CA1328347C - Tubular ceramic articles, methods and apparatus for their manufacture - Google Patents

Abstract

TUBULAR CERAMIC ARTICLES, METHODS AND APPARATUS
FOR THEIR MANUFACTURE
ABSTRACT

The present invention relates to methods and apparatus for producing tubular articles of silicon carbide and silicon.
The articles contain silicon in both metallic and in chemically combined form. The method consists of the steps of concentrically positioning a vertical tubular columns of particulate silicon contiguous to a hollow, vertical tubular columns of particulate silicon carbide, carbon, or mixtures of silicon and carbon, and heating the adjacent columns to a siliciding temperature. The silicon component infiltrates the column containing the particulate silicon carbide, carbon, or mixtures thereof, forming a tubular product. The apparatus consists of supply hoppers for holding the particulate feed material, a loading means comprised of spaced, concentrically arranged, tubular forms. The loading means is positioned within a vertically positioned electrical induction furnace.
Particulate feed materials are dry cast into the spaces between and around the forms. The loading means is then removed leaving separate vertical, hollow columns of particulate feed materials concentrically arranged within the furnace. The furnace is then heated from top to bottom to a siliciding temperature. The silicon component infiltrates the column containing silicon carbide, carbon or mixtures thereof to form a dense, tubular silicon-silicon carbide product.

Description

TUBULAR CERAMIC ARTICLES, METHODS AND APPARATUS
FOR THEIR MANFACTURE
BACKGROUND O~ THE INVENTION
The ~resent invention relates to tubular ceramic articles comprised of silicon and silicon carbide, and to processes and apparatus for the manfacture of such articles.
Silicon carbide, a crystalline compound of silicon and carbon, has long been known for its hardness, strength, and excellent resistance to oxidation and corrosion~ Silicon carbide h~s a low coefficient of expansion, good heat transfer properties and exhibits high strength and excellent creep re~istance at elevated temperatures. These desirable properties may be attributed to a strong covalent chemical bonding, w~ich also is the cause of an undesirable property of llicon carbide, that of being difficult to work or fabricate the mater-ial into useful shapes. For example, because silicon carbide dissociates at high temperatures, rather than melting, it is not feasible to fabricate articles by melt processes, and becau~e silicon carbide has a very slow diffusion rate, fabric~tion by plastic deformation processes is not viable.
It has been proposed to produce shaped silicon carbide articles by forming bodies of silicon carbide particles and e~ther bonding or sintering the particles at high temperature~
to form a consolidated body. If the particulate silicon carbide starting materia~ is fine enough, and suitable ~intering aid~ are added, the fine, particulate material will exhibit sufficient self-diffusion at high temperatures that ~.

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'`, ' ~ ' ' ~ -' ~ . ' the particulate material will sinter and form into qubstantially dense single phase material. Sintering processes, in general, require fine powder starting materials and pre-qsurele~s sintering processes, in particular, require an even finer starting material. Because of the needed fineness and high purity of the starting materials, articles formed by sintering processes are relatively expensive.
Coar~er and less pure silicon carbide powders are known to bond together at high temperatures. However, the resultant products have considerable porosity and for that reason are usually not as strong, or as corrosion resistant, as more fully densified materials. The properties of such materials may be substantially improved by infiltrating the pores of uch materi~ls with silicon, in either vapor or liquid form, to produce a two phase, silicon-silicon carbide product.
Although such processes utilize relatively inexpensive coarse powders as starting materials, they require two high temperature furnacings, one to form thè silicon carbide to flilicon carbide bond and a second, separate furnacing, to infiltrate the formed body with silicon.
Mixtures of coarser and less pure silicon carbide powder~
with partlculate carbon or with a carbon source material may be preformed and subsequently impregnated with silicon at high te~perature to form ~reaction bonded~ or "reaction sintered"
illcon carbide products. The carbon component may be in the form of particulate graphite or amorphous carbon, or may be in he form of a carbon source material, for example a , carbonizable organic material, such as, pitch, resin or similar ~aterials, which will decompose during furnacing to yield carbon. The infiltrating silicon reacts with the carbon in the preformed body to form additional silicon carbide which bonds with the orginal ~ilicon carbide particles to produce a dense ellicon carbide article. Typically reaction bonded ~ilicon carbide materials are characterized by almost zero porosity and the presence of a second phase, or residual, -of silicon, usually greater than about 8% by volume.
In typical siliciding or typical reaction bonding proce~es, the particulate silicon carbide and carbon starting material 1B initially preformed or preshaped into an article, commonly referred to as a "green body", which is subsequently fired. The particulate silicon carbide and carbon starting mixture is co~monly blended with a binder to aid in shaping.
If the binder is dry, or relatively dry, the powder may be compacted to the desired shaped green body using a press or isopress. If the binder i8 liquid, or seml-liquid, and i~
used in sufficient quantity, the mixture may suitably be 81ip ~ast, extruded or injection molded to form a shaped green body.
High temperature heat exchanqe components desirably have relatively thin wall~ to facilitate high rates of heat transfer. There have been previou~ attempts to fabricate tubular article~ of silicon carbide by variou~ methods, however, none have proven commercially successful. For .
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example, US Patent 801,296 discloses a method of producing a hollow silicon carbide tube by siliciding a solid carbon rod to form an outer layer of silicon carbide and subsequently burning out the carbon interior leaving the outer layer of silicon c~rbide. US Patent 1,266,478 describes a typical method of preforming a tubular body of silicon carbide and cnrbon and siliciding to obtain a tubular silicon carbide article. US Patent 1,756,457 teaches the reaction of silicon dioxide and carbon in preformed column~ to produce a silicon carbide tube. US Patent 3,495,939 teaches making tubular ~ilicon carbide by preforming a tube of particulate silicon carbide and carbon, positioning the tube vertically in a furnace and siliciding with the bottom of the tube in contact w~th liquid silicon. US Patent 3,882,210 teaches siliciding a preformed tube of alpha silicon carbide and graphite to produce a tube of silicon carbide. US Patent 4,265,843 de~cribes the manfacture of silicon carbide in tubular form by initially heating at low temperature a rotating preformed carbon tube in the presence of silicon to impregnate the tube and subsequently heating at a higher temperature to react the silicon and Carbon to form a tube of silicon carbide.
It will be appreciated that the fabrication of long, ~e.g., four to eight foot), large diameter, (e.g., four to eight inch OD), thin-walled, (e.g., 1/8 to 1/4 inch), tubes presents a difficult problem. The tubular green bodies that are required to be initially formed by the prior art processes are inherently structrually weak and easily deformed or broken : . . , :

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unless h~ndled with utmost care. In subsequent processing steps, the tubular green bodies must be carefully dried, and/or baked, and positioned in a furnace for siliciding. The fragility of the preformed bodies and the required multiple handling entaillng high labor imput have been major factors in preventinq the use of tubular silicon carbide in many applications purely on the basis of cost. ~he term ~reaction sinter~ as used herein means consolidation by chemical reaction and includes the reaction of silicon with carbon either alone or in mixture with silicon carbide.
The term "carbon" as used herein means carbon or a carbon source material that produces carbon upon heating that will react with the infiltrating silicon to form additional silicon carbide, in ~itu.
The ter~ ~tubular~ as used herein means that the article h~s the for~ of a tube, that is, it i8 fistulous. Although the pre~ent invention will hereinafter be described in terms of tubes having generally round cross-sections, it will be understood that the i~nvention is not so limited and that tubes having eliptical, square or multi-sided cross-section , or having an external surface of one cross-sectional type and an internal surface of another, may as easily be produced. It wlll aloo be understood that the -present invention also contemplates tubular articles that have internal separa~ions, or septums, providing multiple passageways within the tube.

GEN~AL DESCRIPTION OF THE INVENTION

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The preient invention relates to tubular articles of manufactur~ comprised of silicon carbide and silicon and to methods and apparatus for the production of such articles.
The articles are c~aracterized in that they contain silicon in metallic and in chemically com~ined form.
The method consists of the steps of concentrically po~itioning at least one hollow, vertical tubular column of particulate silicon adjacent to, or contiguous to, at least one hollow, vertical tubular column of particulate silicon c~rbide, carbon, or mixtures of silicon and carbon, and heating the adjacent columns to a siliciding temperature, that i8, a temperature above the melting point of silicon (about 1410 to 1~20 degrees C.) and less than about 2400 degree~ C.
At such temperatures the particulate silicon component melts or vaporizes and infiltrates into the pores of the column containing the particulate silicon carbide, carbon, or mixture~ thereof, forming a tubular ceramic product.
The apparatus consists of a plurality of supply hoppers for holding a particulate feed material, a loading means comprised of at leàst two spaced, concentrically arranged, dimensionally stable, tubular form members. The loading means is of a si~e to spacedly fit within the furnace tube of a vertically positioned electrical induction furnace and i8 ~oveable in and out of the furnace tube. Selected particulate feed materialo ~re dry cast, suitably by flowing, into the opaceo between and around the form members. For example, the lo-ding means is initially centrally, or coaxially, positioned '' ' ' ' .': ~ ' '/ ' : .
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in the furnace tube, spacedly surrounding the furnace heating element. After the filling, or dry casting, operation i8 completed, the loading means is removed from the furnace. The ~psce between the outer form member and the inner furnace wall is Ruitably filled with a particulate heat-insulating material, the space between the form members is selectively filled with silicon, carbon, or mixtures thereof and the space between the inner form and the heating element is selectively filled with silicon. After the dry casting operation, eparate vertical, hollow columns of particulate feed ~aterial- remain concentrically arranged within the furnace.
The furnace i3 subsequently progressively, or incrementially, heated from top to bottom to a siliciding temperature. The silicon component infiltrates the column containing silicon carbide, carbon or mixtures thereof. The infiltrated column i8 subsequently cooled to form a dense, tubular silicon-sillcon carbide product.
The particulate silicon carbide starting material is of a sufficiently coarse particle size that the material is easily flowable through the apparatus without plugging. Suitably the particles are greater than 50 microns and less than 500 ~lcrons in diameter, and the term ~particulate" as used herein carries this Deaning. The particulate silicon carbide starting Fateri~l may be of a single particle size or may consist of a co~bination of separate particle sizes to enable higher packing efficiencies.

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Particulate carbon may be utilized as a sole feed material, or may be used in mixture with particulate silicon carbide. The particulate carbon component reacts with the infiltrating 9i licon to form silicon carbide, in situ, reducing t~e amount of free unreacted silicon remaining in the finished product. The amount of free silicon desired in the finished product is dependent upon the use of the product.
For exami-ie, it the end product requires abrasion, oxidation, or corro~ion re~ist~nce, a minimal, or minor, amount of free ~ilicon and free carbon would be desired in the product, as the hardness and chemical inertness of silicon and carbon i8 les~ than that of silicon carbide.
In a particularly useful alternate embodiment of the invention, particulate graphite and particulate silicon are utilized as the starting materials. In such embodiment ~eparate, adiacent columns of particulate graphite and particulate silicon are heated to a siliciding temperature.
The silicon infiltrates the graphite column reacting with the graphite to form silicon carbide. If the particulate graphite is fine, less than about SO microns, the graphite will be substantially completely converted to silicon carbide. If the graphite particles are larger than about 50 microns in ~iameter, a thin layer of silicon carbide will form on the qraphite particles and a three phase material will be produced. Such material has silicon and graphite as major pbases with a minor phase of silicon carbide.
The preQence of a large amount of graphite phase affects ' ' ~, ~ - ' : ; ' ~ , . . :
, , ' ': ' ' the phy~ical properties of the present products. Graphite, a crystalline form of carbon, has a low elastic modulus, low thermal expansion rate, and a high thermal conductivity. When incorportated in the present products in amount~ over about ten percent by volume, the products show improved thermal ~ock and thermal stress resistance. Amounts of greater than about ~ixty percent by volume are difficult to achieve using ~ilicon infiltration processing.
The pre~ent process may be characterized in that no green body, a prerequsite of the previous tube forming methods, is required or produced by the present invention. Particulate material is fed into the furnace, and after firing, a finished ceramic tube i~ removed rom the furnace.

DETAILED DESCRIPTION OF THE INVENTION
The present tubular articles are composites which contain silicon in free, unreacted, and in chemically combined form~.
Tbe compo4ites are comprised of free, unreacted, silicon and a material ~elected from silicon carbide, carbon, or mixtures thereof. The final product contains from about five to about sixty percent, and more typically from about ten to 55 percent by volume ~ree ~ilicon; from about forty to about 95 percent, ~nd more u~ually from about 45 to about ninety percent by volume silicon carbide, and; from about zero to about forty percent by volume free carbon.
The composite tubular articles are produced by dry casting, that i8 by forming, suitably by flowing, adjacent, or ~: , . . . .

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contiguous hollow, coaxially arranged, vertical columns of selected particulate starting materials. The hollow concentric columns of particulate material are subsequently heated to react the materials in the columns to form a tubular product. The columns individually consist of particulate silicon and of particulate silicon carbide, carbon, or mixtures thereof. The attached drawings, discussed in detail below, illustrate apparatus particularly suited to carrying out a dry casting process. The heating step is preferably carried out by induction heating, under an inert atmosphere, or in a vAcuum. Suitable siliciding temperatures are above the melting point of silicon, usually at least about 1500 degrees C., but below about 2400 degrees C.
The ~ilicon component can be particulate, commercial grade sillcon, h~ving an average particle size ranging from about 1500 to le~s than about forty microns. A particularly useful silicon material ranges from about 100 to about 1000 microns in diameter. The size of the silicon particles is not cr$tical, except fo~r flow and packing characteristics, as the silicon component i8 completely melted during the siliciding process .
The silicon carbide component i8 also particulate, that 1~ tbe particles have an diameter of less than about 500 microns, and more preferably have an average particle~ size between about 75 and about 300 microns in diameter. The ~ilicon carbide component may suitably be selected from alpha -' ~

or bet~ ph~se s11icon carbide. Mixtures o alpha and beta phase mater;al may be used. The silicon carbide starting material does not require seperation or purification, minor amounts of unreacted carbon, silicon and silicon dioxide, a3 ~ell a~ minor amounts of impu~ities isuch as iron, calcium, magnesium and aluminum, may be present without deleterious affect.
The carbon component may be either amorphous carbon or graphite provided that it i~ of a size that it is free~flowing and is free-flowing when used in mixtures with silicon carbide. Free-flowing carbon materials having a particle size ranging between about 0.01 and about fifty microns, and preferably having an averaqe particle size between about 0.5 ~nd about 25 microng are aptly suited to use, if no unreacted carbon is desired in the final product. If unreacted carbon i~ desir~d in the final product, a coarser carbon starting material is utilized, and in such case, carbon materials having particle sizes ranging from about~50 to about 1500 microns and more preferably between about 100 to about lO00 micron~ are typlcally useful.
In carrying out the present siliciding operation the hollow column of particulate silicon melts and infiltrate~
into the hollow column containing particulate silicon carbide, carbon, or mixtures thereof. In such event the wall of the latter column may be subject to partial collapse because of , the 1088 . of support of the adjacent wall as the silicon component is removed by melting. This situation can be greatly .~.. ;. ' :

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minimized, or prevented entirely, by blending a small amount of a dry particulate temporary binder, for example, a thermosetting resin, suitably a phenolic resin, in the feed material used for the column.comprised of silicon carbide, carbon, or mixture~ thereof. Alternatively resin may be added to the ~eed material by dissolving the resin in a solvent, such as, acetone, and blending the resin solution into the feed material. Subsequent drying will deposit the resin in a coherent, ~ubstantially even manner on the particles of the feed material. Amounts of resin between about one-half and about ten percent by weight of the feed material are generally useful. The binder should be one that will leave a carbon residue in the column upon heating, in such case the residue will provide additional carbon for reaction with the silicon component.
The' siliciding step is carried out at temperatures above the melting point of silicon, about 1410 to 1420 degrees C., and at a temperature less than about 2400 -degrees C. The siliciding step is carried out in an inert atmosphere, or in a vacuum, the latter being preferred. Vacuums between about 0.001 Torr and about 2.0 Torr are eminently suited to uQe. If an inert atmo~phere is utilized slightly higher siliciding temperatures will usually be required. Suitable inert atmospheres are for example, nitrogen and nobel gases,~ s~ch as, argon and helium. An inert atmosphere is one that will not deleteriously affect the siliciding process. After the t ~" :. ' ' . , . :

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~llicidin~ process is complete, the tubular product is preferably allowed to cool in the furnace to a temperature below about 1200 degrees C. while the inert atmosphere or vacuum maintained to prevent oxidation of the product.
The weight amount of silicon to completely infiltrate the hollow column of particulate silicon carbide, carbon, or mixtures thereof, can be calculated from the packing density of the silicon carbide or carbon grain, the amount and type of carbon, the particle size of the components and the de~ired thickness and composition of the tubular product. The proper amount may be calculated from such data, or may be determined emphirically.
The preferred form of heating is by electrical induction heating and a preferred furnace is a vertical vacuum induction furnace which mdy be of a core-type or a coreless type.
Heating ~8 carried out from the top of the furnace to the bottom, that is, the siliciding process is progressively carried out starting from the top~ of particulate, concentric~lly arranged, hollow columns of the starting material~ and procèeding to the bottom, or base, of the columns.
THE DRAWINGS
; The invention will now be further illustrated in greater detail by reference to the attached drawings which illustrate apparatu~ particularly suited to carry out the present invention. Similar components are designated by li~e reference numbers throughout the several views.

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Figure 1 ~s an front elevational sectional view showing a preferred furnace loading apparatus.
Figure 2 is a sectional top view of the loading apparatus taken along lines 1-1' of Figure 1 and also illustrates a centering, or spacing, means that may be utilized.
Figure 3 is a partial vertical section of the induction furnace of Figure 1 showing the loading means positioned within the furnace and the furnace being charged by the present dry casting method.
Figure 4 is a partial vertical section of the induction furnace of Figure 1 as the furnace would appear when fully charged and the loading means has been removed.
Figure 5 is a partial vertical view of the induction furnace of Figure 1 showing the furnace being heated to siliciding temperature and the tubular product being produced.
Figure 6 is a partial vertical view of the induction furnace of Figure 1 showing an alternative arrangement wherein the furnace is of the coreless type, that is, no internal heating element is utilized.
Figure 7 is a partial vertical view of the induction furnace of Figure 1 showing an alternate arrangement in which the particulate columns have an additional, temporary support means.
Looking now in detail at Figures 1 tbrough 4, particulate feed material is supplied through supply hopper ~eans, such a~, 11, 13, 15. Suitably there is one hopper provided for each hollow vertical column of particulate material that is to be formed in the furnace. For example, as shown, one hopper would supply particulate silicon, one would supply particulate silicon carbide, carbon, or mixtures thereor, and one would suppiy particulate heat-insulating material. Loading means 17 is comprised of a plurality, at least two, concentrically arranged, dimensionally stable, hollow, open-ended cylindrical form members, 19 and 21, ~uitably fabricated of thin metal tubes. Loading means 17 is of a size that will spacedly fit within vertical vacuum induction furnace 23. Loading means 17 is positioned on insulating material, such as, 28, which suitably is particulate fuQed quartz. Induction furnace 23 is suitably comprised of a furnace tube 25, a vertically moveable induction coil 27 electrically connected to an electrical induction power supply 29. As shown, in Figures 1 through 5 and 7, induction furnace 23 also includes a heating core, or element, for example, 31. Furnace tube 25 is suitably fabricated of fused quartz, as such material i8 a good electrical insulator, is substantially impervious, can withstand reasonably high temperatures, has good thermal shock resi~t~ce, and i8 commercially available in large tubular forms. Heating element 31 is suitably fabricated of graphite and may be i~ the form of a simple hollow tube of graphlte without spirals or cuts usually required in resi~tive heating elements. Loading means 17 is moveable in and out of furnace tube 25, suitably by means of a reversible lift, such as 30, .

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of a type well known in the art, for example, an adjustable sc~ew, rac~ and pinion, or worm gear arrangement.
Figure 2 illustrates a centering, or spacing, means, 39, that ~ay be positioned on the outside periphery of loading means 17. Spacing means 39 are eminently useful in enabling loading means 17 to be centered within furnace tube 25.
Spacing means 39 may be in the form of extentions such a~
feet, or in the form of narrow, preferably intermittent, strips positioned along the periphery of outer form member 19.

To load furnace 23, loading means 17 is lowered to the position shown in Figure 3, by a reversible lift mean~, such as 30, into contact with insulation 28 positioned on the interior base portion of furnace tube 25. Loading means 17 is positioned so that it is centered ,or substantially centered, within furnace tube 25. Hopper means 11, 13 and 15 have a plurality of feed means, or supply lines, such as, 33, 35 and 37, which may be in the form of hoses or chutes, separately connectinq the individual hoppers with the the spaces around and between form members 19 and 21. The feed means may include valve~, such as 36, to control the flow therethrough.
As shown the spaces in and around form member~ 19 and 21 are annularly defined by the inside of the furnace tube, the form member~ and the core, or heating element.
As shown in Figure 3 loading means 17 is centered, or substantially centered, within furnace tube 25. The annular spaces defined by the interior of furnace tube 25, loading ~j, .: . . . : , - ,.. . .. .
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~'' . ' ' '` " "' ' ~. . " . ' ' .', ~' ' .' ' ` , means 17 and by heating element 31 are being charged with particulate material from hoppers 11, 13 and 15. As shown, the annular space between the interior of furnace tube 25 and the outside of cylindrical form member 19 of loading device 17 is partially filled with particulate insulating material 41.
Insulating material 4~ functions to provide physical support for one ~urf~ce of t~e particulate reactant material, insulate the furnaoe tube from high temperatures and allow the final product to be easily removed from the furnace tube.
In~ulating material 41 may be of any material which does not react with silicon, silicon carbide, carbon, or the material of the furnace tube. The material is one that is not wetted by molted ~ilicon, that is, it is not silicon infilitrated.
Boron nitride, aluminum nitride, silicon nitride, and oxides such as aluminum oxide, zirconia oxide and fused guartz are useful, boron nitride and aluminum nitride and fused quartz Rhave been found to be eminently useful. The annular space defined by the outside of cylindrical form member 21 and the inside of cylinder~ 19 is filled with particulate silicon carbide, carbon, or mixtures thereof, 43. The annular space defined by the inside of cylindrical form member 21 and heating element 31 is filled with particulate silicon, 45.
The out~ide surface of heating element 31 is coated with a thin layer of boron nitride, aluminum nitride or a~licon nitride to prevent molten silicon from wetting or reacting with it. It has been found that heating elements of high . .. .. . ,.. . . . ~ :

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Figure 4 shows the arrangement of Figure 3 after furnace tube 25 has been charged. Loading means 17 has been removed from furnace tube 25 leaving hollow columns of reactant materials and insulatlng material. Cover 32 has been placed on tube 25. The space between the furnace charge and cover 32 may suitably be filled with an insulation material similar to that used in the base portion of the furnace.
Moveable induction coil 27 is then positioned at the top portion of furnace tube 25 and activated causing heatlng element 31 to increase in temperature. When heating element reaches a sufficiently high temperature, the hollow column of particulate silicon is melted and infuqes, or infiltrates, into an appropriate adjacent column of particulate material.
Induction coil 27 is then progressively moved downward along furnace tube 25, suitably by reversible lift means, such as 30, thus incrementally carrying out the siliciding process.
Pigure 5 illustrates the arrangement of Figure 4 after in~tial heating of the furnace has begun. As ~hown the top portion of the silicon column has partially melted and infiltrated into the column containing silicon carbide, carbon, or mixtures thereof forming tube 34. Heating to silicidinq temperature is progressively carried out from the top to the bottom of the furnace.
Fiqure 6 illustrates an alternative arrangement whereby a coreless type furnace is employed, that is no heating element, . , -.

as such, is utilized. In this arrangement a vertical column of carbon, preferably graphite, 47, is used as both a reactant and as the heating element. The center portion, or core, of furnace tube 25 is filled with insulating material 49.
Figure 7 illustrates a further alternative in which temporary supports 5i and 53 are provided to give additional stability to the columns of particulate materials and enable easier removal of loading means 17. Supports 51 and 53 are suitably fabricated of a combustible material such as paper.
Waxed or coated paper may be used. Materials that are completely combustible or materials that leave a carbon residue are equally suitable.
The invention will now be described in greater detail by reference to the following examples, which are intended to illustrate, and not limit the scope of the invention. In the following examples, all parts are parts by weight and all temperatures are in degrees Centigrade.

A loading apparatus and vertical vacuum induction furnace a- lllustrated above was utilized. The loading means had an outside tube, corresponding to 19 in the drawings, having an outside diameter of 2.250 inches, and an inside diameter of 2.152 inches. One end of the tube was beveled toward the inside surface to form knife edge having a diameter of about 2.15 inches. The device had an inner tube, corresponding to 21 in the drawings, having an outside diameter of 2.000 inches : . - . .. . . :

-1 3283~7 and an in~ide diameter of 1.902 inches. One end of the inner tube was beveled toward the outside to form a knife edge with a diameter of 2.000 inches. The inner tube was held in concentric position within the outer tube by mean~ of set 8C rew~.
The loading means was centered in a fused quartz furnace tube having a 2.772 inch inside diameter, a 3.025 inch outside diameter and a length of 24 inches. The furnace tube was positioned vertically in a support frame. The bottom end of the furnace tube was closed with a flat rubber vacuum gasket held by an aluminum plate to which a vacuum hose and pump were connected. The bottom three lnches of the quartz tube were filled with 1/2 inch thick carbon felt discs to thermally insulate the rubber vacuum gasket.
Three feed hoppers were used. One for boron nitride grain SHP-40 grade, a product of Sohio Engineered Materials Company, one for silicon grain, grade Siligrain SGl-20 mesh, a product of Elkem Metals Company, and one for silicon carbide grain, a blend of 95% 50/100 mesh size No. 1, a product of Exolon-ESX Company ànd 5% dry phenolic resin, Dyphene* grade 877P, a product of Sherwin-Williams Company.
The particulate Eeed material was fed through eighteen plastic 1!4 inch inside diameter feeder tubes, six tubes for each of the feed materials. The feed tubes were arranged around the periphery of the top of the loading means in 60 degree increments. The feed tubes were arranged to feed particulate boron nitride in the space between the outer tube *Trade Mark r~ 20 ,, , ;~ . - : : : - .
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1 3~8347 on the loading device and the inside of the furnace tube, particulate silicon carbide within the tubes of the loading means, and particulate silicon in the space between the inside of the loading means and the outside of furnace heating tube.
After filling the loading mean~ was 810wly raised to leave seperate concentrically arranged, hollow columns of particulate boron nitride, silicon carbide-resin, and silicon.
After removal of the loading means, the top space was filled with carbon felt discs and capped with a rubber gasket and a metal plate. A vacuum was applied to the lower end of the furnace tube.
An induction coil having twelve turns of 3/16 inch outside diameter copper tubing with a coil inside diameter of 3 1/8 inches and a length of three inches, was connected to a 450KHZ, 2 1/2XW Lepel induction power supply and the coil ~tarted at the top of the furnace tube using a 0.8 plate current power input. The coil was lowered along the furnace tube at a rate of 0.33 inch per minute. The coil was stopped and the power turned off when the bottom of the quartz tube was approached. The furnace tube was then allowed to cool to room temperature, opened and the tubular product removed. The siliconized ~ilicon carbide tube was easily removed from the quartz furnace tube as the boron nitride was still in loose granular form and unaffected by infiltration process~ The heating element was easily removed from the siliconized silicon carblde tube a~ the silicon column had been removed by $ ~ -,, : . '' : : `
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infiltration into the silicon carbide column. The siliconized silicon carbide tube product was found to be round and staight with little porosity in the microstructure. The silicon carbide volume in the mic~ostructure was estimated by visual inspection to be about 50~. The outside diameter of the product was about 2.160 inches an~ the inside diameter of the the product was about 1.970 inch.

In this Example, graphite powder having an approximate grain size of minus 150 mesh and a tap density of 0.58 g/cm was used in place of the silicon carbide-resin component as was used in Example 1 and in place of the furnace heating element -a ,core of insulating grain was used. The procedure u~ed otherwise followed that of example 1. A photomicrograph of a polished section of the tubular product revealed that thè
graphite particles were not completely converted to silicon carbide and that only a thin layer of silicon carbide was present on the surface of the graphite particles which were in turn surrounded by a matri~ of silicon.
~ EXAMPLE 3 In this Example the furnace tube was charged with concentric layers of insulation grain, silicon grain and graphite powder packed around a core of insulation grain.
Otherwise t~e procedure of Example 1 was followed. The product was similar to that in Example 2.
While the pre~ent invention has been described in detail in connection with specific embodiments thereof, it will be 2~

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Claims (24)

1. A method of making a ceramic tube comprised of silicon and silicon carbide which comprises the steps of:
a). concentrically positioning a first hollow, vertical tubular column of particulate silicon adjacent a second hollow, vertical tubular column of particulate material selected from the group of silicon carbide, carbon or mixtures thereof, b). heating said columns to a siliciding temperature to infiltrate said silicon from said first column into said second column, and c). cooling said infiltrated column to form a hollow, dimensionally stable ceramic tube.

2. The method of claim 1 wherein said second column is comprised of silicon carbide.

3. The method of claim 1 wherein said second column is comprised of carbon.

4. The method of claim 1 wherein said second column is comprised of silicon carbide and carbon.

5. The method of claim 1 wherein the columns are heated to a temperature above the melting point of silicon and less than about 2400 degrees C.

6. The method of claim 1 wherein the siliciding step is carried out under a vacuum.

7. The method of claim 1 wherein the siliciding step is carried out in an inert atmosphere.

8. The method of claim 1 wherein the column containing silicon carbide, carbon, or mixtures thereof also contains a resin binder.

9. The method of claim 8 wherein the binder is added in a dry particulate form.

10. The method of claim 8 wherein the binder is added in a liquid form and is subsequently dried on the particulate material.

11. The method of claim 1 wherein the heating step is by electric induction.

12. The method of claim 1 wherein the heating step is carried out in an electrical induction furnace having a resistive heating core.

13 The method of claim 3 wherein the heating step is carried out in a coreless type electric induction furnace.

14. A hollow, tubular ceramic article fabricated by the method of claim 1.

15. The article of claim 14 wherein the article is comprised of silicon and silicon carbide.

16 The article of claim 14 wherein the article is comprised of silicon, silicon carbide and graphite.

17. An apparatus for charging a tubular vertical electrical induction furnace with columns of particulate material which comprises:
a). a loading means comprised of a plurality of annularly spaced, open cylindrical form members of a size to spacedly fit within said induction furnace, b). means for placing said loading means within said furnace, c). a hopper means for holding a supply of particulate feed material, d). a plurality of feed means arranged to selectively feed a supply of particulate material from said hopper means into the spaces around and between said form member,s and e). means for removing said form members from said furnace leaving columns of particulate material.

18. The apparatus of claim 17, further including f). induction coil means for heating said furnace.

19. The apparatus of claim 17 or 18, wherein said furnace is a vacuum induction furnace.

20. The apparatus of claim 17 or 18, wherein said feed means are hoses.

21. The apparatus of claim 17 or 18, wherein said furnace is a core-type furnace.

22. The apparatus of claim 17 or 18, wherein said furnace is a coreless furnace.

23. The apparatus of claim 17, or 18, wherein said outer form member has a peripheral spacing means thereon to spacedly position said form members within said furnace.

24. The method of claim 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12 or 13, including a step of dry casting said first column, and dry casting said second column contiguous to, and in concentric relation to, said first column.