Patent Grant
8501050
The present invention relates to composite materials for use in electrolytic aluminum production cells, and more particularly relates to composites comprising titanium diboride, silicon carbide and carbon-containing scavenger additives useful as cathodes in aluminum production cells.
Materials used in electrolytic aluminum production cells, also known as Hall-Héroult cells, must be thermally stable at high temperatures on the order of 1,000° C., and must be capable of withstanding extremely harsh conditions such as exposure to molten cryolite, molten aluminum, and oxygen at elevated temperatures. Although various types of materials have been used as cathodes and to line the walls of electrolytic aluminum production cells, a need still exists for improved materials capable of withstanding such harsh conditions.
Titanium diboride (TiB2) would be desirable for use as a cathode material in electrolytic aluminum production cells. When titanium diboride is used as a wettable cathode, the energy used for operation of the cell can be greatly reduced. Titanium diboride has many desirable properties including wettability by molten aluminum, high temperature stability and exceptional corrosion resistance. However, the manufacture of the titanium diboride cathodes is difficult because titanium diboride powders are not easily sintered and do not readily form dense parts. Titanium diboride powders often require the application of very high pressures and temperatures well in excess of 2,000° C. in order to decrease porosity of the sintered material. Even at such extreme conditions, titanium diboride components are often not fully dense or they exhibit microcracking, both of which decrease performance.
Sintering aids have been added to titanium diboride in attempts to decrease processing temperatures, microcracking and residual porosity. However, conventional sintering aids have been found to decrease the corrosion resistance of titanium diboride components, particularly in harsh environments such as found in electrolytic aluminum production cells.
The present invention provides composite materials comprising titanium diboride, silicon carbide (SiC) and minor amounts of carbon-containing scavenger additions such as tungsten carbide (WC), boron carbide (B4C) and/or carbon. The TiB2/SiC composite materials may be used as cathodes in electrolytic aluminum production cells. The amounts of titanium diboride, silicon carbide, and carbon-containing scavenger(s) are controlled in order to provide optimum performance. The TiB2/SiC composite materials are electrically conductive, exhibit desirable aluminum wetting behavior, and are capable of withstanding exposure to molten cryolite, molten aluminum and oxygen at elevated temperatures during operation of electrolytic aluminum production cells.
An aspect of the present invention is to provide a composite cathode for use in an electrolytic aluminum production cell, the composite cathode comprising from about 70 to about 98 weight percent titanium diboride, from about 2 to about 30 weight percent silicon carbide, and at least about 0.2 weight percent of at least one carbon-containing scavenger.
Another aspect of the present invention is to provide a method of making a composite cathode for use in an electrolytic aluminum production cell. The method comprises mixing powders of titanium diboride, silicon carbide and at least one carbon-containing scavenger, and consolidating the mixture to form the composite cathode.
These and other aspects of the present invention will be more apparent from the following description.
The present invention provides composite materials comprising titanium diboride, silicon carbide and carbon-containing scavenger additives that are particularly suited as cathode materials in electrolytic aluminum production cells.
Each of the cathode 12 and side walls 14 and 16 must be thermally stable at the elevated temperatures experienced during the electrolytic process, and must be capable of withstanding exposure to molten cryolite, molten aluminum, and oxygen at such elevated temperatures. In addition, the cathode 12, and side walls 14 and 16, should have satisfactory aluminum wetting characteristics and controlled levels of electrical conductivity. The cathode 12, and side walls 14 and 16, of the cell 10 may be fabricated in the form of plates that are installed in the interior side walls of the cell. The plates may have any suitable thickness.
In accordance with an embodiment of the present invention, the cathode 12 of the cell 10 may be made of a composite material comprising titanium diboride, silicon carbide and at least one carbon-containing scavenger additive such as tungsten carbide, boron carbide and/or carbon. The titanium diboride phase of the composite material typically forms a continuous interconnected skeleton in the material, while the silicon carbide phase may be either continuous or discontinuous, depending upon the relative amount that is present in the material.
The composite materials of the present invention typically comprise from about 70 to about 98 weight percent titanium diboride, for example, from about 85 to about 98 weight percent. In a particular embodiment, the titanium diboride comprises from about 90 to about 96 weight percent of the composite material. When used as a cathode material, the TiB2-based composite possesses desirable electrical conductivity and aluminum wetting behavior, and is corrosion resistant, i.e., is capable of withstanding exposure to molten cryolite, molten aluminum and oxygen at elevated temperatures during operation of electrolytic aluminum production cells.
In accordance with an embodiment of the present invention, silicon carbide is present in the composite material in typical amounts of from about 2 to about 30 weight percent, for example, from about 3 to about 10 weight percent. In a particular embodiment, the silicon carbide is present in an amount of from about 4 to about 8 weight percent. The use of silicon carbide as an additive aids in sintering and provides good corrosion resistance to both molten salts and molten aluminum.
In accordance with the present invention, at least one carbon-containing scavenger is present in the TiB2/SiC composite material. The scavenger additives provide a source of carbon that preferentially reacts with oxygen to reduce or eliminate the presence of unwanted oxide species such as titanium dioxide and boron oxide. Suitable carbon-containing scavenger materials include metal carbides such as tungsten carbide, boron carbide and the like. Furthermore, carbon in various forms such as phenolic resin, carbon black and/or graphite may be used. The carbon-containing scavenger addition(s) are typically present in relatively small amounts of from about 0.2 to about 10 weight percent, for example, from about 1 to about 8 weight percent.
In certain embodiments of the present invention, tungsten carbide is used as the carbon-containing scavenger. The WC may be added to the TiB2/SiC composite materials in typical amounts of from about 0.25 to about 6 weight percent, for example, from about 1 to about 5 weight percent. In a particular embodiment, the tungsten carbide may be provided in an amount of from about 2 to about 3 weight percent. The tungsten carbide acts as an oxygen scavenger, aids in sintering, and forms a solid solution with the TiB2. The WC may be bound in the structure and may improve corrosion resistance to molten salts and molten aluminum. The WC may be added as a discrete powder before or during powder mixing, or may be introduced during the mixing operation as a result of erosion of WC-containing mixing aids, e.g., through the use of WC milling media and/or milling linings.
In accordance with another embodiment of the present invention, boron carbide is used as the scavenger material in typical amounts of from about 0.5 to about 10 weight percent, for example, from about 1 to about 8 weight percent. In a particular embodiment, the boron carbide comprises from about 2 to about 5 weight percent. The B4C may be added to create the following reaction which reduces or eliminates surface oxides on the TiB2 particles:
2TiO2+B4C+3C→2TiB2+4CO.
The use of boron carbide may provide transient phases that reduce oxide species that would otherwise be detrimental to sintering and performance of the composite material.
In a further embodiment of the present invention, carbon is used as the scavenger material. In this embodiment, the total amount of carbon typically ranges from about 0.2 to about 10 weight percent, for example, from about 0.3 to about 8 weight percent. In a particular embodiment, the total amount of carbon added is from about 0.5 to about 4 weight percent. The carbon source may be provided in the form of amorphous phenolic resin, carbon black, graphite or the like. Such carbon sources may reduce oxide species that would otherwise be detrimental to sintering and performance of the composite material.
Other materials may optionally be added to the present TiB2/SiC composite materials, for example, molybdenum, chromium, iron, cobalt, nickel, niobium, tantalum and/or the carbides or borides of such metals. Such optional additives may be added to the composite materials in a total amount of up to about 10 weight percent, for example, a total amount of up to about 2 weight percent. These materials may increase the ability to densify the TiB2/SiC composite materials.
In accordance with an embodiment of the present invention, the TiB2/SiC composite materials may be substantially free of additional materials, i.e., such additional materials are not purposefully added to the composite materials and are only present in trace amounts or as impurities.
The present composite materials may be made by consolidating powder mixtures of the titanium diboride, silicon carbide and carbon-containing scavenger additives. In one embodiment, consolidation may be achieved by hot pressing the powders. In another embodiment, consolidation may be achieved by pressing the powders at ambient temperature, e.g., cold isostatic pressing, followed by vacuum sintering.
The titanium diboride powder typically has an average particle size range of from about 1 to about 50 microns, for example, from about 2 to about 10 microns. The silicon carbide powder typically has an average particle size range of from about 0.5 to about 20 microns, for example, from about 2 to about 10 microns. When tungsten carbide is used as a carbon-containing additive, it may have a typical average particle size range of from about 0.5 to about 15 microns, for example, from about 1 to about 3 microns. In an embodiment of the invention where the carbon-containing additive comprises boron carbide, the B4C powder may typically have an average particle size range of from about 0.5 to about 15 microns, for example, from about 1 to about 3 microns. By providing relatively small particle sizes, the WC and/or B4C tend to react with the surface oxides more readily.
The powders may be mixed in the desired ratio by any suitable mixing method such as dry blending or ball milling. The resultant powder mixture is consolidated by any suitable process, for example, hot pressing at pressures typically ranging from about 10 to about 40 MPa, and at temperatures typically ranging from about 1,800 to about 2,200° C. The resultant hot pressed powders have high densities, typically above 95 percent, for example, above 98 or 99 percent.
The consolidation step may include sintering of the powder mixture at elevated pressures, e.g., by hot pressing, sintering at ambient pressures, or sintering under vacuum. In one embodiment, the powder mixture may be sintered by spark plasma sintering or field assisted sintering techniques in which heating is achieved by passing electric current through hot press dies and the workpiece. Use of this method may reduce the processing temperature to a range of from about 1,600 to about 2,000° C.
An embodiment of the invention provides for hot pressing of a body of the composite material to greater than 90 percent of theoretical density at 1,800° C. with 30 MPa of pressure, and about 100 percent of theoretical density at 1,900° C. with 30 MPa of pressure. To accomplish this, TiB2 powder is combined with from 2 to 30 volume percent (1.5 to 24 weight percent) SiC powder, typically from 2 to 10 volume percent (4 to 8 weight percent) and milled with WC media. The milling process adds controlled amounts of WC, which aids in sintering. The addition of WC from processing is generally from 1 to 10 weight percent, typically from 2 to 3 weight percent.
Another embodiment of the invention provides for the densification of a body of the composite material to greater than 90 percent of theoretical density at 2,000° C., and greater than 95 percent of theoretical density at 2,100° C. under ambient pressure or vacuum. To accomplish this the same treatment is employed as described in the embodiment above, but using from 2 to 10 weight percent boron carbide, typically from 5 to 7 weight percent. In conjunction with B4C, carbon additions in the form of phenolic resin, amorphous carbon black, graphite or the like may be used in amounts of from 1 to 5 weight percent, typically from 2 to 3 weight percent.
The following examples are intended to illustrate various aspects of the invention, and are not intended to limit the scope of the invention.
Composite plates were made from TiB2, SiC and B4C powders having the specifications set forth in Tables 1, 2 and 3 below.
Starting powders of TiB2 and SiC having specifications as set forth in Tables 1 and 2 and at selected weight ratios were milled for 4 to 16 hours with a ball milling process using WC milling media. The ratios employed were: 96 weight percent TiB2-4 weight percent SiC; and 92 weight percent TiB2-8 weight percent SiC. The blended powders were loaded into a graphite die for hot pressing. The hot pressing schedule was as follows, with the maximum temperature being 1,900° C.: pull vacuum to <100 mtorr; heat at 25° C./min to 1,650° C. while under vacuum; hold for 1 hour under vacuum; after hold backfill with Ar, apply 10 MPa of pressure and heat at 10° C./min to maximum temperature; once maximum temperature is reached gradually increase pressure over 10 min to 30 MPa; after maximum pressure is reached maintain maximum pressure of 30 MPa until ram travel stops, which is typically 60 to 90 min at maximum temperature and pressure; once ram travel stops remove pressure and allow the furnace to cool to room temperature.
After the materials were hot pressed, their densities were measured. Vickers hardness was measured on polished cross-sections of the materials and Young's modulus was determined with a time-of-flight calculation using an ultrasonic transducer. The properties of the different compositions are shown in Table 4.
A sample of the TiB2/SiC/WC composite is shown in the micrograph of
Starting powders of TiB2, SiC and B4C having specifications as set forth in Tables 1, 2 and 3, and phenolic resin were milled for 4 to 16 hours with a ball milling process using WC milling media. The ratios employed were: 92 weight percent TiB2-4 weight percent SiC-2 weight percent B4C-2 weight percent phenolic resin; 88 weight percent TiB2-8 weight percent SiC-2 weight percent B4C-2 weight percent phenolic resin; 82 weight percent TiB2-15 weight percent SiC-2 weight percent B4C-1 weight percent phenolic resin; and 75 weight percent TiB2-22 weight percent SiC-2 weight percent B4C-1 weight percent phenolic resin. The blended powders were pressed in a steel die at ˜65 MPa and then cold isostatically pressed at ˜200 MPa. The sintering schedule was as follows, with the maximum temperature being 1,900-2,100° C.: pull vacuum to <100 mtorr; heat at 10° C./min to 1,650° C. while under vacuum; hold for 1 hour under vacuum at 1,650° C.; after hold backfill with Ar and heat at 15° C./min to maximum temperature; once maximum temperature is reached hold for 3 hours; after final hold allow to cool to room temperature.
After the materials were sintered, their densities were measured. Vickers hardness was measured on polished cross-sections of the material and Young's modulus was determined with a time-of-flight calculation using an ultrasonic transducer. The properties of the different compositions are shown in Table 5.
A sample of the TiB2—SiC composite with B4C additions is shown in the micrographs of
Whereas particular embodiments of this invention have been described above for purposes of illustration, it will be evident to those skilled in the art that numerous variations of the details of the present invention may be made without departing from the invention as defined in the appended claims.
| Number | Name | Date | Kind |
|---|---|---|---|
| 3808012 | Bailey et al. | Apr 1974 | A |
| 4097567 | Cebulak et al. | Jun 1978 | A |
| 4224128 | Walton | Sep 1980 | A |
| 4297180 | Foster, Jr. | Oct 1981 | A |
| 4338177 | Withers et al. | Jul 1982 | A |
| 4349427 | Goodnow et al. | Sep 1982 | A |
| 4374761 | Ray | Feb 1983 | A |
| 4376690 | Kugler | Mar 1983 | A |
| 4399008 | Ray | Aug 1983 | A |
| 4478693 | Ray | Oct 1984 | A |
| 4514355 | Montgomery | Apr 1985 | A |
| 4544469 | Boxall et al. | Oct 1985 | A |
| 4560448 | Sane et al. | Dec 1985 | A |
| 4582553 | Buchta | Apr 1986 | A |
| 4664760 | Jarrett | May 1987 | A |
| 4929328 | Besmann et al. | May 1990 | A |
| 4983340 | Montgomery | Jan 1991 | A |
| 5028301 | Townsend | Jul 1991 | A |
| 5100845 | Montgomery | Mar 1992 | A |
| 5158655 | Townsend | Oct 1992 | A |
| 5217583 | Sekhar et al. | Jun 1993 | A |
| 5227045 | Townsend | Jul 1993 | A |
| 5310476 | Sekhar et al. | May 1994 | A |
| 5340448 | Sekhar et al. | Aug 1994 | A |
| 5364442 | Sekhar | Nov 1994 | A |
| 5378325 | Dastolfo, Jr. et al. | Jan 1995 | A |
| 5378327 | Sekhar et al. | Jan 1995 | A |
| 5538604 | Keller et al. | Jul 1996 | A |
| 5683663 | Keller et al. | Nov 1997 | A |
| 5961811 | Keller | Oct 1999 | A |
| 6146559 | Zank | Nov 2000 | A |
| 6371746 | Shiomi et al. | Apr 2002 | B1 |
| 6402926 | Sekhar et al. | Jun 2002 | B1 |
| 6403210 | Stuivinga et al. | Jun 2002 | B1 |
| 6419812 | Beck et al. | Jul 2002 | B1 |
| 6419813 | Brown et al. | Jul 2002 | B1 |
| 6616829 | Keller et al. | Sep 2003 | B2 |
| 6783656 | De Nora et al. | Aug 2004 | B2 |
| 7462271 | Dionne et al. | Dec 2008 | B2 |
| 7723247 | Zhang et al. | May 2010 | B2 |
| 20070270302 | Zhang et al. | Nov 2007 | A1 |
| 20080227619 | Zhang et al. | Sep 2008 | A1 |
| 20090048087 | Zhang et al. | Feb 2009 | A1 |
| 20100126877 | Luo et al. | May 2010 | A1 |
| 20110114479 | Yeckley et al. | May 2011 | A1 |
| Entry |
|---|
| Li et al “Research Progress in TiB2 Wettable Cathode for Al Reduction”, TMS/JOM (Aug. 2008) pp. 32-37. |
| Finch et al., “Crack Formation and Swelling of TiB2-Ni Ceramics in Liquid Aluminum”, Communications of the American Ceramic Society, Jul. 1982, pp. C-100 and C-101. |
| Kang et al., “Effect of Iron and Boron Carbide on the Densification and Mechanical Properties of Titanium Diboride Ceramics”, J. Am. Ceram. Soc., 1989, pp. 1868-1872, vol. 72, No. 10. |
| Einarsrud et al., “Pressureless Sintering of Titanium Diboride with Nickel, Nickel Boride, and Iron Additives”, J. Am. Ceram. Soc., 1997, pp. 3013-3020, vol. 80, No. 12. |
| Zhang et al., “Microstructure and Mechanical Properties of TiB2/(Ni+Mo) Composites Fabricated by Hot Pressing”, J. Mater. Sci. Technol., 2000, pp. 634-636, vol. 16, No. 6. |
| Chamberlain et al., “High-Strength Zirconium Diboride-Based Ceramics”, J. Am. Ceram. Soc., 2004, pp. 1170-1172, vol. 87, No. 6. |
| Chamberlain et al., “Pressureless Sintering of Zirconium Diboride”, J. Am. Ceram. Soc., 2006, pp. 450-456, vol. 89, No. 2. |
| Zhang et al., “Pressureless Densification of Zirconium Diboride with Boron Carbide Additions”, J. Am. Ceram. Soc., 2006, pp. 1544-1550, vol. 89, No. 5. |
| Zhang et al., “Pressureless Sintering of ZrB2-SiC Ceramics”, J. Am. Ceram. Soc., 2008, pp. 26-32, vol. 91, No. 1. |
| Number | Date | Country | |
|---|---|---|---|
| 20130075669 A1 | Mar 2013 | US |
