CA1111664A - Polycrystalline diamond body/silicon carbide or silicon nitride substrate composite - Google Patents

Abstract

Abstract of the Disclosure A mass of diamond crystals in contact with a mass of eutectiferous silicon-rich alloy and a silicon carbide or silicon nitride ceramic substrate axe disposed in a container and placed within a pressure transmitting powder medium. Pressure in applied to the powder medium resulting in substantially isostatic pressure being applied to the container and its contents sufficient to dimensionally stabilize the container and its contents. The resulting shaped substantially isostatic system of powder-enveloped container is hot-pressed, whereby fluid eutectiferous sili-con rich alloy is produced which infiltrates through the interstices between the diamond crystals and contacts the contacting face of the substrate sufficiently to produce, upon cooling, an adherently bonded integral composite.

Description

POLYCRYSTALLINE DIAMOND BODY/
SILICON CARBIDE OR SILICON NITRIDE SUBSTRATE COMPOSITE

This invention relates to the production of a polycrystalline diamond body/silicon carbide or silicon nitride substrate composite comprised of a dense mass of diamond crystals bonded to a silicon carbide or silicon nitride substrate. The diamond crystals are bonded together and to the silicon carbide or silicon nitride substrate by a silicon atom-containing bonding medium.
loOne of the technical barriers to a high density ~high volume o-f diamond in a body) diamond base compact made below the diamond stable pressure region has been the development of a suitable binder material which will infiltrate the ; capillaries of a densely packed fine particle size diamond powder The binder must form a thermally stable strong bond with diamond and should not graphitize or excessively react with the diamond.
The present in~ention utilizes a eutectiferous silicon-rich alloy which infiltrates well through the ~ocapillaries of a compressed mass of diamond crystals and which wets the crystals to form a strong cemented diamond body. In addition, the infiltrating alloy forms a strong bond in a situ with a silicon carbide or silicon nitride substrate. The present process also utilizes pressures substantially below those required by the diamond stable .~ ,, `:
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RD-1033~/10335 region to produce a polycrystalline diamond body/silicon carbide or silicon nitride substrate composite in a number of ` configurations and a wide range of sizes. It is useful as an abrasive, cutting tool, nozzle or other wear resistant part.
Briefly stated, the present proeess for preparing a polycrystalline diamond body/silicon carbide or silicon nitride composite includes a hot-pressing step and comprises placing within a protective container or cup a mass of solid eutectiferous silicon-rich alloy, or solid components for producing eutectiferous silicon-rich alloy, a mass of diamond crystals and a silicon carbide or silicon nitride substrate, said mass of diamond crystals being intermediate and in contacts with said substrate and said mass of solid eutectiferous silicon-rich alloy, or with at least one of said components for providing eutectiferous silicon-rich alloy, said eutectiferous silicon-rich alloy being composed of silicon and a metal which forms a silicide with said silicon, disposing said container and i~s contents wi-thin a pressure transmitting powder medium that transmits applied pressure substantially undiminished and remains substantially unsintered during said hot-pressing applying sufficient substantially isostatic pressure to said container and its contents via said powder medium to substantially stabilize the dimensions of said container and said contents substantially uniformly producing a shaped substantially isostatic system of powder-enveloped container wherein the density of the resulting compressed mass of diamond crystals is higher than 70/0 by volume of the volume of said compressed diamond crystals, hot-pressing the resulting substantially isostatic system producing fluid infiltrating eutectiferous silicon-rich alloy and infiltrating said fluid eutectiferous silicon-rich alloy through the interstices of said compressed mass of diamond crystals and into contact with the contacting surface of said substrate, said hot-pressing being carried out at an hot-pressing temperature below 1600C under a hot-pressing pressure sufficient to infiltrate said fluid silicon-rich alloy through the interstices of said compressed . RD-10334/10335 mass of diamond crystals, s~id solid eutectiferous silicon-rich alloy, or solid components for eutectiferous silicon-rich alloy being used in an amount sufficient to produce suEficient fluid eutectiferous silicon-rich alloy at said hot-pressing temperature to fill the interstices of said compressed mass of diamond crystals and contact the contacting surface of said substrate, said hot-pressing being carried out at an atmosphere which has no significant deleterious effect on said diamond crystals or on said infiltratiug fluid silicon-rich alloy or on said silicon carbide or silicon nitride substrate, said hot-pressing converting less than 5% by volume of said diamond crystals to non-diamond elemental carbon, said non-diamond carbon or the surfaces of said diamond crystals reacting with said fluid infiltrating silicon-rich alloy ~orming carbide, maintaining sufficient pressure on the resulting hot-pressed substantially isostatic system during cooling thereof to at least substantially maintain the dimensions of said hot-pressed system, and recovering the resulting polycrystalline ` 20 diamond body/silicon carbide or silicon nitride substrate composite wherein the diamond crystals are present in an amount of at least 70% by volume of the volume of the bonded polycrystalline diamond body.
In an alternative embodiment of the present process no protective container or cup is used, and in such embodiment the mass of solid eutectiferous silicon-rich alloy, or solid componènts for eutectiferous silicon-rich alloy, and mass of diamonds and silicon carbide or silicon nitride substrate are placed directly in a pre formed cavity of predetermined size in the pressure transmitting powder medium. The cavity can be formed in the powder by a number of techniques. For example, the pressure transmitting powder medium can be placed in a die, a solid mold of desired size can be inserted in the - powder, and the resulting system pressed at ambient temperature under pressure sufficient to ma~e the powder ~` stable in form, i.e. give the pressed powder sufficient ~`~ strength so that the mold can be withdrawn there~rom leaving '` .
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RD-1033~/lQ335 the cavity it has depressed therein to function as a container for the silicon carbide or silicon nitride substrate, mass of diamonds and silicon-rich alloy. After ~he silicon carbide or silicon nitride substrate, mass of diamonds and silicon-rich alloy are placed within the cavity wi-th the mass of diamonds intermediate said substrate and said alloy, additional pressure transmitting powder is added to seal the cavity and the entire system cold-pressed at ambient temperature to dimensionally stabilize the cavity and its contents producing a substantially isostatic system of powder-enveloped cavity and contents.
Those skilled in the art will gain a further and better understanding of the present invention from the detailed description set forth below, considered in conjunction with the figures accompanying and iorming a part of the speciication, in which:
Figure 1 is a portion of a silicon zirconium alloy phase diagram showing the equilibrium diagram for eutectiferous silicon-rich zirconiurn alloy useful in the present invention;
~o Figure 2 is a cross-sectional view of a cell, i.e.
container and contents, for carrying out infiltration of silicon-rich alloy according to this invention;
` Figure 3 schematically represents apparatus for applyinglight pressure to the cell of Figure 2 whi]e the cell is bPing vibrated to increase the density of the mass of diamond crystals;
Eigure 4 is a sectional view through an apparatus for applying at least substantially isostatic pressure to the cell by means of a pressure trarlsmitting powder medium to dimensionally stabilize the cell producing a substantially isostatic system;
Figure 5 is a sectional view through a graphite mold or the simultaneous application of heat and pressure9 i.e. hot-pressing to the substantially isostatic system showing the cell enclosed therein;
Figure 6 is an elevational view of a polycrystalline diamond body/silicon carbide or silicon nitride substrate composite prepared accordingly to this invention; and .~:
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: 5 RD-lO334/~0335 -Figure 7 is a photomicrograph (magnified 690 X) of a polished cross~sectional surface of the composite of the present invention.
~ n carrying out the present process, the structure comprised of the mass of diamond crystals intermedia-te and in contact with a silicon carbide or silicon nitride subs-trate and mass of the solid eutectiferous silicon-rich alloy is subjected to a cold-pressing step at ambient or room temperature to substantially stabilize their dinlensions substantially uniformly and then to a ho-t-pressing step whereby the silicon alloy produces fluid silicon-rich alloy which is infiltrated throughout the mass of compressed diamond crystals, and into contac~ with the silicon carbide substrate.
Alternatively~ the mass of diamond crystals can be in contact with at least one of the components used for forming the eutectiferous silicon-rich alloy in situ, i.e. silicon or alloying metal, and the silicon carbide or silicon nitride substrate, mass of diamond crystals as well as the components for forming the silicon-rich alloy, are subjected to a cold-pressing step at ambient or room temperature to substantially stabilize their dimensions and then to a hot-pressing step whereby fluid eutectiferous silicon-rich alloy is produced and infiltrated throughout the mass of compressed diamond crystals and into contact with the silicon carbide or silicon nitride substrate. The components for forming the silicon alloy are positioned to form the silicon alloy before hot-pressing is initiated, i.e. before the hot-pressing temperature is reached.
The mass of diamond crystals~ mass of starting solid silicon-rich alloy, or solid components for forming the silicon-rich alloy, and silicon carbide or silicon nitride substrate can be in a number of forms. For example, each mass can be in the form of a layer with the layer of diamond crystals intermediate the other layers. ~lternatively, the starting silicon-rich alloy can be in the fo~m of a tube or cylinder with a core extending through it, the alloy tobe :

being ca~t so that it forms a close fit wi-th the inner wall of the container, and the substrate can be in the form of a bar which can be centrally positioned within-the core of the alloy tube, and the encircling space between the silicon alloy tube and substrate bar packed wi-th diamond crystals.
The diamond crystals used in the present process can be natural or synthetic, i.e. man-made. They range in size in largest dimension ~rom about 1 micron to about 1000 microns, and the particular size or sizes used depends largely on the particular packing or density of diamond crystals desired and also on the particular use of the resulting body. ~or most abrasive applications, for example, diamond crystals no greater than about 60 microns are preferred. Preferably, to maximize the packing of the diamond crystals in the present process, they should be si~e-graded to contain a range oi sizes, i.e. small, medium and large-si~ed crystals.
Preferably, the size-graded crystals range from about 1 micron to about 60 microns, and preferaly within this size range, about 60~/o to about 80% by volume of the total mass of crystals are of the larger sized portion of the range, about 5/0 to about 10% by volume are of medium size with the balance . constitu~ing the small-sized crystals or particles.
Sizing of the diamond crystals is facilitated by the jet-milling of larger diamond crystals. Preferably, the diamond crystals are chemically cleaned to remove any oxides or other impurities from the surface thereof before use in the present process. This may be accomplished by heating the diamond crystals in hydrogen at abou~ 900C for about one hour.
In the present invention the starting solid eutectiferous silicon-rich alloy, i.e. the term alloy herein including intermetallic compound, is comprised of silicon and a metal, i.e. alloying me-tal, which forms a silicide with the silicon. Preierably, the present eutectiferous silicon-rich alloy is comprised o~ silicon and a metal selected from the group consisting of cobalt (Co), chromium (Cr), iron (Fe), halnium (Hf), manganese (Mn), molybden~m (Mo), niobium (Nb), ., -RD-1033~/ 335 nickel (Ni), palladium (Pd), platium (Pt), rhenium (Re), rhodium (Rh), ruthenium (Ru), tantalum (Ta)~ thorium (Th), titanium (Ti), uranium (U), vanadium (V), tungsten (W) 9 yttrium (Y), zirconium (Zr) and mixtures thereof.
The present starting eutectiferous silicon-rich alloy is a solid at room temperature and contains more than 50 atomic %
but less than 100 atomic % of silicon. Usually, it contains a maximum of about 99.5 atomic % silicon depending largely on the specific effect that the alloying metal has on the resulting silicon-rich alloy. The present starting solid silicon-rich alloy is eutectiferous in that it contains some eutectic structure and can be of hypoeutectic, hypereutectic or of eutectic composition. Using Figure 1 as an example, the eutectic (2) is an alloy of specific composition which, under equilibrium conditions, on cooling freezes at constant temperature forming a solid of at least two phases, and which on heating melts completely at the same constant temperature, this constan~ temperature being referred to as the eutectic temperature also given at (2). The eutectic (2) is the composition at which two descending liquidus curves (3) and (4), meet at eutectic point (2), and therefore, it has a lower melting point than its neighboring hypoeutectic or hypereutectic compositions. The liquidus is a curve or line on a phase diagram representing under equilibrium conditions the temperatures at which melting ends during heating of the silicon alloy or freeæing begins during cooling thereof.
Speci~ically, the present starting solid eutectiferous silicon rich alloy is one of the series of alloys on a eutectic horizontal (1), i.e. the horizontal passing through the eutectic point (2), and which e~tends from any alloy whose composition lies to the left of -the eutectic (2) on an equilibrium diagram and which contains some eutectic structure, i.e. hypoetectic, to any alloy whose composition -; lies to the right of the eutectic (2) on the equilibrium diagram and which contains some eutectic structure, i.e.
` hypereutectic alloy.
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8 RD-1033~/10335 The star~ing solid silicon-rich alloy may or not be of the same composition as the infiltrating silicon-rich alloy.
If all of the starting solid silicon-rich alloy becomes fluid at the hot-pressing temperature then it will have the same composition as the infiltrating silicon-rich alloy. However, if only a portion of the starting silicon-rich alloy, i.e.
hypoeutectic or hypereutectic~ becomes fluid at the hot-pressing temperature, the s-tarting alloy does not have the same composition as the fluid infiltrating silicon-rich alloy, and in such instance the infiltrating silicon-rich alloy will be more rich in silicon than the starting hypoeutectic eutectic alloy bu~ less rich in silicon than the starting hypereutectic silicon-rich alloy.
Using Figure 1 as an example, the composition oi the present infiltrating eutectiferous silicon-rich alloy and its melting temperature is found on liquidus curves (3~ and (4) and includes eutectic point (2). The area (5) defined by (1),

(2) and (4) is comprised of a solid phase, (Si) and a liquid phase, i.e. liquid infiltra~ing alloy phase, with the amount of solid phase increasing and the amount of liquid phase decreasing correspondingly as the distance to the right from eutectic point (2) along horizontal (1) is increased, i.e. as the amount of silicon in the alloy is raised from that contained in the eutectic. Likewise, the area (6) defined by tl), (2) and (3) is comprised of a solid phase ~rSi2 and a liquid phase, i.e. liquid infiltrating alloy phase, with the amount of solid phase increasing and the amount of liquid ~ phase decreasing correspondingly, as the distance to the left `. from eutectic point (2) along horizontal (1) is increased, i.e. as the amount of silicon in the alloy is lowered from that contained in the eutectic.
In carrying out the present process, the desired composition of the present infiltrating eutectiierous silicon-rich alloy and its melting temperature are found as a point on the liquidus curves including the eutectic poin~ of the phase diagram for the present silicon-rich alloy, and the hot-pressing temperature is the temperature at which such -R~-10334/10335 desired infiltrating silicon-rich alloy composition is fluid, i.e. sufficiently flowable to infiltrate through -the compressed diamond mass. When a starting solid silicon-rich alloy is used that has the same composi-tion as tha~ of the desired infiltrating alloy, the hot-pressing temperature is the temperature at which the alloy is fluid ~7hich ranges from about 10C to preferably a maximum of about 100C higher than the melting point of the alloy, bu~ if desired hot-pressing temperatures higher than this preferred maximum are useful depending largely upon the particular alloy used. However, hot-pressing temperatures higher than 1600C are not useful since they tend to graphiti~e the diamonds excessively.
However, when the starting alloy does not have the same composition as that of the desired infiltrating alloy, but when it is heated to the melting point of the desired infiltrating alloy it produces such infiltrating alloy as a liquid phase, then the hot-pressing temperature is a temperature at which such infiltrating alloy phase is produced in fluid form, i.e. about 10C higher than the melting point of the infiltrating alloy phase.
Using Figure 1 as an example, for a specific infiltrating alloy of hypereutectic composition, its melting point is found on liquidus line 4. For example, if the ; desired infiltrating hypereutectic alloy contains 95 atomic/O
Si, its melting point is found on liquidus line 4 to be about 1400C as shown by line 7. When the starting silicon-rich alloy is of the same composition as the desired infiltrating alloy as shown by line 7, all of the starting alloy would melt at the melting temperature of 1400C, and the fluid or hot-pressing temperature would range from about 1410C to about preferably 1510C, or if desired, up to but below 1600C.
However, when the starting silicon-rich alloy is any hypereutectic alloy to the right of line 7, on horizontal line 1 in the equilibrium diagram in Figure 1, the hot-pressing temperature is the temperature at which the desired infiltrating 95 atomic % Si-5 atomic % Zr alloy is produced in fluid form which would be ~bout 14L0C

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Also, at the hot-pressing temperature the starting alloy should produce the desired infiltrating alloy in fluid form in an amount sufficient to fill the voids of the compressed diamond mass herein having a density of crystals higher than 70% by volume and into contact with the contacting surface of the silicon carbide substrate filling pores or voids in the interface between the contacting polycrystalline body and substrate so that the resulting composite has an inter~ace which is pore-iree or at least substantially pore-free. As a practical matter the fluid infiltrating alloy should be ` produced at hot-pressing temperature in an amount of at least about 1% by volume of the starting silicon-rich alloy.
The present hot-pressing is carried out at a temperature at which the infiltrating silicon-rich alloy is fluid under a pressure which need only be sufficient at the ho-t-pressing temperature to break up interfacial refractory layers in the diamond mass which prevent penetration by the fluid alloy through the voids thereof and usually this requires a minimum pressure of about 500 psi. Specifically, the hot-pressing pressure can range from about 500 p9i to about 20,000 psi, but usually it ranges from about 1000 psi to about 10,000 psi.
Hot-pressing pressures in the present process higher ~han .- 20,000 psi provide no significant advantage.
By a temperature at which the infiltrating alloy is flui~ it is meant herein a temperature at which the infiltrating alloy is readily flowable. Specifically, a-t its melting point given on the liquidus line, or eutectic point in the case of a eutectic alloy, the infiltrating alloy is a liquid thick viscous substance, but as its tempera~ure is raised from its melting point, the infiltrating alloy becomes less viscous, and at a temperature about 10C higher than its melting point, the liquid infiltrating alloy becomes readily flowable, i.e fluid. The temperature at which the infiltr~ting silicon-rich alloy i8 fluid is the temperature at which it will infuse or infiltrate through -~he capillary-size passages, interstices or voids of the present compressed mass of diamond crystals having a crystal density higher than , .

70~ by volume. With still additional increase in temperature the flowability of the fluid infiltrating silicon-rich alloy increases resulting in a faster rate of penetration throughout the mass of diamond crystals, and at a temperature of about 100C
higher than its melting point/ the infiltratlng alloy usually has its highest flowability and temperatures higher than this maximum ordinarily need not be used.
The present silicon-rich alloy of eutectic composition melts at a temperature below about 1~30C. For the preferred group of silicon-rich alloys herein, the eutectic melting point ranges from 870C for siPd eutectic alloy, i.e~ about 56 atomic % Si, to 1410C for SiMo eutectic alloy composition, i.e. about ; 97 atomic % Si. As shown in Figure 1, the SiZr eutectic alloy (2) contains 90.4 atomic % Si and has a eutectic melting temperature o 1360C. The major phase of the present solid silicon-rich eutectic alloy is almost pure silicon.
The present infiltrating eutectiferous silicon-rich alloy has a melting point below about 1500C, usually from about 850C to about 1450C, and the temperature at which it becomes fluid is at least about 10C higher than its melting point.
~` The starting solid silicon-rich alloy or solid components for producing the present silicon-rich alloy can be in the form of a con-tinuous solid or in the form of a powder. The particular amount or volume of starting solid silicon-rich alloy used can vary depending on the amount of fluid infiltrating silicon-rich alloy it produces and the capacity of the equipment. Generally, the infiltrating silicon-rich alloy ranges in amount from about 25~ by volume to about 80% by volume, but preferably for best results, it ranges from about 30~ to about 60% by volume of the present compressed mass ~ of diamond crystals having a density of crystals higher than `~ 70% by volume.
The present hot-pressing step is carried out in an atmosphere which has no significant deleterious effect on the - `~

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diamond crystals, or infiltrating silicon-rich alloy, or silicon carbide substrate. Specifically, the hot-pressing step can be carried out in a substantial vacuum or in an inert gas such as argon or helium, or it can be carried out in nitrogen or hydrogen.
The present hot-pressing is carried out sufficiently rapidly so that there is no significant reaction between the infiltrating silicon-rich alloy and nitrogen or hydrogen. The hot-pressing step cannot be carried out in air because diamond graphiti~es readily in air above 800C and the fluid infiltrating silicon-rich alloy would oxidi~e to form solid silica before any significant infusion by the fluid alloy of the diamond mass occurred.
The silicon carbide substrate is a polycrystalline body having a density ranging from about 85% to about IOO~ of the theoretical density of silicon carbide. Silicon carbide density given herein is the fractional density based on the theoretical density for silicon carbide of 3.21 gm/cc. A silicon carbide polycrystalline body having density less than ~bout 85%
is not useful because it would not have the required mechanical strength for most applications, for example for use as a tool insert. Ordinarily, the higher the density of the silicon carbide body, the higher is its mechanical strength.
The silicon nitride substrate is a polycrystalline body having a density ranging from about 80% to about 100~ of the theoretical density of silicon nitride. Silicon nitride densi-ty given herein is the fractional densi~y based on the theoretical density for silicon nitride of 3.18 gm/cc. A silicon nitride polycrystalline body having a density less than about 80~ is not useful because it would not have the required mechanical strength for most applications, for example for use as a tool insert.
Ordinarily, the higher the density of the silicon nitride body, the higher is its mechanical strength.
In the present invention the polycrystalline silicon carbide or silicon nitride substrate is a hot-pressed or sintered body comprised of silicon nitride, i.e. it contains ' silicon nitride in an amount of at Least 90% by weight and usually at least 95% by weight, and generally from 96% to 99% or higher by weight, of -the body. An constituent or component of the present polycrystalline silicon nitride body other than silicon nitride should have no significant deteriorating effect on the mechanical properties of the resulting composite. SpeciEically, it should have no slgnificant deteriorating effect on the properties of the silicon nitride and all other materials used in the present process in preparing the composite or on the properties of the ; 10 composite itself.
Preferably, the present silicon carbide body can be ;prepared by sintering processes disclosed in U.S. Patent 4,004,934 issued January 25, 1977 and U.S. Paten~ 4,209,A74 issued June 24, m~ 1990, both in the name of Svante Prochazka and both assigned to the . 15 assignee hereof.
: Briefly stated, the sintered silicon carbide body can be prepared by providing a submicron particulate mixture of B-silicon . carbide, boron additive and a carbonaceous additive which is free carbon or a carbonaceous organic material which is heat-:20 decomposible to produce free carbon, and shaping the mixture into a green body. In an alternative method a-SiC, submicron in size but with an average particle size twice that of -SiC, is admixed with the particulate mixture in an amount of 0.05% to 5% by weight based on the -SiC. The green body is sinteredat a temperature - 25 ranging from about 1900C to 2300C to the required density.
~ Specifically, the boron additive may be in the form of -: elemental boron carbide or a boron compound which decomposes at a temperature below sintering temperature to yield boron or boron carbide and gaseous products of decomposition and is used in an amount equivalent to 0.3% to 3.0% by weight of elemental boron based on the amount of silicon carbide. During sintering, the boron additive enters into solid solu~
tion with the silicon carbide, and when amounts of the ~..' .

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additive in excess of that equivalent to about 1% by weight of elemental boron are used, a boron carbide phase also precipitates.
The carbonaceous additive is used in an amount equivalent to about 0.1% by weight to about 1.0% by weight of Eree carbon based on the amount o~ silicon carbide. The additive can be free carbon or a solid or li~uid carbonaceous organic ma-terial which completely decomposes at a temperature of 50C to 1000C
to submicron size free carbon and gaseous products of decomposi-tion. Examples of carbonaceous additives are polymers of aromatic hydrocarbons such as polyphenylene or polymethlphenylene which are soluble in aromatic hydrocarbons.
~he sintered body is comprisea of silicon carbide and based on the amount of silicon carbide, from about 0.3% to about 3~ by weight of boron and up to about 1% by weight o~
free carbon. The boron is in solid solution with the silicon carbide or, alternatively, in solid solution with the silicon carbide also present as a boron carbide phase. The free carbon, when it is detectable, is in the form of submicron par-ticles dispersed throughout the sintered body.
Preferably, hot-pressed silicon carbide bodies can be prepared by processes disclosed in U. S. Patent 3,853,566 issued December 10, 1974 to Prochazka and U. S. Patent 4,108,929 issued August 22, 1978 in the names of Svante Prochazka and ~illiam J. Dondalski, all assigned to the assignee hereof.
In one hot-pressing process, a dispersion of submicron powder of silicon carbide and an amount of boron or boron carbide equivalent to 0.5-3.0% by weight of boron, is hot-pressed at lgO0-2000C under 5000-10,000 psi to produce a boron-containing silicon carbide body. In another hot-pressing process, 0.5-3.0% by weight of elemental carbon or carbonaceous additive heat-decomposible to elemental carbon is included in the dispersion.
Preferably, the polycrystalline silicon nitride body can be prepared by sintering processes disclosed in Canadian Serial ..
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Numbers 2~7,187 filed February 17, 1978 and 293,743 filed December 22, 1977 in the names of Svante Prochazka et al and assigned -to the . assignee hereof.
Briefly stated, Serial No. 297,187 disclosed a sintered `: silicon nitride body prepared by providing a homogeneous dispersion of submicron size of silicon nitride and a beryllium additive selected from the group consisting of beryllium, beryllium carbide, beryllium fluoride, beryllium nitride, beryllium silicon nitride and mixtures thereof, in an amount wherein the beryllium component is equivalent to from about 0.1% to about 2% by weight of elemental beryllium based on the amount of silicon nitride, shaping the disper-sion into a green body and sintering the green body from about 1900C to about 2200C in a sin-tering atmosphere of nitrogen at a superatmospheric pressure which at the sintering temperature prevents significant thermal decomposition of the silicon nitride and produces a sintered body with a density of at least about 80% of the theoretical density of silicon nitride, the minimum pressure of said nitrogen ranging from about 20 atmospheres at a sintering temperature of 1900C to a minimum pressure of about 130 atmospheres at a sintering temperature of 2200C.
The process of Serial No. 293,743 is similar to that of Serial No. 297,187 except that a magnesium additive is included in the dispersion of silicon nitride and beryllium additive, the green body is sintered from about 1800C to about 2200C in a sintering atmosphere of nitrogen at superatmos-pheric pressure which ranges from a minimum of about 10 atmospheres at a sintering temperature 1800C to a minimum of about 130 atmospheres at a sintering temperature of 2200C. The magnesium additive is selected from the group consisting of magnesium, magnesium carbide, magnesium nitride, magnesium cyanide, magnesium fluoride, magnesium silicide, magnesium silicon nitride and : mixtures thereof. The magnesium additive is used in an amount wherein the magnesium component is equivalent to from about ; 0.5~ by weight to about 4% by weight of elemental magnesium based on the amount of silicon nitride.

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RD-1033~/10335 ~ he polycrystalline body disclosed in Serial No. 297,187 has a density ranging from about 80% to about 100% of the theoretical density of silicon nitride and is comprised of silicon nitride and beryllium ranging in amount from less than about 0~ eight to less than about 2.0~ by weight of said silicon nitride. The poly-crystalline body disclosed in Serial No. 293,743 is similar to that disclosed in Serial No. 297,187 except that it also contains ma~nesium ranging in amount from less than about 0.5% by weight to less that about 4.0% by weight of the silicon ni-tride.
Preferably, hot-pressed polycrystalline silicon ni~ride bodies can be prepared by processes disclosed in Canadian Serial No. 295,379 filed January 20, 1978 and 297,237 Ei.led February 17, 1978 in the names of Greskovich et al and both assigned to the assignee hereof Briefly stated, Serial No. 295,379 disclosed a hot-pressed silicon nitrlde body prepared by providing ahomogeneous powder dis-persion, submicron size, of silicon nitride and magnesium silicide in an amount ranging from 0.5% to about 3% by weight based on the amount of silicon nitride, and hot-pressing the dispersion in an atmosphere of nitrogen from about 1600C to about 1850C under a minimum pressure of about 2000 psi. The resulting polycrystalline silicon nitride body has a density of about 80% to about 100% of the theoretical density of silicon nitride and is comprised of silicon nitride and magnesium ranging in amount from about 0.3% by weight to about 1.9% by weight of the silicon nitride.
Briefly stated, Serial No. 297,237 discloses a hot-pressed polycrystalline silicon nitride body prepared by providing a powder disperson of submicron size of silicon nitride and a beryllium additive selected from the group consisting . of beryilium, beryllium nitride, beryllium fluoride, 30 beryllium silicon nitride and mixtures thereof, in an amount wherein the beryllium component is equivalent to about 0.1% by weight to about 2% by weight of elemental .~

' -. ' ~:; ' beryllium based on the amount of silicon nitride, and hot-pressing the dispersion in an atmosphere of nitrogen from about 1600C to about 1850C under a minimum pressure of about 2000 psi. The resulting polycrystalline silicon nitride body has a density of about 80% to about 100% of the theoretical density of silicon nitride and is comprised o~ silicon nitride and beryllium in an amount ranging from about 0.1% by weight to about 2.0% by weight of said silicon nitride.
The thickness of the silicon nitride substrate can vary depending on the final application of the resulting composite, but it should be at least sufficiently thick to provide adequate support for the polycrystalline diamond body adhered thereto. For most applications9 to provide adequate support for the adhered polycrystalline diamond body, the silicon nitride substrate is preferably at least about twice the thickness of the adhered polycrystalline diamond body.
In the arrangement shown in Figure 2, cell 10 consists of cup 11 (right circular cylindrical wall with bottom). Within cup 11 are disposed a disc 12 of eutectiferous silicon-rich alloy, a mass 13 of diamond crystals in contact with silicon-rich alloy 12, and a thick plug 14, e.g. a cylinder of polycrystalline silicon nitride substrate fitting closely into cup 11 and acting as a closure therefor.
Cup 11 is made of a material which is substantially inert during the hot-pressing step, i.e. a material which has no significant deleterious effect on the properties of the present diamond body. Such a material can be a non-metal, such as compressed hexagonal boron nitride, but preferably, it is a metal, and preferably a metal selected from the group consisting of tungsten, yttrium, vanadium, tantalum and : molybdenum.
` No free space should be left within the plugged cup ~hich would allow an intermixing or free movement of the contents therein so that the contents, at least substantially as ; initially positioned, are subjected to the substantially .~ isostatic prPssure of the cold-pressing step.

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' The purpose of using size-graded diamond crystals is to produce maximum packing of the diamond crystals. AlternatiVely, or in addition thereto, the arrangement shown in Figure 3 is useful for increasing the density or packing of the diamond crystals. Specifically, cell 10 is placed on vibrating table 16 and held there under light pressure (about 50 psi) application during the vibration of cell 10 to promote rearrangement of the diamond crystals or particles to fill spaces and decreases void content in order to increase the density of the diamond mass to greater than 70% by volume of the diamond mass. The requisite degree of consolidation is determinable by independent testing on diamonds of the same size in a fixed dimension die.
Cell 10 is subjected to a cold-pressing step as shown in Figure 4 which is carried out at room or ambient temperature whereby only sufficient pressure need be applied to produce a dimensionally stabilized substantially isostatic system.
Specifically, cell 10 is placed in the cylindrical core of pressure mold 20 surrounded by mass 19 of very fine particles, preferably -400 mesh, and more preferably ranging in size from about 2 microns to about 20 microns of a pressure transmitting powder medium which remains substantially unsintered under the pressure and temperature conditions of the present process such as hexagonal boron nitride and silicon nitride. This pressure transmitting particulate or powder medium provides for the application of approximately or substantially isostatic pressure to cell 10, whereby cell 10 and its contents are dimensionally stabilized, i.e. densified, substantially unformly producing a shaped substantially isostatic system of powder enveloped-cell wherein the density of the resulting compressed layer of crystals is higher than 70% by volume of ` 30 the volume of compressed crystals. Pressure mold 20 (ring 22 and pistons 23, 23a) may be made of tool steel and, if desired, ring 22 may be supplied within a sintered carbide sleeve 22a as shown " to permit the application of pressure as high as 200,000 psi.
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Pressures higher that 200,000 psi provide no significant ~, ~' ~ : `
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Specifically, the particular applied cold-pressing pressure used in determinable empirically and a pressure higher ; lO than that pressure which produces a dimensionally stabilized substantially isostatic system produces no signiflcant additional densification or dimensional stabilization of cell 10 and its contents.
The nature of present pressure transmitting power medium, such as hexagonal boron nitride and silicon nitride, is such that it results in an approximation of a hydrostatic action in response to the uniaxially applied pressure to exert substantially isostatic pressure over the entire surface of cell lO. It is assumed that the applied pressure is transmitted substantially undiminished to cell lO. The cold-pressing step diminishes the size of the voids to maximize the pressure of capillary-size voids in the diamond mass, and it also produces the required density of ; diamond crystals in excess of 70% by volume of the diamond mass.
This reduction in void volume also reduces the ultimate content of non-diamond material in the diamond mass and provides more juxtaposed ` crystal-to-crystal areas properly located for effective bonding together.
After completion of the cold-pressing step, the density of the compressed diamond crystals in cell lO should be in excess of 70~ by volume of the volume of crystals. Specifically, the density of the compressed layer of mass of diamond crystals ranges from 71%
up to about but less than 95% by volume, and frequently from about ! 75% to about 90~ by volume of the volume of diamond crystals.
The higher the density of the crystals, the less will be the amount of non-diamond material present between the crystals resulting in a ` proportionately harder diamond body.
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~ he substantially isostatic system 21 of powder en~eloped container resulting from the cold-pressing step is then subjected to a hot-pressing step whereby it is subjected to a hot-pressiny temperature and pressure simultaneously.
Speci~ically, when the cold-pressing step is completed, either one of pistons 23, 23a is withdrawn and the resulting consolidated substantially isostatic shaped system 21 is forced out of liner 22a and into a hole of identical diameter in graphite mold 30, the transferred system 21 now being contained within the wall of hole 31 between graphite pistons 32, 32a. Graphite mold 30 is provided with thermocouple 33 to provide an indication of the temperature being applied to the dimensionally-stabilized substantially-isostatic system 21. The mold 30, with the substantially-isostatic system 21 so contained, is placed inside a conventional hot-pressing furnace (not shown). The furnace chamber is evacuated or at least substantially evacuated causing evacuation of system 21 including cell 10, providing system 21 and cell 10 with a substantial vacuum in which the hot-pressing step can be carried out. However, if desired, at this point, nitrogen, or hydrogen, or an inert gas such as argon can be fed into the furnace chamber to provide the furnace chamber as well as system 21 including the interior of cell 10 with a suitable hot-pressing atmosphere. While piston 32, 32a apply a uniaxial pressure, i.e.
the hot-pressing pressure, to system 21, the temperature thereof is raised to a temperature at which silicon-rich alloy disc 12 produces fluid infiltra-ting silicon-rich alloy.
In the hot-pressing step the hot-pressing temperature should be reached ~uickly and held at such temperatuxe under the hot-pressing pressure usually for at least about one minute to insure satisfactory infiltration through the interstices of the diamond crystal mass. Generally, a hot-pressing time period ranging from about 1 minute to about 5 minutes is satisfactory. Since conversion of diamond to non-diamond elemental carbon depends largely on time and temperature, i.e. the higher -the temperature and the longer , . ~

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the time at such temperature the more likely the conversion to non-diamond elemental carbon, the hot-pressing step must be carried out before 5% by volume of the diamond is converted to non-diamond elemental carbon and this is determinable empirically.
Conversion of 5% or more by volume of diamond to non-diamond elemental carbon is likely to result in elemental non-diamond carbon phase being le~t in t~e final product which would have a significantly deleterious effect on its mechanical propertles.
In the hot-pressing step the application of the hot-pressing pressure to the fluid infiltrating silicon-rich alloy breaks up interfacial refractory layer or slag, largely oxide as well as carbide, which usually forms between the fluld silicon-rich alloy and diamond surfaces exposing the capillary void system to the silicon-rich alloy, after which infusion by capillary action occurs. Tests have shown that unless sufficient pressure is applied and maintained throughout hot-pressing to system 21 when the silicon-rich alloy is fluid to break up the slag, infusion of the diamond mass by the silicon-rich alloy will not occur.
During hot-pressing, as the fluid silicon-rich alloy infiltrates and flows through the diamond mass and into contact with the substrate, it encapsulates the surfaces of the compressed diamond crystals reacting wi-th the diamond surfaces, or any non-diamond elemental carbon which may form to produce a carbide which at least in major amount and usually in substantial amount is silicon carbide. During hot-pressing, the infiltrating alloy also fills the interface ` between the contacting surfaces of the polycrystalline diamond `~ body and substrate resulting in the production of a strong adherent bond in situ. The resulting product is an integral well-bonded composite. The infiltrating alloy may also pentrate or diffuse into the substrate.
It is during this hot-pressing step that it is particularly important that substantially isostatic conditions be maintained so that when the silicon-rich alloy is converted to the fluid state, this fluid will not be able ~r 6~

to pass between mass 13 and cup 11 and escape to any significant extent, but will be forced to move throughout the mass 13 of diamond crystals.
When the hot-pressing step is completed, at least sufficient pressure should be maintained during cooling of the hot-pressed system 21 so that hot-pressed cell 10 is subjected to substantially isostatic pressure sufficient to preserve its dimensional stability. Preferably, hot-pressed system 21 is allowed to cool to room temperature. Hot-pressed cell 10 is then removed from the system, and the present composite 36 is recovered comprised of polycrystalline diamond body 13a bonded in situ directly to substrate l~a. Adherent metal, if any, from the protective container and any squeezed out excess silicon alloy at the outside surfaces of the composite can be removed by conventional techniques such as grinding.
When the present process is carried out with the components in the form of layers, coextensive with each other the resulting composite can be in a number of forms such as a disc, square or rectangle, rod or bar and can have a flat face of bonded diamonds.
When the present process is carried out with the - silicon-rich alloy in the form of a tube or a cylinder with a core or hole extending through it and the substrate is in the form of a bar centrally positioned within the core of the tube and the encircling space between the silicon alloy tube and substrate bar packed with diamond crystals, the resulting composite is in the form of a ~` circular bar.
The present composite is comprised of a polycrystalline ; 30 diamond body integrally bonded to a substrate of a polycrystalline i silicon carbide or silicon nitride body by a bond formed in situ.
The adhered polycrystalline diamond body of the present composite is comprised of diamond crystals adherently bonded to each other by a silicon atom-containing bonding medium, said diamond crystals ranging in size from about 1 micron to about 1000 microns, the density of said diamond crystals : ~ .

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ranging from at least about 70% by volume up to about but less than 90% by volume and frequently about 89% by volume of said polycrystalline diamond body, said silicon atom-containing bonding medium being present in said diamond body in an amount ranging up to about 30% by volume of said diamond body, said bonding medium being distributed at least substantially uniformly throughout the polycrystalline diamond body, the portion or surface of said bonding medium in contact with the surfaces of the bonded diamonds being at least in major amount silicon carbide, i.e. m~re than 50~ by volume of the portion or surface of the bonding medium in direct contact with the surfaces of the diamond crystals in silicon carbide. Preferably, the portion or surface of said bonding medium in contact with the surfaces of the bonded diamonds is silicon carbide at least in substantial amount, i.e. at least about 85% by volume and preferably 100% by volume of the bonding medium in direct contact with the surfaces of the bonded diamond crystals is silicon carbide. The diamond body of the present composite is pore-free or at least substantially pore-free.
In the composite, the polycrystalline silicon nitride substrate ranges in density from about 80% to about 100% of the theoretical density of silicon nitride and contains silicon nitride in an amount of at least 90% by weight of said body and is free of constituents which have a significantly deleterious effect on the mechanical properties of said ` composite.
In the composite, the polycrystalline silicon carbide substrate ranges in density from about 85% to about 100% of the theoretical density of silicon carbide and contains silicon carbide in an amount of at least 90% by weight of said body and is free of constituents which have a significantly deleterious effect on the mechanical properties of said composite.
In the present composite, at the interface between the polycrystalline diamond body and silicon carbide or s~ilicon nitride substrate, the bonding medium extends Erom the ` 24 RD-1033~/10335 polycrystalline diamond body into contact with -the substrate at least substantially -filling any pores throughout the interface so that the interface is pore-free or at least substantially pore-free, i.e. it may contain voids or pores in an amount less than 1% by volume of the total volume of the interface providing such voids or pores are small, less than 0.5 micron, and sufficiently uniformly distributed throughout the interface so that they have no significant deleterious effect on ~he adherent bond at such interface. The void or pore content at the interface is determinable by standard metallographic techniques such as for example, optically examining a cross-section of the composite. Generally, the distribution and thickness of the bonding medium throughout the interface is substantially the same as the distribution and thickness of the bonding medium throughout the polycrystalline diamond body of the composite. Ordinarily, on the basis of a polished cross-section of the composite, the average ~hickness of the bonding medium at the interface would be substantially the same as the a~erage thickness of . 20 bonding medium between the contacting diamond crystals of the polycrystalline diamond body of the composite. Also, on the . basis of a polished cross-section of the composite, the ~, maximum thickness of bonding medium at the interface would be substantially equivalent to the thickness of bonding medium ~ between the largest contacting diamond crystals of the r polycrystalline diamond body of the composite. Alternatively, the maximum thickness of bonding medium at the interface can be defined as about 50% of the largest size diamond crystals : in tlle polycrystalline diamond body measured along their longest edge dimension. The silicon carbide substrate may also contain bonding medium produced by the penetration or diffusion therein by the infiltrating alloy during hot-` pressing.
The present silicon atom-containing bonding medium always contains silicon carbide. ~n one embodiment, the - present bonding medium is comprised of silicon carbide and metal silicide. In ano~her embodiment, the present bonding R~-10334 ~ 25 -medium is comprised of silicon carbide, metal silicide and elemental silicon. In yet another embodiment, the present bonding medium is comprised of silicon carbide, metal silicide and metal carbide. In yet another embodiment, the present bonding medium is comprised of silicon carbide, metal silicide, metal carbide and elemental silicon. In still another embodiment, the present bonding medium is comprised of silicon carbide, metal carbide and elemental silicon. The metal components of the metal silicide and metal carbide in the present bonding medium are produced by the alloying metals present in the infiltrating alloy.
The metal component of the metal silicide present in the bonding medium is preferably selected from the group consisting of cobalt, chromium, iron, hafnium, manganese, rhenium, rhodium, ruthenium, tantalum, thorium, titanium, uranium, vanadium, tangsten, yttrium, zirconium and alloys thereof.
The metal component oE the metal carbide present in the bonding medium is a strong carbide former which forms a stable carbide and is preferably selected from the group consisting of chromium, hafnium, titanium, ~irconium, tantalum, vanadium, tungsten, molybdenum and alloys thereof.
The amount of elemental silicon, if any, and silicon carbide in the bonding medium of the adhered polycrystalline diamond body can vary depending on the extent of the reaction bet~een the surfaces of the diamond crystals and the infiltrating silicon-rich alloy as well as the reaction between non-diamond elemental carbon and infiltrating silicon-rich alloy. Assuming all other factors are equal, the particular amount of silicon carbide present in the bonding medium in the adherent polycrystalline diamond body depends largely on the particular hot-pressing temperature used and the time period at such temperature. Specifically, with increasing time and/or temperature, the amount of silicon carbide increases while the amount of elemental silicon decreases or is reduced to a non-detectable amount.
The production of the present body of bonded diamond crystals .

.;

with a particular desired amount of sillcon carbide to attain certain desirable properties, for example, is determinable empirically.
Specifically, the bonding medium in the adhered polycrystalline diamond will always contain at least a detectable amount of silicon carbide and at least a detectable amount of a silicide and/or carbide of the alloying me-tal present in the infiltrating alloy. The metal silicide is usually in the form of a disilicide depending upon the particular infiltratin~
- 10 alloy used. The bonding medium may also contain at contain at least a detectable amount of elemental silicon. By a detectable amount of silicon carbide, metal silicide, metal carbide or elemental silicon it is meant herein an amount detectable by selective area diffraction analysis of transmission electron microscopy on a thin section of the present body. Generally, however, the present bonding medium in the diamond body contains silicon carbide in an amount ranging from about 1%
by volume to about 25~ by volume of the present polycrystalline diamond body and usually metal silicide in at least a detectable amount, and frequently in a minimum amount of about 0.1% by volume of the polycrystalline diamond body. The particular amount of metal silicide present depends largely on the composition of the infiltrating silicon-rich alloy.
The metal silicides are hard and also frequently have lower linear thermal expansion coefficients than the metals, or in some instances lower than diamond, as for example rhenium, a desirable property for a phase in a polycrystalline diamond body. The particular amount of silicon carbide and elemental silicon present depends largely on the composition of the infiltrating silicon-xich alloy as well as on the extent of the reaction between the infiltrating silicon-rich alloy and a diamond or non-diamond carbon. The particular arnount of metal carbide present depends largely on the composition of the infiltratin~ silicon-rich alloy.
Selective area diffraction analysis of tran.smission electron microscopy on a thin section of the present ,: .
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~ D-10334 composite also will show that the portion of the bonding medium in contact with the surfaces of ~he bonded diamonds is at least in major amount silicon carbide.
The present adhered body of bonded diamond crystals is void or pore-free or at least substantially pore-free, i.e. it may contain voids or pores in an amount less than 1% by volume of the body providing such voids or pores are small, less than 0.5 micron, and sufficiently uniformly distributed throughout the body so that they have no significant deleterious eEfect on its mechanical properties. The void or pore content of the present body is determinable by standard metallographic technique such as, for example, optically examining a polished cross-section of the body.
The present adhered diamond body also is free of non-di~mond carbon phase in that it does not contain non-diamond elemental carbon phase in an amount detectable by X-ray diffraction analysis.
One particular advantage of the present invention is that the polycrystalline diamond body of the present composite can be produced in a wide range of sizes and shapes. For example, the adhered diamond body can be as wide or as long as one inch or longer. Polycrystalline diamond bodies one inch in length or longer and having the present diamond density are not producible as a practical matter, ox are not producible at all, by techniques utiIizing the ultra high pressures and temperatures of the diamond stable region due to the limitations of the equipment necessary to sustain the severe pressure-temperature requirements for the necessary period of time, i.e. the equipment is so complex and massive that its capacity is limited. On the other hand, the present adhered polycrystalline diamond body can be as small or as thin as desired, however, it will always be in excess of a monolaryer of diamond crystals.
The present composite is highly useful as an abrasive, cutting tool, nozzle or other wear-resistant part.
The invention is further illustrated by the following examples where, unless otherwise stated, the procedure was as follows:
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SILICON CARBIDE SUBSTRATE
Hexagonal boron nitride powder of fine particle size, e.g. ranging in size from about 2 microns to about 20 mi~rons, was used as the pressure transmitting medium.
The polycrystalline silicon carbide substrate was in the form of a disc with a thickness of about 120 mils.
The equipment used was substantially the same as that shown in Figures 4 and 5.
Cold-pressing of the charge was carried out at room temperature as shown in Figure 4 to about 80,000 psi.
The amount oE infiltrating alloy was sufficient to completely infiltrate through the compressed diamond mass and to contact the contacting surface of the substrate and fill the pores of the interface.
The infiltrating alloy was a eutectiferous silicon-rich alloy.
Density given herein of the polycrystalline silicon carbide body used as a substrate is the fractional density based on the theoretical density of the silicon carbide of 3.21 gm/cc.
All of the polycrystalline silicon carbide bodies, sintered as well as hot-pressed, used as substrates had substantially the same composition, which was comprised of silicon carbide, about 1~ to 2% by weight of boron based on said , silicon carbide and less than about 1% by weight of submicron elemental carbon based on said silicon carbide. The carbon was in particle form of submicron size.
The diamond powder used ranged in particle size from 1 micron -to about 60 microns with at least 40 weight % of the diamond powder being smaller than 10 microns.
Where a particular diamond density is given as percent by volume of the polycrystalline diamond body, it was determined by the standard point count technique using a photomicrograph of a polished surface magnified 690 times and the surface area analyzed was sufficiently large to represent the microstructure of the entire body.
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Where the ~iamond ~ensity is given as a range greater than 70% by volume but less than gO% by volume oE the polycrystalline diamond body, this range is based on experience, results with similar runs, particularly runs where the polycrystalline diamond body alone was prepared, and the appearance o~ the adhered polycrystalline body as a whole, and also, the volume oE the recovered cleaned polycrystalline diamond body portion of the composite as compared to the volume o~ the starting diamond powder on the assumption that less than 5% by volume of the diamond powder had converted to non-diamond elemental carbon phase.
In Table I, in Examples l to 5, a molybdenum cup with zirconium liner was used and a cast alloy in the form o~ a disc of the given composition and thickness and having essentially the same diameter as the zirconium liner was placed within the zirconium liner at the bottom of the cup. The diamond powder in the given amount wàs packed on top of the disc. Finally, the given polycrystalline silicon carbide disc was placed on top of the diamond powder forming a plug in the cup as shown by 14 in Figure 2.
The resulting plugged cup was then packed in hexagonal boron nitride powder as shown in Figure 4 and the whole charge was pressed at room temperature, i.e. cold-pressed, in a steel die to about 80,000 psi subjecting the cup and contents to substantially isostatic pressure until the pressure became stabiliæed producing a dimensionally stabilized shaped substantially isostatic system of powder-enveloped plugged cup. From previous experiments it was known that in the resulting pressed assembly, i.e. in the resulting shaped substantially isostatic system of powder-enveloped plugged cup, the density of the diamond crystals was higher than 75% by volume of the compressed diamond mass.
The resulting pressed assembly 21 of powder-enveloped plugged cup was then hot-pressed, i.e. it was pushed into a graphite mold of the same diameter size as the steel die, as shown in Figure 5, whicll was placed within an induction heater. The interior Oe the plu~ed cup uas evacuated ~d `

nitrogen atmosphere introduced therein by evacuating the heater to about 10 torr before back filling it with nitrogen.
A pressure of about 5000 psi was applied to the pressed assembly 21 and maintained thereon by the graphite die which was then heated by the induction heater at a rate which reached the given maximum hot-pressing temperature in about 5 to 7 minutes. As the assembly was heated, the pressure increased to the given maximum hot-pressure due to the expansion oE the system.
At the given temperature at which infiltration begins or proceeds, the piston and the pressure dropped to about 5000 psi indicating that the alloy had become fluid and had proceeded to infiltrate through the compressed diamond mass. The pressure was then raised bac~ to the given maximum hot-pressing pressure where it was maintained at the given maximum hot-pressing temperature for one minute to insure complete infiltration by the alloy of the small capillaries of the compressed diamond mass. The powder supply was then turned off but no additional pressure was applied. This provided a firm pressure at high temperature but reduced pressure at low temperature providing adequate geometric stability, i.e. this maintained the dimensions of the hot-pressed assembly until it was sufficiently cool for handling.
The resulting composite was recovered by grinding and grit blasting way can metal, i.e. molybdenum cup and zirconium sleeve, and excess alloy at the outside surfaces of the composite.
The resulting cleaned integral composite bodies had the shape of a substantially uniform disc which in Examples 1 to 3 had a thickness of approximately .195 inch and in Example 4, approximately .160 inch.
` In Examples 6 and 7 of Table I no metallic container, liner or substrate was used but the equipment used was substantially the same as that set forth in Figures 4 and 5.
Specifically, to carry out Examples 6 and 7, the hexagonal boron nitride powder was packed into the die o~ Figure 4 and a cylinder used as a mold was pressed into the power. The . ~
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cylinder was made of cemented metal carbide and was about 0.35 - inch in diameter and 0.25 inch in thickness. The axis of the cylinder was approximately lined up with the central axis of the die.
After the cylinder was inserted in the powder, additional hexagonal boron nitride powder was placed in the die covering the cylinder completely, and the resulting powder-enveloped cylinder was pressed at room temperatures under a pressure of 50,000 psi. Piston 23a was then withdrawn and piston 23 was used to push the resulting pressed powder-enveloped cylinder partially out of the die.
me exposed portion of the pressed powder was removed leaving the cylinder partially exposed. The cylinder was then withdrawn leaving the cavity it had impressed therein. In Examples 6 and 7, a cast alloy disc of the given composition and thickness having a diameter essentially the same as the inner diameter of the cavity was placed in the bottom of the cavity. A layer of diamond powder of the given size, amount and thickness was packed on top of the alloy.
A disc of hot-pressed hexagonal boron nitride powder of about the same diameter as the inner diameter of the cavity was placed within the cavity on top of the diamond powder as a plug to insure that the surface of the resulting polycrystalline diamond body would be flat.
The entire mass was then pushed into the center of the die by piston 23a which was then withdrawn. An additional amount of hexagonal boron nitride powder was added to the die to cover the hot-pressed disc of hexagonal boron nitride resulting in the cavity and contents being enveloped by hexagonal boron nitride as illustrated by Figure 4. The resulting charge was then pressed at room temperature, i.e. cold-pressed~ in the steel die under a pressure of 80,000 psi as shown in Figure 4 subjecting the cavity and its contents to substantially isostatic pressure until the pressure became stabilized producing a dimensionally stabilized shaped substantially isostatic system of powder-enveloped cavity and contents. From previous experiments it was known that in the ~ X~

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resulting pressed assembly, i.e. in the resulting shaped substantially isostatic system of powder-enveloped cavity and contents, the density oE tlle diamond crystals was higher than 75% by volume of the compressed diamond mass.
The resulting pressed assembly of powder-enveloped cavity and contents, which was substantially the same as 21 except that no metal container was used, was then hot-pressed, i.e. it was pushed into a graphite mold of the same diameter size as the steel die, as shown in Figure 5, and placed within 10 an induction hea-ter. The interior of the cavity was evacuated and a nitrogen atmosphere introduced therein by evacuating the heater to about 10 torr before back filling it with flowing dry nitrogen. A pressure of about 5000 psi was applied to the pressed asse~bly and maintained thereon by the graphite die, which was then heated by the induction heater at a rate which reached the given maximum hot-pressing temperature in about 5 to 7 minutes. As the assembly was heated, the pressure increased to the given maximum hot-pressure due to the expansion of the entire system.
At the given temperature at which infiltration begins or proceeds the piston and the pressure dropped to about 5000 psi indicating that the given alloy had melted and become fluid and had infiltrated through the diamond mass. The pressure was then raised back to the given maximum hot-pressing pressure where it was maintained at the given maximum hot-pressing temperature for one minute to insure complete infiltration by the alloy of the smaller capillaries of the compressed diamond mass. The power supply was then turned off but no additional pressure was applied.
This provided a firm pressure at high temperature but reduced pressure 30 at lower temperature providing adequate geometric stability. At room temperature, the resulting polycrystalline diamond body was recovered. me plug did not bond to the diamond body. After removing surface scales of hexagonal boron nitride powder and excess alloy by grinding and grit blasting the resulting integral polycrystalline diamond body had the shape of a disc with the given ` thickness.
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In Table I the hot-pressing temperature at which infiltration begins is that temperature at which the alloy is fluid and proceeds to infiltrate through the compressed diamond mass. The given maximum hot-pressing temperature and maximum hot-pressing pressure were maintained simultaneously for one minute to insure complete infiltra-tion of the smaller capillaries of the compressed idamona crystal mass.
X-ray diffraction analysis given in Table I of 10 Examples 6 and 7 was made on the polycrystalline diamond body in crushed form.

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In Examples l to 5, the interface of each composite disc between the adhered polycrystalline diamond body and silicon carbide substrate could not be detected. Each composite appeared to be a continuous structure through its thickness and the grain size of the diamond portion distinguished it from the substrate.
The external surface of each adhered polycrystalline diamond body appeared to be well-infil-trated with bonding medium which appeared to be uniformly distributed. The diamonds appeared to be well-bonded to each other~
~he adhered polycrystalline diamond body of the composites of Examples 1 to 4 had a diamond density higher than 70~ by volume but ~ess than 90% by volume of the volume of the polycrystalline boby.
The diamond face of the composite of Example 5 was polished on a cast iron scaife. Examination of the polished surface, showed no strings of holes formed from diamond fragment pullout illustrating the strong bonding therein. The density of the diamond crystals was about 73% by volume of the adhered polycrystalline diamond body.
In Examples 6 and 7/ the polycrystalline diamond bodies were well-infiltrated and well-bonded. Using a hammer and wedge, each disc, i.e. polycrystalline diamond body, was fractured substantially in half and the fractured cross-sectional sur~aces were examined ~" optically under a microscope magnified about lO0 times. Examination of their fractured surfaces showed them to be pore-free, that the bonding medium was uniformly distributed throughout the body, and that the fractures were transgranular rather than intergranular, ` i.e. each had fractured through the diamond grains rather than along the grain boundaries. This indicates that the bonding medium was highly adherent and was as strong as the diamond grains or crystals themselves.
The diamond density of the disc of Example 6 was greater than 70% but less than 90% by volume of the body.
. A fractured surface of the disc of Example 7 was pol-;~ ished on a cast iron scaife and examination of the polished :`:
, ~
: .

sur~ace showed no strings of holes formed from diamond fragment pullout illustrating the strong bonding therein. The density of -the diamond crystals was about 80% by volume of the polycrystalline diamond body.

The composite produced in Example 1 was evaluated as a cutting tool. The exposed surface of the polycrystalline diamond body of the composite was ground with a diamond grinding wheel to smooth it out and produce a sharp cutting edge. The substrate 10 of the composite was then clamped in a tool holder.
A portion of the cutting edge was evaluated on a lathe turning of Jackfork Sandstone with a feed per revolution of .005 inch and a depth of cut of .020 inch.
At a cutting speed of 98 surface feet per minute, the wear rate was determined to be .077 cubic inch per minute X
10 . Another portion of the cutting edge was evaluated at a cutting speed of 276 surface feet per minute and was found to have a wear rate of .53 cubic inch per minute X 10 6.
Still another portion of the cutting edge was evaluated at a 20 cutting speed of 290 surface feet per minute and was found to have a wear rate of 1.46 cubic inch per minute X 10 The composite was removed from the tool holder and examination of the interface between the diamond body and '~ substrate showed that it had not been affected by these machining tests.

The procedure used in this example was -the same as that set forth in Example 8 except that the composite produced in Example 2 was used.
A portion of the cutting edge at a cutting speed of 110 surface feet per minute showed a wear rate of .203 cubic inch per minute X 10 . Another portion of the cutting edge at a cutting speed of 320 surface feet per minute showed a wear rate of 1.48 cubic inch per minute X 10 Examination of the composite after machining showed that the interface between the polycrystalline diamond body -,'' , ' ' ' ~

, $.~

and silicon carbide substrate was not affected by these machining tests.
- ExAMæLE 10 The procedure used in this example was the same as that set forth in Example 8 except that the composite of Example 3 was used.
A portion of the cutting edge at a cutting speed of 110 surface feet per minute showed a wear rate of .234 cubic inch per minute X 10 6. ~nother portion of the cutting edge at a cutting speed of 320 surface feet per minute showed a wear rate of 1.85 cubic inch per minute X 10 Examination of the composite after machining showed that the interface between the polycrystalline diamond body and silicon carbide substrate was not affected by these machining tests The procedure used in this example was the same as that set forth in Example 8 except that the composite of Example 4 was used.
; 20 After 4 minutes of successful cutting at a cutting speed of 98 surface feet per minute, small pieces of the cutting edge broke. Using another portion of the cutting edge, after 6 minutes of successful cutting at a cutting speed of 280 surface feet per minute, small pieces of cutting edge broke. It is believed that the cutting edge breakage was due to the hot-pressing temperatures not being sufficiently high to completely infiltrate the small capillaries of the polycrystalline diamond mass during hot-pressing. A comparison with Example 7 of Table I shows that the higher hot-pressing temperatures produced a well-infiltrated and well-bonded polycrystalline diamond body.

; The procedure for preparing a composite was substan-tially the same as that set forth in Example 2 except that 260 mg of the silicon chromium alloy were used, and the alloy disc was .050 inch thick.

f3(~
:

Also, 250 mg of diamond powder were used wherein 60 w/o (weight /0) ranged in size from 53 to 62 microns, 30 w/o ranged from 8 to~ 22 microns, and 10 w/o ranged from 1 to about 5 microns. The diamond powder was packed to an ap-proximate thickness o about .055 inch. Also a zirconium cup with a zirconium liner were used.
The maximum hot-pressing pressure was abou-t 13,000 psi and the hot pressing temperature ranged from about 1250C
when infiltration be~an to a maximum hot-pressing tempera-ture of about 1500C. The composite was recovered in the same manner as Example 2 and was in the form of a substan-tially uniform disc having a thickness of about .060 inch.
The silicon carbide substrate was ground o~f the compo-site and the resulting polycrystalline diamond body was subjected to a thermal stability test. Speciically, it was heated in air to a temperature of 900C, which was the limiting temperature of the furnace. As it was heated9 its linear thermal expansion coefficient was determined for ; temperatures ranging from 100C to 900C. At 900C, the power was cut off.
The test data and inspec~ion of the sample, i.e. the polycrystalline diamond body, after the test indicated that there was no sudden change in length in the sample during the entire range of the heating cycle and there was no evidence of any permanent damage caused to the sample by this heating cycle.

The procedure used in the example was substantially the same as that set forth in Example 2 except that a disc of silicon was used in a zirconium cup with a zirconium liner to form a silicon-rich zirconium alloy in situ.
Six composites were prepared. To p~epare three of the composites, a diamond powder was used wherein 60 w/o ranged in size from 53 to 62 microns, 30 w/o ranged from 8 to 22 microns and 10 w/o ranged from 1 to about 5 microns. The three other composites were prepared using a diamond powder which ranged from 1 to 60 microns in si~e wherein at least 40 w/o was smaller than 10 microns in size.

6~;~

.
~o RD-10334/103~5 The maximum hot-pressing pressure was abou-t 13,000 psi, and the hot-pressing temperature ranged from about 1340C
which is the temperature at which infiltration proceeded, indicating that the silicon-rich zirconium alloy had formed in situ and had become fluid, to a maximum hot-pressing temperature of about 1500C.
Each composite was recovered in substantially the same manner as Example 2 and each was in the form of a disc.
The top and cylindrical faces of the adhered poly-crystalline diamond body of all six composites were surface ground. The difficulty of grinding these composites with a diamond grindin8 wheel indicated that the abrasion resis-tance of these adhered diamond bodies was comparable to commercially available polycrystalline diamond products.
~`~ The three composites prepared with the diamond powder which ranged from 1 to 60 microns in size had improperly mixed aggregates of diamond powder of less than 2 microns in size and inspection of the ground edges of the adhered polycrystalline body showed incomplete infiltration of these aggregates by the alloy but the remainder of the ground diamond area was well-bonded.
Optical examination of the composites showed no detect-able defects or distinctively different interlayer between the silicon carbide subs-trate and the diamond layer. Four of the composites were broken to see the in-ternal structure.
Optical examination of the fractured surfaces showed no visible interlayer or defects at the intexface between the silicon carbide substrate and the adhered polycrystalline diamond layer.
The continuity of structure at the substrate-diamond layer interface was excellent and only the grain size dif-ference in diamonds and silicon carbide enabled recognition of the boundary between the substrate and diamond layers.
Two of the composites were evaluated as cutting tools by lathe turning of a very abrasive sand-filled rubber bar.
The cutting parameters were 30 mil depth of cut, S mil feed per revolution, and 600 surface feet per minute of cutti.ng -~1 - speed. After 16 minutes, 22 seconds of cutting, both tools showed about 5 mil size uniform flank wear indicating that the wea~ resistance of cutting edge was excellent.

The composite produced in Example 1 was fractured substantially in half by means of a hammer and wedge, and the fractured cross-sectional surfaces were examined opti-cally under a microscope magnified about 100 X. Examination of the fractured surfaces showed that the polycrystalline diamond body as well as the interface of the composite were pore-free, that the bonding medium was distributed uniformly throughout the diamond body and that the fracture was trans-granular rather than intergranular, i.e. that the fracture occurred through the diamond grains rather than along the grain boundaries. This indicates that the bonding medium was highly adherent and was as strong as the diamond grains or crystals themselves. Also, no visible interlayer or defects at the interface between the silicon carbide sub-strate and the adhered polycrystalline diamond layer could be detected. The fractured surface of the composite appear-ed to have a continuous structure and only the difference in grain size between the diamond and strongly adhered sub-strate enabled recognition of the boundary between the substrate and adhered polycrystalline diamond body.
The fractured cross-section of the composite was polish-: ed on a cast iron scaife. Optial examination of the polish-ed cross-sectional surface, which is shown in Figure 7, showed no strings of holes formed from diamond fragment pullout illustrating the strong bonding therein. The poly-crystalline diamond body is shown in the upper portion and the substrate in the lower portion of Figure 7, and the interface therebetween can be distinguished by the di-ffer-ence in crystal structure between the diamond body and the substrate. The density of the diamond crystals was about 71% by volume of the polycrystalline diamond body in Figure 7.

.

~2 RD- 10334/1033g - SILICON NITRIDE SUBSTRATE
.
Hexagonal boron nitride powder of fine particle size, e.g. ranging in size from about 2 microns to about 20 mi-crons, was used as the pressure transmitting medium.
The polycrystalline silicon nitride substrate was in ` the form of a disc which in Examples 2 and 3 had a thicknessof about 125 mils and in Examples 5 and 6 had a thickness of about 100 mils. It was a commercially available hot-pressed material with a density higher than 99~, i.e. it was almost 100~ dense, and was comprised, by weight of the silicon nitride hot-pressed body, of 1/2% MgO, about 1/2/~ Fe, about 1/200% metallic impurities such as Ca, A1 and Cr, 2% free .- Si, 1~ SiC with the remainder being silicon nitride.
The equipment used was substantially the same as that shown in Figures 4 and 5.
Cold-pressing of the charge was carried out at room temperature as shown in Figure 4 to about 80,000 psi, and in the resulting pressed assembly, the density of the diamond crystals was higher than 75% by volume of the compressed diamond mass.
The amount of infiltrating allow was sufficient to ` completely infiltrate through the compressed diamond mass and to contact the contacting surface of the substrate and fill the pores of the interface.
- The infiltrating alloy was a eutectiferous silicon-rich alloy.
Density given herein of the polycrystalline silicon nitride body used as a substrate is the fractional density based on the theoretical density of the silicon nitride of

3.18 gm/cc.
Fracturing of a composite or a polycrystalline diamond body was carried out with a hammer and wedge.
Optical eXaminatiOt1 was under a microscope magnified about 100 X.
Polishing was carried out on a cast iron scaife.
Where a particular diamond density is given as percent .; by volume of the polycrystalline diamond body, it was ``'', ' ` ,. , ..

. :` .

~3 ~D-10334/103~5 determined by the standard point count technique using a photomicrograph of ~ polished surface magnified 690 times and the surface area analy~ed was sufficiently large to represent the microstructure of the entire body.
Where the diamond density is given as a range greater than 70% by volume but less than 90/O by volume of the poly-crystalline diamond body, this range is based on experience, results with similar runs, particularly runs where the polycrystalline diamond body alone was prepared, and the appearance of the adhered polycrystalline body as a whole, and also, the volume of the recoverd cleaned polycrystalline diamond body portion of the composite as compared to the volume of the starting diamond powder on ~he assumption that less than 5% by volume of the diamond powder had converted to non-diamond elemental carbon phase.
In Examples 15 and 16, the infiltrating silicon-rich alloy was an alloy of silicon and zirconium formed in situ.

In this example a polycrystalline diamond body was prepared witout a substrate.
- A cast silicon disc weighing 330 mg was placed within a zirconium sleeve in a molybdenum cup. About 500 mg of fine diamond powder, particle size ranging from 1 micron to about 60 microns with at least 40 weight /O of the diamond powder being smaller than 10 microns was packed on top of the silicon disc. A molybdenum cup slightly larger in diameter than the original cup, i.e. the cup containing silicon and diamonds, was placed over the opening of the original cup as a cover.
~he resulting container was then packed in hexagonal - boron nitride powder as shown in Figure 4 and the whole charge was pressed at room temperature, i.e. cold-pressed, ` in a steel die to about 80,000 psi subjecting the container and its contents to substantially isostatic pressure until the pressure became stabilized producing a dimensionally stabilized shaped substantially isostatic system oi powder-enveloped container. From previous experiments i-t was known ~` `
. .

~ . .

,;.` . :

4~ 1 RD-1033~/10335 that in the resulting pressed assembly, i.e. in the result-ing shaped substantially isostatic system of powder-envel-` oped container, the density of diamond crystals was higherthan 75% by volume of the compresscd diamond mass. Also, the ; amount of silicon present was about 80% by volume of the compressed diamond mass.
; The resulting pressed assembly 21 of powder-envelopedcontainer was then hot-pressed, i.e. it was pushed into a graphite mold of the same diameter size as the steel die, as shown in Figure 5, which was placed within an induction heater. The interior of the container was evacuated and a nitrogen atmosphere introduced therein by evacuating the heater to about 10 torr before back filling it with nitro-gen. A pressure of about 5000 psi was applied to the pressed assembly 21 and maintained thereon by the graphite die which was then heated to a temperature of 1500C in about 7 min-utes by the induction heater. As the assembly was heated, the pressure also went up to about 10,000 psi due to the expansion of the system. When the temperature reached about 1350C the piston 23a dropped and the pressure dropped to about 5000 psi indicating that silicon-rich zirconium alloy had formed, become fluid and had proceeded to infiltrate through the compressed diamond mass. The pressure was raised to the maximum hot-pressing pressure o~ 10,000 psi and when the tempe-rature reached 15~0C, the assembly was maintained at the maximum hot-pressing ternperature ~f 1500C
under 10,000 psi for 1 minute to insure complet infiltration by the alloy of the smaller capillaries of the compressed diamond mass. The power supply was then turned off but no additional pressure was applied. This provided a firm pres-sure at high temperature but reduced pressure at low temper-ature providing adequate geometric stability, i.e. this maintained the dimensions of the hot-pressed assembly until ~-- it was sufficiently cool ior handling.
The resulting polycrystalline diamond body was recov-ered by grinding and grit blasting away can metal, i.e.
~ molybdenum cup and zirconium sleeve, and e~cess silicon at ` the outside surface and faces of the body.
.
. .
:

.

The resulting integral polycrystalline diamond body had the shape of a disc about 0.115 inch thick. It appeared to . be well-infiltrat~d and bonded.
X-ray dif~raction analysis of the cleaned face through which the alloy entered showed it to be comprised of dia-mond, silicon carbide and elemental silicon, indicating that the silicon carbide and elemental silicon were present in an amount of at least 2% by volume o~ the body. ~owever, the X-ray difraction analysis did not detect non-diamond elemental carbon phase.
Examination of the fractured cross-sectional surfaces of the disc showed that the fracture was transgranular rather than intergranular, i.e., it had fractured through the diamond grains rather than along grain boundaries. This indicates that the bonding medium was highly adherent and was as strong as the diamond grains or cr~stals themselves.
Examination of the fractured surfaces showed them to be pore-free and the bonding medium was uniformly distributed throughout the body.
Examination of the polished cross-sectional surfaces showed no strings of holes formed from diamond ragment pullout illustrating the strong bonding therein and its usefulness as an abrasive.
The density of the diamond crystals was about 81% by volume of the polycrystalline diamond body.
A photomicrograph of the polished surface, magniiied ; 690 times, showed a white phase. X-ray spectral analysis of this phase showed that it consisted of zironium and silicon indicating that this phase was zirconi~m silicide.

In this example, the eomposite was prepared using ` hot-pressed polycrystalline silicon nitride as a substrate.
A cast silicon disc weighing 142 mg was placed within a ` zirconium sleeve in a zirconium cup. 270 mg of diamond powder wherein 85 weight % of the diamond ranged in size rom 53 mi~rons to 62 microns and 15 weight % was about 5 microns in size was packed on the silicon disc producing an . `
.:

~ . :- . - :
t "`

~ ~ ' ` `!

.` ~ .

RD-1033li/10335 approximate powder thickness of .06~ inch. Instead of the : metal can cover used in Example 1, hot-pressed polycrystal-: line silicon nitride was used as a plug~ i.e. plug 14, as shown in Figure 2.
The resulting plugged cup was then pac~ed in hexogonal boron nitride powder as shown in Figure 4 and the whole charge was cold-pressed at room temperature in the same manner disclosed in Example 1 subjecting the plugged cup and its contents to substantially isostatic pressure until the pressure became stabilized producing a dimensionally stabi-lized shaped substant:ially isostatic system of powder-envel-oped plugged cup. From previous experiments it was known that in the resulting pressed assembly, i.e. in the result-- ing shaped substantially isostatic system of powder-envel oped plugged cup, the density of diamond crystals was higher than 75% by volume of the compressed diamond mass. The resulting pressed assembly 21 of powder-enveloped plugged cup was then hot-pressed in the same manner disclosed in Example 15 except as given in Table II.
~o The resulting composite was recovered by grinding and grit blasting away can metal and excess silicon at the outside surface and faces of the composite.
Examples 15 and 16 are shown in Table II. Also, in Table II, in Examples 17, 19 and 20 a cast alloy in the form of a disc of the given composition and thickness and having essentially the same diameter as the given liner was placed within the liner at the bottom of the given cup. The dia mond powder in the given amount was packed on top of the disc. Finally, the given pol~crystalline silicon nitride substrate was placed on top of the diamond powder forming a plug in the cup as shown by 14 in Figure 2. The resulting plugged cup was then cold-pressed and hot-pressed in the same manner disclosed in Example 2 e~cept as given in Table I~. The resulting composite was recovered substantially in the same manner disclosed in Example 16.
.

:

~ L6~L
~7 . RD-10334/1033~
The resulting cleaned integral composite bodies of Examples 1~, 17, 19 and 20 had the shape o~ a substantially uniform disc which in Examples 16 and 17 had a thickness of approximately .185 inch, and in Examples 19 and 20 of ap-proximately .150 inch.
In Example ~8, a polycrystalline diamond body was produced and no metallic container, liner or substrate was used but the equipment used was substantially the same as that set forth in Figures 4 and 5. Specifically, to carry out ~xample 18, the hexagonal boron nitride powder was packed into the die of Figure 4 and a cylinder used as a mold was pressed into the powder. The cylinder was made of cemented metal carbide and was about 0.35 inch in diameter and 0.25 inch in thickness. The axis o the cylinder was approximately lined up with the central axis of the die.
After the cylinder was inserted in the powder, addi-tional hexagonal boron nitride powder was placed in the die covering the cylinder completely, and the resulting powder-enveloped cylinder was pressed at room temperatures under a pressure of 50,000 psi. Piston 23a was then withdrawn and piston 23 was used to push the resul-ting pressed powder enveloped cylinder partially out of the die.
The exposed portion of the pressed powder was removed leaving the cylinder partially exposed. The cylinder was then withdrawn leaving the cavity it had impressed therein.
In Example 4, a cast alloy disc of the given composition and thickness having a diameter essentially the same as the inner diameter of the cavity was placed in the bottom of the cavity. A layer of diamond powder of the given size, amount and thickness was packed on top of the alloy disc.
A disc of hot-pressed hexagonal boron nitride powder of about the same diameter as the inner diameter of the cavit~
. ~ .

. ~

.'` ' ~

' ' ~ .

RD-1033~/10335 was placed within the cavity on top o~ the diamond powder as a plug to insure that the surface o~ the resulting polycrys-talline diamond body would be flat.
The entire mass was then pushed into the center of the die by piston 23a which was then withdrawn. An additional amount of hexagonal boron nitride powder was added to the die to cover the hot-pressed disc of hexagonal boron nitride resulting in the cavity and contents b~ing enveloped by hexagonal boron nitride as illustrated by Fi~ure 4. The rèsulting charge was then pressed at room temperature, i.e.
cold-pressed, in the steel die under a pressure of 80,000 psi as shown in Figure 4 subjecting the cavity and its contents ~o substantially isostatic pressure until the pressure became stab~ ed producing a dimensionally stabi-lized shaped substantially isostatlc system of powder-enveloped cavity and contents. From previous experiments it was known that in the resulting shaped substantially iso-static system of powder-enveloped cavity and contents, the density of the diamond crystals was higher than 75% by volume of the compressed dismond mass.
The resulting pressed assembly of powder-enveloped cavity and contents, which was substantially the same as 21 except that no metal container was used, was then hot-pressed, i.e. it was pushed into a graphite mold of the same diameter size as the steel die, as shown in Figure 5, and placed within an induction heater. The interior of the cavity was evacuated and a nitrogen atmosphere introduced therein by evacuating the heater to about 10 torr before back filling it with flowing dry nitrogen. A pressure of ` 30 about 5000 psi was applied to the pressed assembly and maintained thereon by the graphite die, which was then heated by the induction heater at a rate which reached the given maximum hot-pressing temperature in sbout 5 to 7 .~

RD-1033~/103315 minutes. As the assembly was heated3 the pressure increased to the given maximum hot-pressure due to the expansion of the entire system.
At the given temperature at which infiltration begins or proceeds the piston and the pressure dropped to about 5000 psi indicating that the given alloy had melted and become fluid and had infiltrated through the diamond mass.
The pressure was then raised back to the given maximum hot-pressing pressure where it was maintained at the given maximum hot-pressing temperature for one minute to insure complete infiltration by the alloy o~ the smaller capillar-ies of the compressed diamond mass. The power supply was then turned off but no additional pressure was applied.
This provided a firm pressure at high -temperature but reduced pressure at lower temperature providing ade~uate geometric stability. At room temperature, the resulting polycrystalline diamond body was recovered. The plug did not bond to the diamond body. After removing surface scales of hexagonal boron nitride powder and excess alloy by grinding and grit blasting the resulting integral poly-crystalline diamond body had the shape of a disc with the given thickness.
In Table II the hot-pressing temperature at which infiltration begins is that temperature at which the alloy is fluid and proceeds to infiltrate through the compressed diamond mass. The given maximum hot-pressing temperature and maximum hot-pressing pressure were maintained simulta-neously for one minute to insure complete infiltration of the smaller capillaries of the compressed diamond crystal mass.

RI3-to334/lû335 TABLE II

g ¦ Atol~ic 11 . ~=51 ~prox.(ln) Dl=nd od~r ¦~ ¦ r Plu~
silicou ~ I iJ~ bout j I Ho cup /lth Hun;dP-I I ~allcr than I I co~er _ . I l l 16 Csi;icon 1 142 1 .03D S3~-62,q, ~ l 2r li~nr nltrid~
l I ~ '~ __ 17 as A/o 51 1 260 1 .040 S~o a 1290 1 .063 Zr-lLnor pro~aod 15 A/o Cr ~ ~ Ex. ~ I nit~ido . _ I I I _~ , _ 18 ô6 A/o 51 1 210 1 .040 l l llono 1 __ ~ I ~
19 06 A/o Si 1 133 ! ~tO30 S~o ao ! 227 ! ?lo cup wlth pro ord l l l l nltrido _ I I l l

5 A/o Re 1 121 ¦ 60u. wh r~ Mo cu~p ~llth h~POil8ic d I and 30~1/o ! ! nitrid~
Ip,-~5,~ 1 1 ~ ~ - _ ! ! " , RD-10334/10~35 TABLE II (Continued) ~1 lltlo8 YolDt Pre~Rlng ~t Pr~ ln& T~ rlltln3 Alloy Yolycry~t~llln- Dl~d ~1~
Pr~ uro Inflltrlltlonl~ls~ In Lltora- Ap ro~ r~ Ancl~ of ~y~l (C~ Tc IP.& turo C ool ~cb~ I Dla oDd 3Ody 15 ,0.OOO 1350 1 1500 ~Sl-9c6~ o ~r ! di~, 81C ~nd _ I _ T
1613 000 "~300 11525 1360 .060 . l ~51-9.6A/o Zr t~ctlc) _ _ I
17Il,ooo 1260 11450 1335 .055 l (SlCr blm~ry~
I _ _ __ __ 1813,000 1345 11540 1330 .060 1 <of cruo~ ody) l ~ T1512 l 1~
_ _ r -- 19 13.000 1322 1 1525 1330 050 1 ~ I_ _ ~
20 13.000 1340 !1540 ~prl2i5ctod~ .045 1 l ll ll _ l I __~

R~-10 34/10335 Examples 16, 17, 19 and 20 illustrate the produc-tion of the present composite. ~n these examples, on optical examination, each composite appeared ~o be a continuous structure, bu~ the boundary between the diamond body and substrate could be detected by the difference in grain size as well as the difference in color between the diamond body and substrate, i.e. the silicon ni-tride substrate being darker in color than the grey diamond body.
The external surface of each adhered polycrystalline diamond body appeared to be well-infiltrated with ~onding medium which appeared to be uniformly distributed. The diamonds appeared to be well-bonded to each other.
The adhe~ed polycrystalline diamond body o the compos-ites of Examples 17 and 18 had a diamond densit~ higher than 7Q/O by volume but less than 90~ by volume of the volume of the polycrystalline body.
The diamond face of the composite of Example 16 was polished and optical examination of the polished face showed no strings of holes formed from diamond fragment pullout illustrating the strong bonding therein. The density of the diamond crystals was about 71% by Yolume of the adhered polycrystalline diamond body of Example 16.
In ~xample 18, the polycrystalline diamond body was a well-infiltrated~ well-bonded hard disc. The diamond body was fractured substantially in hal-f. Optical examination of the fractured cross-sectional surfaces showed them to be pore-free, that the bonding medium was uniformly distributed throughout the body, and that the fracture was transgranular rather than intergranular, i.e. it had fractured through the diamond grains rather than along the grain boundaries. This indicates that the bonding medium was highly adherent and was as strong as the diamond grains or crystals themselves.
A fractured surface of the disc of Example 18 was polished and examination of the polished surface showed no RD-1033l~/1033~
strings of holes formed from diamond fragment pullout illustrating the strong bonding therein. In Example 18 the density of the diamond crystals was about 80% by volume of the polycrystalline diamond body.
EXAMP~E 21 The composite produced in Example l7 was evaluated as a cutting tool. The exposed surface of the polycrystalline diamond body of the composite was ground with a diamond grinding wheel to smooth it out and produce a sharp cutting edge. The substrate of the composite was then clamped in a tool holder.
A portion of the cutting edge was evaluated on a lathe turning of Jackfork Sandstone with a feed per revolution of .005 inch and a depth of cut of .020 inch.
At a cutting speed of 9~ surface feet per minute, the wear rate was determined to be .22 cubic inch per minute X 10 6. Another portion of the cutting edge was evaluated at a cutting speed of 260 surface feet per minute and was found to have a wear of .501 cubic inch per minute X 10 6.
The composite was removed from the tool holder and examination of the interface between the diamond body and substrate showed that it had not been affected by these machining tests.

The procedure used in this example was the same as that set forth in Example 21 except that the composite produced in Example 19 was used.
A portion of the cutting edge at a cutting speed of 100 surface feet per minute after two minutes of cutting time generated very small wear scar indicating excellent wear resistance, but the Jackfork Sandstone had a deep recess and since the composite was brittle, a small piece of the cutt-ing edge broke.

Examination of the composite after the cutting showed that the interface between the polycrystalline diamond body and silicon nitride substrate was not affected by these cutting tests.

The composite produced in Example 20 was fractured sub-stantially in half, and the fractured cross-sectional surfaces were exa~ined optically. Examination of the fractured surfaces showed that the polycrystalline diamond body as well as the interface of the composite were pore-free, that the bonding medium was distributed uniformly throughout the diamond body -and that the fracture was transgranular rather than intergranular, i.e. that the fracture occurred through the diamond grains rather than along the grain boundaries. This indicates that the bonding medium was highly adherent and was as strong as the diamond grains or crystals themselves. Also, no ~isible inter-layer or defects at the interface between the silicon nitride substrate and the adhered polycrystalline diamond layer could be detected. The fractured surface of the composite appeared to have a continuous structure. However, the difference in grain size between the diamonds and the strongly adhered substrate as well as the darker color of the substrate, enabled recogni-tion of the boundary between the substrate and adhered polycrystal-line diamond body.
The fractured cross-section of the composite was polished.
Optical examination of the polished cross-sectional surface, as in Example 14, showed no strings of holes formed from diamond fragment pullout illustrating the strong bonding therein. A micro-pho-tograph of the surface revealed this to be almost identical to that illustrated in Figure 7, and the body-substrate interface was distinguished by the difference in crystal structure and RD-1033~/10335 color between the diamond body and the substrate. The density of the diamond crystals was about 75% by volume of the polycrystalline diamond body.

The composite produced in Examples 16, 17 and 19 were fractured substantially in half, and the fractured cross-sectional surfaces were examined optically. Examination of the fractured surfaces showed that the polycrystalline diamond body as well as the interface of each compositè were pore-free, that the bonding medium was distributed uniformly throughout the diamond body and that the fractures were transgranular rather than intergranular, i.e. the fractures occurred through the diamond grains rather than along grain boundaries. This indicated that the bonding medium was highly adherent and was as strong as the diamond grains or crystals themselves. Also, no visible interlayer or defects at the interface between the silicon nitride substrate and the adhered polycrystalline diamond layer could be detected.
The fractured surface of each composite appeared to have a continuous structure. However, the difference in grain si~e between the diamonds and the strongly adhered substrate as well as the darker color of the substrate enabled recogni-tion of the boundary between the substrate and adhered poly-crystalline diamond body.
The fracture cross-section of the composite of Example l9 was polished. Examination of the polished cross-sectional surface showed no strings of holes formed from diamond fragment pullout illustrating the strong bonding therein.
A photomicrograph taken of the polished surface magnified 690 X indicated an interlayer of bonding medium through the interface. A scanning of electron micrograph of the polished surface magnified 1000 X showed an interlayer of bonding medium through the interface which had a maximum thickness of about 3 microns.
.

`\

X-ray spectral analysis of the bonding medium in the interlayer and in the polycrystalline diamond body sho~ed that the components in each were the same.

Claims (17)

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:
1. A process for preparing an integral composite of a polycrystalline diamond body and silicon carbide or silicon nitride substrate at pressures substantially below those required by the diamond stable region which includes a hot-pressing step and which comprises:
(a) placing within a protective container or cup a mass of solid eutectiferous silicon-rich alloy or solid components for providing eutectiferous silicon-rich alloy, a mass of diamond crystals and a silicon carbide or silicon nitride substrate, said mass of diamond crystals being intermediate and in contact with said substrate and said mass of solid eutectiferous silicon-rich alloy, or with at least one of said components for providing eutectiferous silicon-rich alloy, said eutecti-ferous silicon-rich alloy being composed of silicon and a metal which forms a silicide with said silicon and which is selected from the group consisting of cobalt chromium, iron, hafnium, manganese, molybdenum, nickel, palladium, platinum, rhenium, rhodium, ruthenium, tantalum, thorium, titanium, uranium, vanadium, tungsten, yttrium, zirconium, and alloys thereof, said substrate consisting essentially of a hot-pressed or sintered polycrystalline silicon carbide or silicon nitride body;
(b) disposing said container and its contents within a pressure transmitting powder medium that trans-mits applied pressure substantially undiminished and.
remains substantially unsintered during said hot-pressing;
(c) applying sufficient substantially isostatic pressure to said container and its contents via said powder medium to substantially stabilize the dimensions of said container and said contents substantially uni-formly producing a shaped substantially isostatic system of powder-enveloped container, wherein the density of the
1. Claim 1 Cont'd. - 58 -resulting compressed mass of diamond crystals is higher than 70% by volume of the volume of said compressed diamond crystals;
   (d) hot-pressing the resulting substantially isostatic system producing fluid infiltrating eutectiferous silicon-rich alloy and infiltrating said fluid eutectiferous silicon-rich alloy through the interstices of said compressed mass of diamond crystals and into contact with the contacting surface of said substrate which forms an interface with said compressed mass of crystals, said hot-pressing being carried out at a hot-pressing temperature below 1600°C
   under a hot-pressing pressure sufficient to infiltrate said fluid silicon-rich alloy throughout the interstices of said compressed mass of diamond crystals, said solid eutectiferous silicon-rich alloy or said solid components for providing eutectiferous silicon-rich alloy being used in an amount sufficient to produce sufficient fluid eutectiferous silicon-rich alloy at said hot-pressing temperature to fill the interstices of said compressed mass of diamond crystals and contact the contacting surface of said substrate and fill the pores through the interface so that it is at least substantially pore-free, said hot-pressing being carried out in an atmosphere which has no significant deleterious effect on said diamond crystals or said infiltrating fluid silicon-rich alloy or said substrate, said hot-pressing converting less than 5% by volume of said diamond crystals to non-diamond elemental carbon, said infiltrating silicon-rich alloy encapsulating the surfaces of the compressed diamond crystals and reacting with the diamond surfaces or non-diamond elemental carbon and producing a carbide which at least in major amount is silicon carbide;
   (e) maintaining sufficient pressure on the resulting hot-pressed substantially isostatic system during cooling thereof to at least substantially maintain the dimensions of said hot-pressed system; and (f) recovering the resulting composite of poly-crystalline diamond body bonded to silicon carbide or silicon nitride substrate wherein the diamond crystals are present in an amount from at least 70% by volume up to about but less than 95% by volume of said polycrystalline diamond body, said diamond body being at least substantially pore-free and being free of elemental non-diamond carbon phase in that it does not contain non-diamond elemental carbon phase in an amount detectable by x-ray diffraction analysis.
2. 2. The process of claim 1, wherein said diamond crystals are size-graded ranging from about 1 micron to about 60 microns.
3. 3. The process of claim 1, wherein the amount of fluid infiltrating silicon-rich alloy ranges from about 25% by volume to about 80% by volume of said compressed mass of diamond crystals.
4. 4. The process of claim 1, 2 or 3, wherein the density of said compressed mass of diamond crystals ranges from about 71% by volume to about 90% by volume of the volume of compressed crystals.
5. 5. The process of claim 1, 2 or 3, wherein said mass of solid silicon-rich alloy is in particulate form.
   6. A process for preparing an integral composite of a polycrystalline diamond body and silicon carbide or silicon nitride substrate at pressures substantially below those required by the diamond stable region which includes a hot-pressing step and which comprises:
   (a) pressing a cavity in a pressure transmitting powder medium that transmits applied pressure substantially undiminished and remains substantially unsintered during said hot-pressing;
   (b) placing within said cavity a mass of solid eutectiferous silicon-rich alloy or solid components for providing eutectiferous silicon-rich alloy, a mass of Claim 6 continued:
   diamond crystals and a silicon carbide or silicon nitride substrate, said mass of diamond crystals being inter-mediate and in contact with said substrate and said mass of solid eutectiferous silicon-rich alloy, or with at least one of said components for providing eutectiferous silicon-rich alloy, said eutectiferous silicon-rich alloy being composed of silicon and a metal which forms a silicide with said silicon and which is selected from the group consisting of cobalt, chromium, iron, hafnium, manganese, molybdenum, nickel, palladium, platinum, rhenium, rhodium, ruthenium, tantalum, thorium, titanium, uranium, vanadium, tantalum, thorium, titanium, uranium, vanadium, tungsten, yttrium, zirconium, and alloys thereof, said substrate consisting essentially of a hot-pressed or sintered polycrystalline silicon carbide or silicon nitride body;
   (c) covering said cavity and its contents with an additional amount of said pressure transmitting powder medium thereby enveloping said cavity with said pressure transmitting powder medium;
   (d) applying sufficient substantially isostatic pressure to said cavity and its contents via said powder medium to substantially stabilize the dimensions of said cavity and its contents substantially uniformly producing a shaped substantially isostatic system of powder-enveloped cavity, wherein the density of the result-ing compressed mass of diamond crystals is higher than 70% by volume of the volume of said compressed diamond crystals;
   (e) hot-pressing the resulting substantially isostatic system producing fluid infiltrating eutecti-ferous silicon-rich alloy and infiltrating said fluid eutec-tiferous silicon-rich alloy through the interstices of said compressed mass of diamond crystals and into contact with the contacting surface of said substrate which forms an interface with said compressed mass of crystals, said hot-pressing being carried out at a hot-
6. Claim 6 continued:
   pressing temperature below 1600°C under a hot-pressing pressure sufficient to infiltrate said fluid silicon-rich alloy throughout the interstices of said compressed mass of diamond crystals, said solid eutectiferous silicon-rich alloy or said solid components for providing eutecti-ferous silicon-rich alloy being used in an amount sufficient to produce sufficient fluid eutectiferous silicon-rich alloy at said hot-pressing temperature to fill the inter-stices of said compressed mass of diamond crystals and contact the contacting surface of said substrate and fill the pores through the interface so that it is at least substantially pore-free, said hot-pressing being carried out in an atmosphere which has no significant deleterious effect on said diamond crystals or said infiltrating fluid silicon-rich alloy or said substrate, said hot-pressing converting less than 5% by volume of said diamond crystals to non-diamond elemental carbon, said infiltrating silicon-rich alloy encapsulating the surfaces of the compressed diamond crystals and reacting with the diamond surfaces or non-diamond elemental carbon and producing a carbide which at least in major amount is silicon carbide;
   (f) maintaining sufficient pressure on the resulting hot-pressed substantially isostatic system during cooling thereof to at least substantially maintain the dimensions of said hot-pressed system; and (g) recovering the resulting composite of poly-crystal line diamond body bonded to silicon carbide or silicon nitride substrate wherein the diamond crystals are present in an amount from at least 70% by volume up to but less than 95% by volume of said polycrystalline diamond body, said diamond body being at least substantially pore-free and being free of elemental non-diamond carbon phase in that it does not contain non-diamond elemental carbon phase in an amount detectable by X-ray diffraction analysis.
7. 7. The process of claim 6, wherein said mass of solid silicon-rich alloy is in particulate form.
8. 8. A composite consisting essentially of a polycrystalline diamond body integrally bonded to a substrate of polycrystalline silicon carbide or silicon nitride, said polycrystalline diamond body consisting essentially of a mass of diamond crystals adherently bonded together by a bonding medium consisting essentially of silicon carbide and a carbide and/or silicide of a metal component which forms a silicide with silicon, said metal component of said metal silicide being selected from the group consisting of cobalt, chromium, iron, hafnium, manganese, molybdenum, nickel, palladium, platinum, rhenium, rhodium, ruthenium, tantalum, thorium, titanium, uranium, vanadium, tungsten, yttrium, zirconium, and alloys thereof, said metal component of said metal carbide being selected from the group consisting of chromium, hafnium, titanium, zirconium, tantalum, vanadium, tungsten, molybdenum, and alloys thereof, said diamond crystals ranging in size from about 1 micron to about 1000 microns, the density of said diamond crystals ranging from at least about 70% by volume up to about but less than 95% by volume of said body, said bonding medium being present in an amount ranging up to about 30% by volume of said body, said bonding medium being distributed substantially uniformly throughout said body, the portion of said bonding medium in contact with the surfaces of said diamond crystals being at least in a major amount silicon carbide, said diamond body being substantially pore-free, said substrate consisting essentially of a hot-pressed or sintered polycrystalline silicon carbide or silicon nitride body ranging in density from about 85% to about 100% of the theoretical density of silicon carbide or silicon nitride and containing silicon carbide or silicon nitride in an amount of at least 90% by weight of said substrate and being free of constituents which have a significantly deleterious effect on the mechanical properties of said composite, said polycrystalline diamond body forming an interface with said substrate wherein said bonding medium extends from said polycrystalline diamond body into contact with said substrate at least substantially filling any pores throughout said interface so that said interface is substantially pore-free.
9. 9. The composite of claim 8, wherein said bonding medium contains elemental silicon.
10. 10. The composite of claim 8, wherein the density of said diamond crystals ranges from about 70% by volume to about 89% by volume of said body.
11. 11. The composite of claim 8, 9 or 10, wherein said diamond crystals are size-graded ranging from about 1 micron to about 60 microns.
12. 12. The composite of claim 8, wherein said bonding medium is comprised of silicon carbide and said metal silicide.
13. 13. The composite of claim 12,wherein said bonding medium contains elemental silicon.
14. 14. The composite of claim 8, wherein said bonding medium is comprised of silicon carbide and said metal carbide.
15. 15. The composite of claim 14, wherein said bonding medium contains elemental silicon.
16. 16. The composite of claim 8, wherein said bonding medium is comprised of silicon carbide and said metal carbide and said metal silicide.
17. 17. The composite of claim 16, wherein said bonding medium contains elemental silicon.