US 20070194503 A1
A translucent polycrystalline material suitable for use in ceramic discharge vessels for metal halide lamps is produced by sintering an alumina powder doped with a MgO sintering aid in a nitrogen atmosphere containing a partial pressure of a vapor phase carbon-containing species. The sintered polycrystalline alumina has a grain boundary phase containing aluminum, oxygen and nitrogen. The formation of the Al—O—N grain boundary phase is believed to facilitate the transport of nitrogen from entrapped pores during sintering. Preferably, the PCA is sintered in a carbon-element furnace under flowing ultra-high-purity nitrogen.
8. A method of sintering ceramic body to translucency, the method comprising:
(a) placing a ceramic body comprised of aluminum oxide doped with MgO in a furnace containing a carbon source and a nitrogen atmosphere formed by a nitrogen gas source having a total impurity level of no more than about 0.005% by volume;
(b) sintering the ceramic body at a temperature from about 1800° C. to about 2000° C. to form a sintered translucent ceramic body.
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20. A method of sintering a ceramic body to translucency, the method comprising:
(a) placing a ceramic body comprised of aluminum oxide doped with about 100 ppm to about 1000 ppm MgO in a carbon-element furnace containing a nitrogen atmosphere formed by a nitrogen gas source having a total impurity level of no more than about 0.005% by volume;
(b) sintering the ceramic body at a temperature from about 1800° C. to about 2000° C. for about 1 hour to about 70 hours to form a sintered translucent ceramic body, the furnace atmosphere during sintering containing from about 1×10−12 atm to about 1×10−7 atm of carbon and less than about 0.2% hydrogen by volume.
Translucent polycrystalline alumina (PCA) ceramic has made possible present-day high-pressure sodium (HPS) and ceramic metal halide lamps. The arc discharge vessels in these applications must be capable of withstanding the high temperatures and pressures generated in an operating lamp as well be resistant to chemical attack by the fill materials.
In HPS lamps, the discharge vessels are tubular as shown in
In the past, some of the key elements in sintering polycrystalline alumina (PCA) to translucency involved the use of (1) a high-purity powder, (2) a small concentration of a MgO sintering aid, and (3) sintering in an H2-containing atmosphere. It has been reported in the literature that air, N2, He, and Ar atmospheres may not be used, but H2, O2, or vacuum did permit the attainment of translucency. This was due to the solubility of the gases in the lattice and grain boundaries allowing entrapped gaseous species to diffuse to the surface. In a vacuum environment, or in a gaseous atmosphere that is soluble and diffused rapidly in PCA, the sintering process is not kinetically limited, and pore-free microstructures are achieved. Later work has indicated that translucent alumina may be sintered in dissociated ammonia (25% N2-75% H2) and even in a CO atmosphere. The sintering of alumina has been reported in N2-H2 atmospheres containing as low as 2% hydrogen. Because of cost and safety issues, it would be desirable to eliminate the need to add hydrogen gas and use nitrogen gas only. However, a N2 atmosphere alone has not been able to produce translucent PCA
It has been discovered that polycrystalline alumina can be sintered to translucency in a nitrogen gas atmosphere in a carbon-element furnace. As used herein, translucency means a total transmittance of at least 92% in the visible wavelength region from about 400 nm to about 700 nm. Preferably, the total transmittance of the discharge vessel according to this invention is at least 95%.
The sintering results in the carbon-element furnace are drastically different from those using the W-element, Mo-shield or alumina tube muffle furnace. Microstructural analysis of the PCA sintered in N2 in a carbon-element furnace indicates the formation of a grain-boundary Al—O—N phase which is believed to facilitate the transport of nitrogen from the entrapped pores. The formation of the grain-boundary Al—O—N phase is believed to result from the combination of the nitrogen atmosphere and vapor phase carbon-containing species, in particular, C, CO and CO2, emanating from the carbon furnace components. For example, the formation of aluminum oxynitride (either Al7O9N or Al23O27N5) may proceed by the following reaction:
The partial pressure of carbon at aluminum oxide sintering temperatures is estimated to be about 10−9 atm. Preferably, the furnace atmosphere should contain from about 1×10−12 atm to about 1×10−7 atm of carbon. The furnace atmosphere may also contain partial pressures of CO, CO2, H2, CH4 and C2H2. In particular, the partial pressures of these gases during sintering is estimated as: 10−3 to 10−4 PCO; 10−6 to 10−7 atm PCO2; 10−3 atm PH2, 10−10 atm PCH4 and 10−7 atm PC2H2. Although it is preferred to sinter the PCA in a carbon-element furnace, a similar sintering atmosphere may be generated by other means, e.g., using graphite trays or placing other sources of carbon in other types of furnaces. However, the atmosphere may be more difficult to control in furnaces that contain W and Mo components because these metals readily getter carbon.
It should be noted that the partial pressure of hydrogen expected from outgassing of the carbon furnace components, 10−3 atm, is more than an order of magnitude less than the partial pressure of hydrogen previously known to be required for sintering aluminum oxide to translucency in a nitrogen-hydrogen mixed gas atmosphere. Preferably, the PCA discharge vessel is sintered in a nitrogen atmosphere containing less than about 0.2% H2 by volume. More preferably, the furnace atmosphere contains about 1×10−9 atm of carbon and about 1×10−3 to about 1×10−4 atm CO.
A relatively pure nitrogen gas source is used to create the furnace atmosphere. Preferably, the nitrogen gas source should contain no more than about 0.005% by volume total impurities. More preferably, the nitrogen gas is an ultra-high-purity grade that is 99.999% nitrogen by volume. The sintering temperature may be in the range from about 1800° C. to about 2000° C. and sintering times may range from about 1 hour to about 70 hours. More preferably, the discharge vessels are sintered at from at about 1850° C. to about 1950° C. for about 4 to about 50 hours, and most preferably, at about 1900° C. for about 10 hours.
For a better understanding of the present invention, together with other and further objects, advantages and capabilities thereof, reference is made to the following disclosure and appended claims taken in conjunction with the above-described drawings.
Ceramic discharge vessels formed from a high-purity, finely divided aluminum oxide (alumina) powder may be consolidated by isopressing, extrusion, slip casting, gel casting, or injection molding. The MgO dopant is generally added to the alumina powder prior to consolidation. The details of various methods of manufacturing green ceramic bodies for discharge vessels are described in, for example, European Patent No. 0 650 184 B1 (slip casting), U.S. Pat. No. 6,399,528 (gel casting), International Patent Application No. W02004/007397 A1 (slip casting) and European Patent Application No. EP 1 053 983 A2 (isopressing).
The sintering method of this invention produces a translucent PCA ceramic that has a second nitrogen-containing phase at grain boundaries. The phase comprises aluminum, oxygen and nitrogen and is believed to be an aluminum oyxnitride. This second phase is believed to facilitate the diffusion of nitrogen out of the entrapped pores making it possible to sinter the PCA to translucency in a N2 atmosphere without having to add at least 2% hydrogen. The sintering method and the resulting translucent PCA are described in more detail in the following examples. However, it should be understood that the present invention is by no means restricted to such specific examples.
A high purity (99.97% pure) Al2O3 powder is preferably used as the starting powder to form the polycrystalline alumina discharge vessel. Forming methods may include isopressing, extrusion, injection molding, gel casting and slip casting. For straight tubes, isopressing or extrusion is preferred. For more complex shapes, injection molding, gel casting or slip casting may be used. Preferred alumina powders are CR30F and CR6 manufactured by Baikowski. CR30F contains ˜80% alpha-Al2O3 and ˜20% gamma-Al2O3, while CR6 is 100% alpha-Al2O3. The crystallite sizes are about 0.05 micrometers with a mean specific surface area of 30 m2/g for CR30F and 6 m2/g for CR6. The reported average particle size is about 0.5 micrometers for both types. Sintering aides such as MgO, Y2O3 and ZrO2 are preferred. MgO is required to sinter the PCA to translucency. Preferably, the amount of MgO is from about 100 ppm to about 1000 ppm. The alumina powders may be doped with the sintering aids by mixing the alumina powder in aqueous solutions of the precursors of the sintering aids. In order to form the green shape, the powders are combined with an appropriate binder material such as polyvinyl alcohol, polyethylene glycol, methylcellulose, or a wax. Prefiring of the shapes is conducted at 850-1350° C. in air for 1-4 h to remove the binders. Discharge vessels of varying sizes (wattages) and their capillaries were made.
Sintering was accomplished in a carbon-element furnace (Centorr Company, Model M10) under one atmosphere of flowing ultra-high-purity (UHP) grade (99.999%) nitrogen gas. More preferably, the UHP-grade nitrogen gas contains <1 ppm CO or CO2, <2 ppm O2, <3 ppm H2O and <0.5 ppm total hydrocarbons. The furnace was a horizontal furnace containing graphite elements and carbon fiber insulation. Prefired PCA parts are placed in an alumina boat with or without setter powder. Two types of setter powders are used: aluminum oxynitride and alumina. The gas flow rate in the furnace corresponded to a linear gas speed of about 0.02 m/s. The sintering temperatures (˜1800-1920° C.) are reached by heating at a rate of about 8-16° C./min. The hold time at the sintering temperature is 4-40 h.
An aluminum oxynitride setter powder bed is preferred to create a partial pressure of aluminum oxynitride so that the grain-boundary aluminum oxynitride phase is retained, which then facilitates diffusion of nitrogen trapped inside pores. PCA parts embedded in the powder bed sintered to significantly higher transmittance than those not buried in the bed. The aluminum oxynitride powder bed may be accomplished by using (1) aluminum oxynitride powder, (2) alumina powder that would gradually form an aluminum oxynitride phase in flowing nitrogen in a carbon furnace, or (3) a mixture of aluminum nitride and alumina powder which would then react to form aluminum oxynitride in the carbon furnace.
The total transmittance of the sintered part involved placing a miniature incandescent lamp or a fiber-optical source inside the sintered part and measuring the total amount of diffuse light transmitted and integrated over a sphere. The wavelength range for the measurement was from about 400 nm to about 700 nm. The following table provides the total transmittance of various PCA parts that were sintered in flowing N2 in a carbon-element, carbon-fiber insulation furnace.
The microstructures of the PCA sintered according to the method of this invention were examined by optical microscopy and scanning electron microscopy (SEM) with energy dispersive x-ray analysis (EDXA). The morphology of the grains on the as-sintered surface is highly etched with cleavage steps, making it difficult to measure the grain size. SEM/EDXA of the surface showed the presence of nitrogen in PCA, indicating the formation of aluminum oxynitride on the surface.
While there have been shown and described what are present considered to be the preferred embodiments of the invention, it will be apparent to those skilled in the art that various changes and modifications can be made herein without departing from the scope of the invention as defined by the appended claims.