REFRACTORY COMPOSITION AND PRODUCTS RESULTING THEREFROM

Abstract: The present invention is a formed refractory composition of matter made up of a mixture of silicon carbide, molybde­ num disilicide, and silicon nitride or aluminum nitride or boron nitride. An electrical resistor is also disclosed which is particularly suited for use as an igniter in liquid and gas fuel burning systems. The resistor is made up of a sintered, preferably hot-pressed, mixture of fine powders of alumi­ num nitride or silicon nitride, silicon carbide and molybde­ num disilicide where all three are present in substantial quantities.

Description: REFRACTORY COMPOSITION AND PRODUCTS RESULTING THEREFROM The invention is concerned with ceramic or refractory compositions ani their particular utility as electrical resistors, particularly heating elements, igniters, and heat sensors, as well ab their use in more typical refractory products. The utility of ceramic or refractory compositions for electrical resistors has been known for many years. Silicon carbide heating elements have found widespread use. In more recent years, primarily as a result of the to-called energy crunch, attention has been focused on the application of ceramic resistors as igniters in, for example, gas fired furnaces and appliances like stoves and clothes driers. An example of such an igniter is taught in U.S. Patent No. 3,R75.477. The igniter 35 mainly composed of 95 to 99. by weight of silicon carbide and 0.05 to 0.50% by weight of aluminum, vith optional minor quantities of silica and iron. The terminal connecting ends, or so-called cold ends, are formed in the conventional manner by meta3 coating said ends by dipping n a molten metal or flame spraying. Tnese igniters are relatively lov density bodies as a result of the process used to fabricate them viz. slip casting. Therefore they are susceptible to degradation. An earlier approach to protecting very porous (35% by volume silicon carbide type heating elements from oxidative degradation is that taught by U.S. Patent No. 3,252,827. This is accomplished by first forming b porous self-bonded silicon carbide rod which is then immersed in an aqueous suspension of finely divided molybdenum disilicide for a sufficient amount of time to allow the molybdenum disilicide particles to fully penetrate the silicon carbide body and coat the walls of the pores contained therein. The body is then fired in an inert atmosphere to sinter the silicide to form the final coating. been to twenty five percent molybdenum disilicide can be used. While this approach is effective for a relatively large body such as a beating element e.g. having a diameter of 0.5 inch (1.27 cm) or larger, they are porous and therefore relatively mechanically weak. Therefore the teachings of this patent would not produce a commercially acceptable product where the product must have a small cross section of, for example, an igniter such as that of U.S. latent o. 3,675,477 with a cross sectional area of frorn 0.012 to 0.072 in2 (0.77 x 10-3 to 0.46 % 10-2 cm2). The composition of U.S. Patent No. 3,252,827 would result in an igniter that would simply be too fragile for practical use. U.S. Patent No. 4,174,971 offers a solution to the problem of relatively weak heating elements and the like. This reference impregnates a silicon carbide body with what is referred to as a molybdenum-silicon alloy which finally ends up as 2St of the structure: the impregnant is made up of about 506 by weigh; of silicon and 50% by weight of molybdenum disilicide. High strength refractory resistor compositions are taught by U.S. Patent tic. 3,890,250. The product is composed of from 50 to 908 by weight of silicon nitride and 10 to 50* by weight of silicon carbide and has a modulus of rupture in excess of 100,000 psi (6B9 MPa) at 20 C as measured by four point loading. The electrical resistivity varies from 1 to 1 x 107 ohm cm. These high strength characteristics are the result of hot-pressing the mixture of powders which bringE about almost complete densification. However, when this material is used as an igniter the hot tone degrades rather quickly e.g. goes from a resistance of 182.4 to 247.4 ohms after only 311 hours at 12000C and the cold ends or tabs from 40.4 ohms to 154.4 ohms. A dense submicron grained silicon carbide-aluminum nitride body iE disclosed by U.S. Patent No. 3,649,310 which is suitable for use as a heating element, amongst other things. The composition may also contain up to 80e of boron carbide, alumina and silicon nitride. The product is made by hot-pressing a mixture of submicron sited aluminum carbide and silicon nitride at about 2000 C. The two material6 react with each other to form a mixture of submicron particles of aluminum nitride and silicon carbide. The resulting material has a density close or equal to theoretical density. U.S. Patent No. 3,875,476 specifically teaches a heat resistant ceramic electrical igniter which is composed principally (25-88t) of silicon carbide and a pyrex glass bond (5-30%): the composition may also include 1-8% ferro-silicon, 1-10% titania, 1-20% zirconia, and 5-30% silica. While not discussed in detail and not included as an example, the reference states that there are other possible mixtures of components including some containing molybdenum disilicide MoSi2. In order to keep the terminal ends cool, the igniter of this patent has a composition, based on the above compounds which varies from one with a relative high resistance in the center or hot-zone to one with substantially leaser resistance in the terminal ends. To avoid problems resulting from significantly different coefficients of thermal expansion, the reference employs several compositions going from the hot-zone to the terminal ends so that there is a gradual compositiona) transition and a resulting gradual transition in the coefficient of thermal expansion of the various portions of the icniter. This eliminates premature cracking of the igniter as a result t of dramatically different thermal expansion characteristics. While the reference does not limit the configuration of the igniter, i.e. apparently the igniter may take any known shape, what is shown is a U-shaped device with the ends of the legs of the U being the terminal connector ends. The shape could of course be straight or more complexly configured as shown in Canadian Patent o. 1,058,673 and U.S. Patent No. 3,875,477. A complex refractory composition is the subject of U.S. Patent No. 3,813,252. The sintered refractory material is made up of 10-20E of boron nitride with 20-808 of the remainder being selected from the group consisting of aluminum nitride, aluminum boride and silicon nitride, and 20-80% of that remainder being selected from the group consisting of graphite, boron carbide, titanium carbide, zirconium carbide, chromium carbide, silicon boride, beryllium boride, magnesium boride and calcium boride. The closest this teaching comes to the present invention is a mixture of boron nitride, aluminum nitride (or silicon nitride) and silicon carbide. What is missing is the all important molybdenum disilicide. Lastly, Canadian Patent No. 1,058,673 discloses a complexly shaped igniter element wherein the hot-tone is made up essentially of recrystallized silicon carbide and the hot-zone includes a continuous groove therein. The silicon carbide contains an electrical resistivity modifying agent such as aluminum oxide, molybdenum disilicide, magnesium fluoride, magnesium chloride or magnesium titanate or a combination of these compounds. The quantity of electrical resistivity modifier to be added, according to the patent is about 10% by weight although as much as 25% alumina in tbe silicon carbide is taught. Silicon nitride is also mentioned as another electrical resistivity modifying agent usuable to change the resistance of the shape and to impart desirable physical properties to the igniter. The principal differences between the present invention and the prior art are the superiority of the invention resistor, particularly when utilized as an igniter, and the novel composition thereof which is whet produces the superior results. None of the prior art teaches an electrical resistor or other refractory product made up of major quantities of all materials, silicon nitride, aluminum nitride, boron nitride mixtures thereof, and molybdenum disilicide with silicon carbide. The total structure developed in the refractory body of the invention is essentially that of 2 separate but intertwined structures with one structure being contained within the other structure. Figures 1 ad 2 are Semes taken at 2000x of polished sections of two different mixtures showing similar structures of a dark gray continuous phase and a light gray continuous phase, with continuities being made 3 dimensionally. The dark gray structure is a dense nitride that is strong and rigid with connecting paths up to about 10 microns in width. The light gray structure is a dense continuous structure that because of its softer nature at elevated temperature has flowed into the interstices of the rigid structure. Figure 1 shows an example of a SO volume % aluminum nitride rigid structure with a 50 volume t MoSi2 and SiC metallic structure with 30 volume t MoSi2 and 20 volume t SiC. Figure 2 shows a 60 volume 8 AlN rigid structure with 40 volume t of the mixture of MoSi2 and SiC where the MoSi2 is 15 volume % and the SiC is 25 volume %. X-ray diffraction patterns show three distinct and well defined phases of A1N, 5i2 and SiC with no additional phases. The light gray metallic phase is seen in figure 3 as an SEM taken at 1700Ox and shows sharp definition between the AlN structure and the MoSi2 and SiC structure but does not shos any distinction between MoSi2 and SiC. It is believed that an essential feature of this type of total structure is that even though there is intimate contact between the two intertwined structures there is no or very little chemical reaction between or diffusion of cat ions from one structure to the other. This has been shown by EDAX analysis in the AIN; MoSi2 and SiC system. Because of this, each structure can contribute its distinctive properties to the total system without interference of an undesired phase between the two structures. In this way the total system can have special characteristics because of interplay of properties. An example would be to select structures with different thermal expansions in which the metallic structure would put the brittle structure into compression for increased toughness of the total system. Another example would be a relatively softer metallic structure to act as an energy absorber for improved impact resistance. Another example would be for a strong high temperature resistant structure to act as a reinforcement for a structure that would be weak or soft at high temperature. Another important example would be as a strong high temperature electrically, non conductive structure to act as a reinforcement for an electrically conductive structure that cn be varied in its electrical characteristics as desired. The strong rigid structure may be made from nitrides such as Si3N4. A1S, or BN or combinations. In the case of Si3s4, a sintering aid would be required to achieve high density but no sintering aid woulc be necessary for AlN. The unusual combination of properties of the present composition makes it suitable for a wide variety of end uses, such as for example, resistors like glow-plugs, heating elernents and igniters, refractory engine components, heat exchangers, structural refractories, etc. The electrically conductive structure may have varying ratios of MoSi2 and sic to vary both the magnitude and the nature of the conductivity. For example, ratios that are high in MoSi2 are 10w in resistivity and ratios that are low in MoSi2 are high in resistivity. When the ratio of MoSi2 to SiC is higher than 0.65 in a composition containing 60 volume t AIN, the resistivity at elevated temperatures is higher than the resistivity at room temperature. The slope of the resistivity curve with temperature is positive similar to that of metallic conduction. When the ratio is less than 0.65 in the 60 volume t Al?: composition, the resistivity curve has a negative slope similar to that of a semiconductor such as SiC. When the ratio equals 0.65, the slope is tero and the hbt resistivity is equal to the cold resistivity. Table 1 shows summarized data of electrical igniters made from various mixtures of AlN,'MoSi2 and SiC. Figure 4 shows the relationship of the slope of the resistivity curve, and the ratio of MoSi2 to SiC for a semi log curve with the equation as shown. With a composition based on 50 volume % Al?: instead of 60 volume %, the ratio of MoSi2 to SiC is .33 when the elope is equal to zero. A main feature of the embodiment of this invention which is an electrical resistor, is that both the magnitude of resistivity and the slope of the resistivity curve may be controlled by varying the two structures with these three ingredients. Increases in the nitride structure will result in increases in the magnitude of the resistivity and vice versa. Increases in the ratio of MoSi2 and siC in the conductive structure will result in decreases in the ratio of cold resistivity to hot resistivity. These decreases in turn, result in decreases in the response time of an igniter. Figure 5 shows the relationship of the ratio of cold resistivity to ho resistivity with the ratio of MoSi2 to SiC. In a composition with 60 volume z AlN, resistivity ratios of 5 or less would be at MoSi2:SiC ratios of .33 or greater. Similarly in a composition with 50 volume E AIN for a resistivity of 5 or less the MoSi2:SiC would be 1.E or greater. TABLE 1 Example # III IV V VI VII VIII IX AlN, Vol% 60 60 60 50 60 60 50 MoSi2, # 5 7.9 10 12.5 15 20 30 SiC, # 35 32.5 30 37.5 25 20 20 Density, % Theor. 96.1 92.9 95.9 96.1 95.5 91.1 99.0 Resistivity; 52cm(%) Measured, 30 89.0 70 5.22 .27 .33 .0029 .0006 " , 12000 12.8 - 1.03 .24 .12 .019 .0035 Calculated 30 * 214 27.2 6.12 - .18 .0050 1200 ** 10.8 3.06 1.23 - .14 .016 Ratio, R30:R1200 19.8 8.9 5.0 1.1 1.3 .3 .2 Slope*** (x 10-3) -2.55 -1.87 -1.37 -.10 -.20 +.99 +1.5 Ratio, MoSi2:SiC .143 .246 .333 .333 .60 1.0 1.5 * R30 = 7457.3 x E (-.7105 x M) correlation coefficient = .984 ** R1200 = 54.244 x E (-.4338 x M) " " = .997 *** RT = A x E (B x T) Semitog curves where: R = Resistivity M = Vol% MoSi2 T = Temperature E = Natural logarithm A = Intercept B - Slope Tne major disadvantages possessed by prior art ceramic electrical resistors, particularly igniters, are the tendency tc oxidize and degrade in use causing the resistivity tc increase unacceptably, ane an inherently high ratio of roon temperature resistivity to resistivity of elevated temperature e.g. 1200 C which requires t high energy input to get the resistor up to the desired temperature. The ceramic igniter taught by U.S. Patent No. 4,120,827, one of the best igniters available, suffers from both of the foregoing shortcomings. Because it is cornposed of essentially only silicon carbide, it oxidizes. The patented igniter in sortie cases has a ratio of room. temperature to elevated temperature resistivities of 5.5 which is good relative to other prior art devices but is still undesirably high. It has now been found that the deficiencies of the prior art are greatly n,inimized by utilizing the composition of the present invention. Electrical igniters with ratios of room temperature resistivity to resistivity at 1200'C as low as 0.2 result from a sintered or hot-pressed volume percent mixture of from 30% to 70E of a nitride of aluminum, silicon, or boron: 10E to 45% of silicon carbide; 5% to 50% of molybdenum disilicide; and 0 to 3% of a sintering aid such as a source of magnesium oxide; which has been hot-pressed or sintered to a density of at least 85% of theoretical density. Sintering or pressing aids such as magnesium carbonate are well known and while the use of such a material is not always necessary, it always is advantageous to the processing and the end product, to utilize such a material. All percentages recited herein are volume percentages unless otherwise indicated. The folloving material densities were used to calculate weight percentages from volume percentages: Si3N4 3.20 Mg/m AlN 3.26 MoSi2 6.26 SiC 3.20 Treoretical densities were determined from the material densities assuring the law of mixtures. Whether the device be a heating element or a fuel igniter, so-called cold ends are absolutely necessary to a successful device. Terminal ends or cold ends are made cold by making them much more conductive than the hot-one. T}liE can be done, for example, by impregnating the terminal ends with metal, or, by varying the composition of a monolithic ceramic resistor from the hot zone out to the terminal ends, with a gradually changing ceramic composition starting with a high resistivity formulation in the hot-zone of the resistor workino out to b highly conductive composition in the terminal ends. zone present invention favors the latter approach. To accomplish that end the present resistors preferably have cold ends (terminal ends) n,ade up of 40t to 60E of a nitride, 5% to 30% of silicon carbide and 30E to 502 of molybdenum disilicide and a hot-zone made up of 40% to 60e of a nitride, 10% to 408 of silicon carbide and 5e to 20E of molybdenum disilicide. The compositional transition from the hot-zone into the cold ends may be an abrupt one or a gradual one. bhen using some compositions of the present invention, a gradual compositional transition is desirable to avoid problems caused by differences in coefficients of thermal expansion of the two tones. On the other hand somme compositions are so similar in coefficients of thermal expansion that an abrupt compositional change can be used. Another method for creating cold ends is to design the igniter such that the volume of the terminal ends is at least 5 times greater than the volume of the hot-zone and preferably 5 to 10 times greater. The preferred nitride is aluminum nitride. To acquire the optimum density and electrical properties the particle sizing of the powders, including the silicon carbide, molybdenum disilicide and sintering aid is not critical except that the particle sizes should be fine enough to allow the resistor itself or the billet from which a heating element or igniter is to be machined, to be pressed to near theoretical density. A. suitable particle sizing for the materials involved is an average particle size of 3 microns and finer for all materials. The electrical resistor of the invention can be any one of variety of configurations, depending on its intended end use. It may be very simple in shape such as a straight rod shape with the cold ends or terminal connecting ends on the opposite ends of the body such as that of U.S. Patent 3,252,827. On the other hand the shape could be more complex suck as those shown in U.S. Patents 3,875,477 and 3,875,476 and Canadian Patent 1,05E,673. For use in a gas rance for example, a small 1-1/2 inch (4 cm) long 1/4 inch (1/2 cm) wide and 0.4 inch (.1 cm) thick igniter in a horseshoe or hairpin shape would be most suitable because of stringent space restrictions. However, other configurations may be more desirable in other applications as for example in a clothes drier where the igniter may have to withstand occasional high mechanical forces in which case any igniter shape such as that taught by U.S. Patent 3,875,477. Because electrical resistivity may be varied over several orders of magnitude, configurations may be designed to accommodate the application rather than the electrical characteristics of the material as is frequently found with silicon carbide igniters. For example, high voltage, low power systems could be designed with reasonable, easily machinable dimensions instead of thin very long rods or coiled wire. A 50 watt igniter operating at 220 volts could be a hairpin with a hot one 2.1 cm long for each leg with leg width of .16 cm and thickness of .06 cm. This igniter would require a resistivity of 2.2 ohm cm which would be achieved by a mixture of 50 volume % AIN, 7.8 volume t NoSi2 and 42.2 volume B SiC. Similarly a low voltage, low power igniter may be designed as a hairpin with a hot tone leg length of 1.0 cm, a leg width of .15 cm and a thickness of .063 cm. This igniter would operate at 24 volts and 24 watts. A resistivity of 0.09 ohm cm would be achieved by a fixture of 60 volume z A1N, 15.9 volume @ MoSi2, and 24.6 volume 4 SiC. The present electrical resistor can be further improved by providing a protective coating thereon. If a resistor of the invention is heatec at 1300'C for 6 hours in air, a protective coating of what is believed to be a mixed oxide is formed on the surface. This coating prevents oxidation of the main body of the resistor particularly the molybdenum disilicide which can undergo oxidation at 400-500'C which can result in an undersirable volume change. Another approach is coating an igniter for example with very fine silicon carbide followed bg oxidation of the coating to silica. Still a third means of enhancing the life of a resistor is to coat it with either silicon nitride or silicon oxynitride providing such coating is impervious to air. The invention resistor is ideal for use as a fuel igniter. A very critical property of an igniter, especially if gas is the fuel, is the heat up time i.e. the time for the hot-tone of the igniter to get from room temperature to the ignition temperature of the gas. This is is controlled primarily by the ratio of room temperature resistivity to resistivity at 1200-C: the higher that ratio the longer the heat up time. U.S. Patent 4,120,827 boasts of ratios less than 12, preferably 9 and contains an example where said ratio was as low as 5.5. The same ratio for igniters of the present invention can easily be designed to be less than 5 and as low as .2 thus providing igniters with very rapid response or heat up times. Similarly, because igniters are small, mechanical strength becomes important. The composition of the present invention results in an igniter with a modulus of rupture at room temperature using 2 inch (5.08 cm) span with 3 point loading of about 66,000 psi 450 MPa when the mixture of nitride, carbide and silicide is hot pressed to 99.7% of theoretical density. Of great importance to the commercial success of a ceramic igniter is that devices ability to survive for long periods of time in a very hostile environment without being physically destroyed. A gas igniter for a gas range, for example, should be able to withstand numerous heat-up and cool-down cycles; it should also be able to survive many hours exposure to elevated temperatures ane the chemical environment of a gas flairte. The present igniters can easily undergo 12,000 cycles and prolonged exposure to a gas flame for over 400 hours without significant physical damage. However, resisting physical dairage is only part of the survival characteristics required in a successful igniter. The other part iE the ability of the igniter to go through the foregoing severe and prolonged exposure without a drastic change in the ratio of roon temperature resistivity to resistivity of 1200 C, for the reason stated above. Because the resistors of the invention are so stable to deterioration the ratio remains relatively constant. With reference to the accompanying drawings: Figures 1 and 2 are scanning electron microscope (SEM) photomicrographs of two different compositions of the invention, taken at 2000x. Figure 3 is a scanning electron microscope (SEM) photomicrograph of the composition of Figure 2 taken at 17000x. Figure 4 graphically shows the relationship between the slope of the resistivity curve and the ratio of MoS2:SiC. Figure 5 graphically shows the relationship of the ratio of hot resistivity to cold resistivity as a function of MoS2:SiC. EXAMPLE I Two igniters were fabricated and compared in use. One was a silicon carbide - silicon nitride igniter made according to the Richerson patent U.s. Patent No. 3,890,250 and the other was made according to the present invention. A mixture of 60% by weight of silicon nitride and 408 by weight of silicon carbide, according to the Richersor. patent, was hot pressed into a billet to a density of 3.08 Ng/m3. The mixture was made up of 3 micron silicon nitride containing 2-5E magnesium, carbonate and 3 micron silicon carbide containing .8% of aluminum and hot pressed at 1775'C. From the billet an igniter was machined with a hot-zone which measured 0.104 cirri x 0.106 cm x 2.46 cm long which had 8 resistivity at room temperature of 1.60 ohm-cm and at 1200 C a resistivity of 0.82 ohm-cm. The igniter was life tested at 1200*C and it WbaE found that after only 311 hours the resistance of the hot-zone at 12000C had increased from 182.4 ohms to 274.4 ohms1 an increase of 35.6t. The resistance of the cold ends and electrical connections increased from 40.4 ohms to 154.4 ohms or a change of 2825. It was found that by mixing a substantial quantity of molybdenum disilicide with the silicon carbide, and blending with silicon nitride many of the problems with low density, hot-zone degradation, and high resistance of the cold ends, were overcome. A mixture of 58.5t silicon nitride 30t silicon carbide, 108 molybdenum disilicide, and 1.58 magnesium carbonate was prepared as follows: The silicon nitride was made from 3 micron silicon and was about 95% alpha silicon nitride. This was blended with reagent grade MgC03 powder in isopropyl alcohol in a blender. The silicon carbide used was 3 micron material and was balled milled with finer than 200 mesh molybdenum disilicide for 7-8 hours in isopropyl alcohol using tungsten carbide milling balls. The two mixtures were then blended by rolling together in a ball mill for 30 minutes. This was done to insure that the conductive matrix of silicon carbide and molybdenum disilicide was a homogeneous mixture and yet had a coarse structure without a lot of fine bridges when combined with the silicon nitride. A disc measuring 7.62 cm in diameter and 0.79 cm thick was hot pressed using 155 g of the above mixture dried. The pressing was done in a graphite mold at 1775'C and a load of 8 Mg with a soak at 1775*C of approximately one hour. The density of the pressed mixture was 3.356 Mg/m with theoretical density being 3.366 Mg/m ; the presence piece was 99.7% of theoretical. An igniter was machined from this billet or disc. It had a hot-zone measuring 3.16 cm x 0.12 cm x 0.06 cm with e tab on each end measuring 1.91 cir x 0.7 cm x 0.06 cm. The ratio cf cross section of the cold ends to the cro6E section of the hot zone was about 11 to 1. The igniter was placed in a furnace and heated at 1300 C in air for 6 hours. This produced a thin oxide protective coating on the igniter. Electrical contacts were made on the tabs by first machining 0.25 cn wide by 0.63 cm in frorr. the ends. The igniter was then masked so that only the slotted ends were exposed and the protective oxide film was sand blasted off the exposed ends. A machine screw 2-56 x 1/2. and 4 Belleville washers and a nut were assembled and tightened in the slot on each end. The four washers flattened with a load of 40 kg; a section of 0.3 mm nickel wire was looped around the screw and held in place with a second nut; the wire was connected electrically. Resistivity at room temperature was 0.252 ohm-cm and dropped to a minimum of 0.146 at 1100 C then increased to 0.148 ohm-cm at 1300 C. The ratio of resistivities at room temperature to 1200 C was 1.7. A life test was run at 1200-C in air comparing the igniter according to the Richerson patent (Prior Art) and the above invention igniter with the following results: Prior Art Invention Size of hot zone: Width x thick (cm2) .104 x .106 .109 x .064 length (cm) 2.46 3.18 Total voltage at start 86.0 56.8 Total aperage at start .386 .754 Total power at start (watts) 33.2 42.8 Power for hot zone (watts)PH 27.1 38.0 Hot zone resistance start, RH 182.4 66.8 Hours of operation 311 908 Hot zone resistance at end, RH 247.4 70.5 %RH 35.6 5.5 e R!hr 0.114 0.006 These data show that the aging of the Invention igniter is consideraly less than that of the Prior Art igniter. The resistance change for the Invention igniter took place essentially during the first 30 hours when the total change was only 7t. There was essentially no change for an additional 500 hours after which the resistance slowly decreased by about 5.5E based on the original resistance after 908 hours. The igniter actually became more conductive with time at 1200 C The e voltage remained stable after a slight initial increase frorn 56.2 to 57.0 volts; this was due to a small increase in the resistance of the cold ends. The cold ends operated at a temperature of 260 C and were stable after the initial 125 hours with essentially no further change taking place. The resistance of the cold ends of the Invention igniter decreased from 8.5 ohms to 5.8 ohms after the first 56 hours, showed an increase to 6.6 ohms after 160 hours remaining steady for 600 hours, after which the resistance gradually increased to 7.5 ohms at the 908th hour. The Invention igniter changed a total of 29% while the Prior Art igniter changed resistance by 282%. Furthermore, the cold ends or tabs of the Prior Art device were running at 394'C and 456 C while the Invention igniters cold ends remained at 280'C and 250-C. EXAMPLE II A double-legged dual composition hairpin or U-shaped igniter made up of aluminum nitride, silicon carbide and molybdenum disilicide was fabricated in the following manner: Two batches of 101.8 grams and 90.4 grams of througb¯325 mesh aluminum nitride were ball milled in isopropyl alcohol for 1 hour using a tungsten carbide lined mill and tungsten carbide inilling media. Two mixtures of 98.2 grams and 139.6 grams of molybdenum disilicide and silicon carbide were prepared in the same way; the first of these ruixtures was made up of 75% molybdenun disilicide and 25% silicon carbide, and the other mixture was 50% molybdenum disilicide and 50% silicon carbide, all percentages being by volume. Two mixtures containing all three materials were prepared to give one with 50-30-20 and the other 60-20-20 volume percent aluminum nitride, molybdenum disilicide and silicon carbide respectively. 40 grams of the high silicon carbide mixture and 47.2 grams of the high molybdenum disilicide mixture in the form of alcohol slips were placed side-by-side in c graphite mold in the form of slips with a graphite spacer between the two; the mold had a cavity measuring 2- x 2.5" (5.08 cm x 6.35 cm). The e alcohol was removed, and the materials were hot pressed, after completing the assembly of the mold at about 1.2 tons/in2 (16.6 MPa= and 1760-1820iC in an argon atmosphere to maximum contraction followed by a 60 minute hold. A double-legged hairpin or U-shaped igniter was machined from the billet with the high silicon carbide mix making up the hot tone and the high molybdenum disilicide material being in the legs or terminal connecting ends. The hot-zone measured 1.4 cm x 0.242 cm x 0.061 cm. The igniter was given a protective glaze or coating by firing it in air at 1350 C for about 6 hours. The e device was electrically connected with alligator clips and caused to heat up to 1200-C; it was allowed to maintain this temperature for a total lift test of 1988 hours. The resistivity at room temperature was 0.0073 ohm-cm and 0.019 ohm-cm at 12000Ci at the start the voltage was 13.71, power at 1200'C was 16.6 watts and the load at 1200-C was 24.1 watts/cm2. The terminals were stable and remained at a relatively constant temperature of 1200C for 1988 hours. During the life test the total change in resistance was 0.06E of which the hot zone gained 1.64% and the terminal connection lost l.70t.

Claims: CLAIMS 1. A formed refractory composition consisting essentially of 30% to 70% by volume of a nitride which is silicon nitride, aluminum nitride, boron nitride or a mixture thereof, 5% to 40% by volume of silicon carbide, 5% to 50% by volume of molybdenum disilicide, and 0 to 3% by weight of a sintering aid, wherein said formed refractory composition has a density of at least 85% of theoretical density. 2. The formed refractory composition of claim 1, wherein said composition varies from one section thereof to another such that one of said sections is made up of essentially all molybdenum disilicide. 3. The composition of claim 1, formed into an electrical resistor, including a hot zone and cold ends. 4. The electrical resistor of claim 3, wherein the composition changes gradually from hot zone to cold ends. 5. The electrical resistor of claim 3, wherein the composition varies abruptly from hot zone to cold ends. 6. The electrical resistor of any one of claims 3 to 5, wherein said cold ends are made up of essentially all molybdenum disilicide. 7. The electrical resistor of claim 3, wherein said resistor is a heating element or an igniter. 8. The resistor of claim 3, having cold ends and a hot zone wherein the resistivity differential between the cold ends and the hot zone is the result of said cold ends being made up of 30% to 708 by volume of said nitride, 5% to 30% by volume of silicon carbide, and 30% to 50% by volume of molybdenum disilicide; and said hot zone is made up of 30% to 70% by volume of said nitride, 10% to 40% by volume of silicon carbide, and 5% to 20% by volume of molybdenum disilicide. 9. The resistor of clain 3, wherein said nitride is silicon nitride and sintering aid is a source of magnesium oxide. 10. The resistor of claim 9, wherein said resistor is formed from 40% to 70% by volume of silicon nitride powder having an average particle size of about 3 microns, 10% to 40% by weight of silicon carbide having an average particle size of about 3 microns, 5% to 30% by weight of molybdenum disilicide having a particle size of about 3 microns and .5t to 3.0% by weight of a source of magnesium oxide having an average particle size of about 3 microns, and wherein said resistor has a density of at least 3 2.62 Mg/m 11. The resistor of claim 3, wherein said nitride is aluminum nitride. 12. The resistor of claim 11, wherein said resistor is formed from 40% to 65% by weight of aluminum nitride powder having an average particle size of about 3 microns, 10% to 40% by weight of silicon carbide having an average particle size of about 3 microns, 5% to 50% by weight of molybdenum disilicide having a particle size of about 3 microns, and wherein said resistor has a density of at 3 least 2.80 Mg/m 13. The resistor of claim 3, having cold ends and a hot zone wherein the resistivity differential between the cold ends and the hot zone is a result of the cold ends having a volume 5 to 10 times greater than the volume of the hot zone. 14. The resistor of claim 3, which includes a protective coating thereon which is silica, silicon oxynitride, silicon nitride or a protective mixed oxide coating. 15. The formed refractory composition of claim 1, made up of two separate but intertwined structures including a first dense continuous phase made up of a nitride selected from the group consisting of silicon nitride, aluminum nitride, boron nitride and mixtures thereof, and a second dense continuous phase made up of a mixture of silicon carbide and molybdenum disilicide.

Inventors: WASHBURN, MALCOLM E.
Applicants: NORTON COMPANY
Application year: 1985
Main classification: C04B35
IPC codes: C04B35, F23Q7, H01C7, H05B3