of composition on the substrate. For additional details regarding plasma spraying, see, for example, U.S. Pat. No. 7,179,526 (Rosenflanz et al.), the disclosure of which is incorporated herein by reference.

[0070]Gas atomization involves melting feed particles to convert them to melt. A thin stream of such melt is atomized through contact with a disruptive air jet (i.e., the stream is divided into fine droplets). The resulting substantially discrete, generally ellipsoidal glass particles are then recovered. Melt-extraction can be carried out, for example, as disclosed in U.S. Pat. No. 5,605,870 (Strom-Olsen et al.), the disclosure of which is incorporated herein by reference. Containerless glass forming techniques utilizing laser beam heating as disclosed, for example, in PCT application having Publication No. WO 01 / 27046 A1, published Apr. 4, 2001, the disclosure of which is incorporated herein by reference, may also be useful in making glass according to the present invention.

Problems solved by technology

Although a large number of metal oxides can be obtained in an amorphous state by melting and rapidly quenching, most, because of the need for very high quench rates to provide amorphous rather than crystalline material, cannot be formed into bulk or complex shapes.

Generally, such systems are very unstable against crystallization during subsequent reheating and therefore do not exhibit typical properties of glass such as viscous flow.

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