US20080248305A1

US20080248305A1 - Superabrasive Particle Synthesis with Controlled Placement of Crystalline Seeds

Info

Publication number: US20080248305A1
Application number: US12/059,422
Authority: US
Inventors: Chien-Min Sung
Original assignee: Individual
Current assignee: Individual
Priority date: 1997-04-04
Filing date: 2008-03-31
Publication date: 2008-10-09
Also published as: US20080047484A1; US20060016127A1; US7368013B2

Abstract

An improved method for synthesizing superabrasive particles provides high quality industrial superabrasive particles with high yield and a narrow size distribution. The synthesis method can include forming a growth precursor of a substantially homogeneous mixture of raw material and catalyst material or layers of raw material and metal catalyst. The growth precursor can have a layer of adhesive over at least a portion thereof. A plurality of crystalline seeds can be placed in a predetermined pattern on the layer of adhesive. The growth precursor can be maintained at a temperature and pressure at which the superabrasive crystal is thermodynamically stable for a time sufficient for a desired degree of growth. Advantageously, the patterned placement of crystalline seeds and disclosed processes allow for production of various morphologies of synthetic diamonds, including octahedral and cubic diamonds, and improved growth conditions generally. As a result, the grown superabrasive particles typically have a high yield of high quality particles and a narrow distribution of particle sizes.

Description

RELATED APPLICATIONS

This application is a divisional of U.S. patent application Ser. No. 11/175,017, filed Jul. 5, 2005, which is a continuation-in-part of U.S. patent application Ser. No. 10/926,576, filed Aug. 25, 2004, which is a continuation-in-part of U.S. patent application Ser. No. 10/791,300, filed Mar. 1, 2004, which is a continuation-in-part of U.S. patent application Ser. No. 10/259,168, filed Sep. 27, 2002, which is a continuation-in-part of U.S. patent application Ser. No. 09/935,204, filed Aug. 22, 2001, now issued as U.S. Pat. No. 6,679,243, which is a continuation-in-part of U.S. patent application Ser. No. 09/399,573, filed Sep. 20, 1999, now issued as U.S. Pat. No. 6,286,498, which is a continuation-in-part application of U.S. patent application Ser. No. 08/835,117, filed Apr. 4, 1997, now issued as U.S. Pat. No. 6,039,641, and of U.S. patent application Ser. No. 08/832,852, filed Apr. 4, 1997, now abandoned, all of which are incorporated herein by reference.

FIELD OF THE INVENTION

The present invention relates generally to methods of synthesizing superabrasive particles. Accordingly, the present invention involves the fields of chemistry, metallurgy, and materials science.

BACKGROUND OF THE INVENTION

Diamond and cubic boron nitride (cBN) particles have found widespread use as superabrasives in a variety of abrading and cutting applications. The worldwide consumption of diamond particles currently exceeds 400 metric tons. Common tools which incorporate superabrasive particles include cutting tools, drill bits, circular saws, grinding wheels, lapping belts, polishing pads, and the like. In general, diamond grits can be classified into three distinct size ranges: coarse mesh saw grits (U.S. mesh 18 to 60 or 1 mm to 0.23 mm) for sawing applications, medium sized grinding grits (U.S. mesh 60 to 400, 230 microns to 37 microns) for grinding applications, and fine powder of micron diamond (U.S. mesh <400 mesh) for polishing applications.
Among diamond superabrasives, saw diamond has the largest particle size at about 18 to 60 mesh. High quality saw diamonds are generally euhedral having fully grown crystallographic faces. Further, high quality saw diamond should have very few defects or inclusions. Standard applications for saw diamonds require high quality diamonds. This is at least partially due to the high impact force encountered during cutting, particularly at high speeds. In contrast, smaller diamond particles, i.e. 60 to 400 mesh or 0.25 mm to 37 μm, such as those used in grinding wheels, create scratches in the surface which gradually removes material from a workpiece. In such grinding applications, the impact force is typically much less than for cutting applications. Thus, commercially satisfactory smaller diamonds can be produced with less concern for flaws and impurities than is generally acceptable for larger diamonds such as saw diamonds.
Superabrasives are typically formed under ultrahigh pressure, e.g., about 5.5 GPa and high temperature, e.g., 1300° C. The quality of diamond grits is typically controlled by the growth rate. A slower growth rate can allow for more complete formation of the crystal morphology and a lower amount of interior defects. High quality, well-crystallized diamond grits will exhibit higher impact strength suitable for more aggressive sawing action. The amount of defects (e.g. metal inclusion) will also affect the thermal stability of the diamond grit. A less included diamond can withstand a higher processing temperature (e.g. 1000° C.) typically used for making diamond tools without deterioration. Diamonds having a lower amount of inclusions can also wear slower at the cutting tips where heat is generated.
Diamond grits are typically grown by converting graphite to diamond under catalytic action of a molten metal. The molten metal also serves as a solvent of carbon. Typical catalysts used to synthesis diamond include iron, nickel, cobalt, manganese or their alloys. The growth rate of diamond is controlled by pressure and temperature. Typically, the lower the over-pressure required to make diamond stable and/or the lower the over-temperature needed to melt the catalyst metal, the slower the growth rate. For example, to grow saw grits in a molten alloy of iron and nickel of Invar composition (Fe65-Ni35), the pressure is about 5.2 GPa and temperature is about 1270° C.
Once the growth rate is determined for synthesizing a certain quality of grade of diamond, its size can be determined by the growth time. Because the saw grits are much larger than grinding grits, they require much longer growth time. For example, the growth of 30/40 mesh may require 45 minutes; and 40/50 mesh, 25 minutes. In contrast, the growth of 100/120 mesh may need 2 minutes; and 200/230, 1 minute. Micron diamond is typically produced by pulverizing larger diamond, particularly, larger diamonds with a large amount of defects.
As the time for diamond growth increases, the more difficult it is to control pressure and temperature. However, under ultrahigh pressure conditions during crystal growth, the pressure tends to continually decay due to the volume contraction associated with diamond formation. Further, temperatures within the growth regions can increase due to increases in electrical resistance associated with the diamond formation. Hence, it is very difficult to maintain optimal conditions of pressure and temperature for homogeneous growth of diamond grits. Saw diamond grits are typically grown under ultrahigh pressure over a much longer time, e.g., 40 minutes than that required to grow smaller grinding grits, e.g., about 1 minute. Consequently, saw diamond grits are very difficult to grow, particularly those having high quality. Saw grits with high impact strength are characterized by a euhedral crystal shape and very low inclusions of either metal or graphite. Hence, very tight controls of pressure and temperature are required over extended periods of time to produce high quality diamonds.
These difficulties partially account for the abundance of companies which can grow saw grits, while very few companies are capable of growing high grade saw grits having larger sizes. As a result, very few companies can master the technology of growing coarse saw grits, in particular, those with high quality, high impact strength, and high thermal stability.
Typical methods for synthesizing larger high quality diamonds involve ensuring uniformity of raw materials such as graphite and metal catalyst and carefully controlling process temperature and pressures. High pressure high temperature (HPHT) processes used in diamond growth can employ reaction volumes of over 200 cm³. Most often, the graphite to diamond conversion in the reaction volume can be up to about 30%. Unfortunately, typical processes also result in the crystals having external flaws, e.g., rough surfaces, and undesirable inclusions, e.g., metal and carbon inclusions. Therefore, increased costs are incurred in segregating acceptable high strength diamonds from weaker, poor quality diamonds.
One major factor to consider in diamond synthesis of high grade saw diamonds is providing conditions such that nucleation of diamond occurs uniformly and nearly simultaneously. Random nucleation methods typically allow some regions of raw materials to be wasted while other regions are densely packed with diamond crystals having a high percentage of defects. Some diamond synthesis methods have improved nucleation uniformity somewhat; however, during diamond growth local changes in pressure can occur. If heating is accomplished by passing electrical current directly through the reaction cell, then diamond growth can also interfere with the electrical current used to control heating. The results of such interference are non-uniformities and fluctuations in the temperature and pressure gradients across the reaction cell and thus a wide distribution of crystal sizes, crystal shapes, and inclusion levels. Despite these difficulties, by providing highly homogeneous starting materials and carefully controlling process conditions, the volume efficiency of the reaction cell is still typically less than 2 to 3 carats per cubic centimeter. This marginal yield still wastes large amounts of raw materials, reduces production efficiencies, and leaves considerable room for improvement.
Other methods for synthesizing large industrial diamond particles include forming layers of solid disks of graphite and/or catalyst. Diamond nucleation then occurs at the interface between graphite and catalyst layers. However, such materials are intrinsically heterogeneous. For example, the firing temperature for graphite rods that are cut into disks can vary from region to region, thus affecting the microstructure and composition of the disk. Further, during mechanical formation of graphite into a rod, the graphite microstructure can change, e.g., the outer regions exhibit a skin effect during extrusion. As a result, graphite disks tend to have regions which vary in porosity, degree of graphitization, ash content, and the like. Similarly, catalyst disks have varying alloy composition as metal atoms and crystal structure tend to segregate during cooling. Additionally, during extrusion and mechanical forming processes the alloy composition in various regions changes even further. As a result, local concentrations and properties of graphite and catalyst metals can vary by several percent across solid disks. Diamonds grown under such conditions tend to nucleate at different times and experience varying growth rates, thus producing diamonds having a wide size distribution and increasing the number of flawed diamonds due to intergrowth, overgrowth, i.e. fast growth rates, and uneven growth, i.e. asymmetric growth, as shown in FIGS. 19A, 19B, and 22.
Recently, efforts have been made in using powdered materials to further increase yields of industrial diamond particles. These methods attempt to uniformly mix graphite and catalyst powders to achieve improved diamond nucleation. However, diamond nucleation still occurs randomly, i.e. broad size distribution, but somewhat uniformly throughout the powder under HPHT conditions, as shown in FIG. 23. Such methods have met with some success and have resulted in improved yields of up to 3 carat/cm³. Further, yields of high quality diamond of specific sizes have also improved up to five times over those achievable using conventional layered disk methods. However, powdered mixture methods can be difficult to control. For example, the density of graphite and metal catalyst materials differ significantly, making uniform mixing very difficult. In addition, powdered mixture methods generally require even more strict control of process conditions than in layered methods.
Therefore, methods which further increase the quality and yields of large diamond particles suitable for commercial use continue to be sought through research and development.

SUMMARY OF THE INVENTION

It has been recognized by the inventor that it would be advantageous to develop a method for synthesizing superabrasive particles which provides high quality industrial superabrasive particles with a high yield and narrow size distribution.
In one aspect, the present invention resolves the problems set forth above by providing a method for synthesizing superabrasive particles. The above method can include forming at least a portion of a growth precursor. The growth precursor can include a raw material and a particulate catalyst material. Crystalline seeds can be arranged in a predetermined pattern on a layer of adhesive. The layer of adhesive can coat at least a portion of the growth precursor. In some embodiments, the growth precursor can be a substantially homogenous mixture of particulate raw material and particulate catalyst material. Alternatively, the growth precursor can comprise layers of raw material and catalyst material.
The layer of adhesive can be coated over the growth precursor by any number of methods such as, but not limited to, spraying, film coating, spin coating, and the like.
The method of the present invention can be applied to formation of superabrasives such as diamond and cubic boron nitride (cBN). In either case, the crystalline seed can be diamond seed, cBN seed, SiC seed, or combinations thereof.
Suitable catalyst materials for diamond synthesis can include carbon solvents such as Fe, Ni, Co, Mn, Cr, and alloys thereof. Alloys of iron and nickel have proven useful in connection with the present invention and are readily commercially available. Catalyst materials suitable for cBN synthesis can include alkali, alkali earth metal, and compounds thereof.
The composition of the raw material can depend on the type of superabrasive being synthesized. Diamond synthesis typically involves using a carbon source. In another detailed aspect of the present invention, the carbon source can be primarily graphite. Further, in accordance with the present invention, the degree of graphitization can preferably be greater than 0.50. The carbon source can be formed as a particulate layer or as a solid plate of graphite. Similarly, the raw material suitable for cBN synthesis can be a hexagonal boron nitride source.
In another aspect of the present invention, the growth precursor can include a plurality of alternating raw material and catalyst layers. Depending on the reaction volume of the HPHT apparatus used, the number of layers can vary from a single layer to thirty layers or more. In yet another detailed aspect, the growth precursor can include a plurality of particulate catalyst layers each having a plurality of crystalline seeds placed in a predetermined pattern. These predetermined patterns can involve crystalline seeds of different sizes or type. Further, the predetermined pattern can involve crystalline seed placement within each layer and specific patterns with respect to patterns of crystalline seeds among layers, which patterns can differ from layer to layer.
Appropriate growth conditions can be maintained using any number of known HPHT apparatuses such as, but not limited to, belt apparatus, cubic press, toroidal apparatus, sliding anvils, split sphere, split die, and the like. Using such devices, the growth precursor can be maintained at a temperature and pressure at which diamond or cBN is thermodynamically stable for a time sufficient for growth of the superabrasive. Advantageously, placing the crystalline seeds at least partially in a particulate catalyst layer provides highly uniform growth conditions which are less demanding than is required in typical synthesis processes. Thus, the placement of crystalline seeds in a predetermined pattern helps to improve uniformity of crystal growth, nucleation times, and reduces intergrowth of crystals and non-growing regions, while providing a particulate catalyst layer aids in increasing uniformity of crystalline growth with few defects.
In accordance with yet another aspect of the present invention, the crystalline seeds can be placed in a predetermined pattern using any number of methods. One method involves placing a template having a pattern of apertures upon the adhesive layer. Each of the apertures can be configured to receive a single crystalline seed. The apertures can then be filled with the crystalline seeds. Optionally, the crystalline seeds can then be pressed at least partially into the growth precursor.
In an alternative embodiment, a transfer sheet can be used to place the crystalline seeds in a predetermined pattern on the adhesive layer. In still another alternative embodiment, a vacuum chuck can be used to orient and place the crystalline seeds in the predetermined pattern. The adhesive layer can preferably be an organic binder which minimizes shifting or movement of the crystalline seeds during subsequent manipulation of the growth precursor. Such a method can reduce disruption of the predetermined pattern when the template is removed, when pressure is applied to the crystalline seeds, and/or when the growth precursor is moved during processing, e.g. oriented adhesive side down.
In accordance with yet another aspect of the invention, the crystalline seeds can be grown having various morphologies. Diamond growth can be controlled by preferentially growing diamond to existing crystal faces through careful temperature control under pressure, resulting in various morphologies including octahedral and cubic.
The grown superabrasives of the present invention have a high yield of high quality diamond particles and a narrow distribution of diamond sizes. Typically, yields of diamond particles can range from about 30% to about 80% conversion of carbon to diamond can be expected. Further, the percent of high quality diamond can range from 50% to about 90% of the total yield. As a further example of the effectiveness of the present invention, the grown diamonds of the present invention can have a narrow size distribution with a standard deviation less than half of conventional methods described above. Also, the grown diamonds of the present invention can have significantly fewer inclusions.
There has thus been outlined, rather broadly, various features of the invention so that the detailed description thereof that follows may be better understood, and so that the present contribution to the art may be better appreciated. Other features of the present invention will become more clear from the following detailed description of the invention, taken with the accompanying claims, or may be learned by the practice of the invention.
Additional features and advantages of the invention will be apparent from the detailed description which follows, taken in conjunction with the accompanying drawings, which together illustrate, by way of example, features of the invention.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a side view of a raw material layer and particulate catalyst layer having a template thereon in accordance with an embodiment of the present invention;

FIG. 2A is a top view of a template in accordance with an embodiment of the present invention;

FIG. 2B is a top view of a template in accordance with another embodiment of the present invention;

FIG. 3 is a side view of the assembly of FIG. 1 having crystalline seeds placed in a predetermined pattern in accordance with an embodiment of the present invention;

FIG. 4 is a side view of pressing the crystalline seeds into the catalyst layer in accordance with an embodiment of the present invention;

FIG. 5 is a side view of a growth precursor in accordance with an embodiment of the present invention;

FIG. 6 is a side view of a multi-layered growth precursor in accordance with an embodiment of the present invention;

FIG. 7 is a side view of a multi-layered growth precursor in accordance with an alternative embodiment of the present invention;

FIGS. 8A and 8B are photomicrographs of nickel coated diamond seeds for use in one embodiment of the present invention;

FIG. 9A is a perspective view of a single octahedral (111) face of diamond;

FIG. 9B is a perspective view of a single carbon atom having a single unbonded electron;

FIG. 9C is a perspective view of a puckered graphitic plane;

FIG. 10A is a perspective view of graphitic planes;

FIG. 10B is a perspective view of diamond-like carbon formed from the graphitic planes of FIG. 10A;

FIG. 10C is a perspective view of diamond formed from the diamond-like carbon of FIG. 10B;

FIG. 11A is a perspective view of a single cubic (100) face of diamond;

FIG. 11B is a perspective view of a single carbon atom having two unbonded electrons;

FIG. 11C is a perspective view of diamond grown along the cubic face;

FIG. 12A is a side cross-sectional view of a growing diamond having a continuous catalyst envelope in accordance with one embodiment of the present invention;

FIG. 12B is an expanded side cross-sectional view of feature 36 showing a growing cubic face of diamond in accordance with one embodiment of the present invention;

FIG. 12C is an expanded side cross-sectional view of feature 38 showing a growing octahedral face of diamond in accordance with one embodiment of the present invention;

FIG. 13A is a side cross-sectional view of a growing diamond dominated by growth on the octahedral faces to form a more cubic diamond in accordance with one embodiment of the present invention;

FIG. 13B is a side cross-sectional view of a growing diamond dominated by growth on the cubic faces to form a more octahedral diamond in accordance with one embodiment of the present invention;

FIG. 14 is a series of crystal morphologies of diamond and corresponding growth parameters;

FIG. 15 is a photomicrograph of a number of cubo-octahedral diamonds;

FIG. 16 is a graph illustrating a number of growth considerations and effects in using the methods of the present invention;

FIG. 17 shows a side view of a portion of a multi-layered assembly such as shown in FIG. 6 after HPHT processing and identifying various aspects of crystalline growth in accordance with an embodiment of the present invention;

FIG. 18 is a photomicrograph of a grown diamond assembly in accordance with the present invention, which exhibits highly uniform size distribution and uniform crystal shapes.

FIG. 19A is a photomicrograph of a grown diamond assembly in accordance with the prior art, which exhibits non-uniform size distribution and non-uniform crystal shapes;

FIG. 19B is a photomicrograph of unsorted and unsized diamonds recovered from the assembly of FIG. 19A;

FIG. 20A is a photomicrograph of a grown diamond assembly in accordance with one embodiment of the present invention, which exhibits highly uniform size distribution and uniform crystal shapes;

FIG. 20B is a photomicrograph of unsorted and unsized cubo-octahedral diamonds recovered from the assembly of FIG. 20A;

FIG. 21A is a photomicrograph of a grown diamond assembly in accordance with one embodiment of the present invention, which exhibits highly uniform size distribution and uniform crystal shapes;

FIG. 21B is a photomicrograph of unsorted and unsized diamonds recovered from the assembly of FIG. 21A which are predominantly octahedral diamonds;

FIG. 22 is a photomicrograph of a conventional diamond assembly grown from an alternating plate method which highlights the non-uniform size distribution and non-uniform crystal shapes; and

FIG. 23 is a photomicrograph of a diamond assembly grown using known powdered methods which show some improvement over conventional methods, however still suffer from somewhat non-uniform size distributions and non-uniform crystal shapes.

FIG. 24 is a photograph of a post-growth mass having offset patterns of diamond crystals as described in Example 13.

FIG. 25 is a photomicrograph of the post-growth mass of diamond particles having a predominantly cubic morphology and an average size of about 500 μm in accordance with Example 13.

FIG. 26 is an additional photomicrograph of the post-growth mass of FIG. 24 showing cubic diamonds prior to recovery.

FIG. 27 illustrates a collection of unsorted diamonds having a predominantly cubic morphology produced from Example 13.

DETAILED DESCRIPTION

Reference will now be made to the exemplary embodiments illustrated in the drawings, and specific language will be used herein to describe the same. It will nevertheless be understood that no limitation of the scope of the invention is thereby intended. Alterations and further modifications of the inventive features, process steps, and materials illustrated herein, and additional applications of the principles of the inventions as illustrated herein, which would occur to one skilled in the relevant art and having possession of this disclosure, are to be considered within the scope of the invention. It should also be understood that terminology employed herein is used for the purpose of describing particular embodiments only and is not intended to be limiting.

A. DEFINITIONS

In describing and claiming the present invention, the following terminology will be used.
The singular forms “a,” “an,” and “the” include plural referents unless the context clearly dictates otherwise. Thus, for example, reference to “a matrix material” includes reference to one or more of such materials, and reference to “an alloy” includes reference to one or more of such alloys.
As used herein, “particulate” when used with respect to layers indicates that the layer is formed of particulates. Typically, particulate layers of the present invention can be loose powder, packed powder, or compacted powder having substantially no sintered particles. These particulate layers can be porous or semi-porous compacts. Compacted particulate layers can be formed using any known compaction process such as, but not limited to, wet or dry cold compaction such as cold isostatic pressing, die compacting, rolling, injection molding, slip casting, and the like. The particulate materials used in the present invention such as graphite and metal catalyst powders can be preferably handled and stored in an inert environment in order to prevent oxidation and contamination.
As used herein, “substantially free of” or the like refers to the lack of an identified element or agent in a composition. Particularly, elements that are identified as being “substantially free of” are either completely absent from the composition, or are included only in amounts which are small enough so as to have no measurable effect on the composition.
As used herein, “predetermined pattern” refers to a non-random pattern that is identified prior to formation of a precursor, and which individually places or locates each crystalline seed in a defined relationship with the other crystalline seeds. For example, “placing diamond seeds in a predetermined pattern” would refer to positioning individual particles at specific non-random and pre-selected positions. Further, such patterns are not limited to uniform grid or offset honeycomb patterns but may include any number of configurations based on the growth conditions and materials used.
As used herein, “uniform grid pattern” refers to a pattern of diamond particles that are evenly spaced from one another in all directions.
As used herein, “substrate” refers to a solid metal material. While many solid metal materials may be a product of metal particulate sintering or consolidation, it is to be understood, that as used herein, “substrate” does not include powdered or particulate metal materials that have not yet been sintered or consolidated into a solid mass or form.
As used herein, “alloy” refers to a solid or liquid solution of a metal with a second material, said second material may be a non-metal, such as carbon, a metal, or an alloy which enhances or improves the properties of the metal.
As used herein, “crystalline seeds” refer to particles which serve as a starting material for growth of a larger crystalline particle. As used herein, crystalline seeds typically include diamond seeds, cBN seeds, and SiC seeds. For example, growth of superabrasive diamond is commonly achieved using diamond seeds; however cBN and/or SiC seeds can also be used to grow superabrasive diamond. Similarly, cBN can be grown using diamond, cBN, and/or SiC seeds.
As used herein, “diamond seeds” refer to particles of either natural or synthetic diamond, super hard crystalline, or polycrystalline substance, or mixture of substances and include but are not limited to diamond, polycrystalline diamond (PCD). Diamond seeds are used as a starting material for growing larger diamond crystals and help to avoid random nucleation and growth of diamond.
As used herein, “superabrasive particles” refers to particles suitable for use as an abrasive and include diamond and cBN particles.
As used herein, “precursor” refers to an assembly of crystalline seeds, particulate catalyst layer, and a raw material layer. A precursor describes such an assembly prior to the HPHT growth process. Such unsintered precursors are sometimes referred to as a “green body.”
As used herein, “plate” refers to a mass of material which is partially sintered, completely sintered, or non-porous crystalline in structure. This is in distinction to a compact or pressed powder which includes particulates which are substantially unsintered. Plates can typically be circular or disk shaped; however, other shapes which are functional can also be used, e.g., square.
As used herein, “degree of graphitization” refers to the proportion of graphite which has graphene planes having a theoretical spacing of 3.354 angstroms. Thus, a degree of graphitization of 1 indicates that 100% of the graphite has a basal plane separation (d₍₀₀₀₂₎) of graphene planes, i.e. with hexagonal network of carbon atoms, of 3.354 angstroms. A higher degree of graphitization indicates smaller spacing of graphene planes. The degree of graphitization, G, can be calculated using Equation 1.
G=(3.440−d ₍₀₀₀₂₎)/(3.440−3.354) (1)
Conversely, d₍₀₀₀₂₎can be calculated based on G using Equation 2.
d ₍₀₀₀₂₎=3.354+0.086(1−G) (2)
Referring to Equation 1, 3.440 angstroms is the spacing of basal planes for amorphous carbon (L_c=50 Å), while 3.354 angstroms is the spacing of pure graphite (L_c=1000 Å) that may be achievable by sintering graphitizable carbon at 3000° C. for extended periods of time, e.g., 12 hours. A higher degree of graphitization corresponds to larger crystallite sizes, which are characterized by the size of the basal planes (L_a) and size of stacking layers (L_c). Note that the size parameters are inversely related to the spacing of basal planes. Table 1 shows crystallite properties for several common types of graphite.

TABLE 1

Graphite Type	d₍₀₀₂₎	L_a(Å)	L_c(Å)	I₁₁₂/I₁₁₀

Natural	3.355	1250	375	1.3
Low Temp (2800° C.)	3.359	645	227	1.0
Electrode	3.360	509	184	1.0
Spectroscopic	3.362	475	145	0.6
High Temp (3000° C.)	3.368		400	0.9
Low Ash	3.380	601	180	0.8
Poor Natural	3.43	98	44	0.5

As used herein, “aperture” refers to an opening through a template surface which has a predetermined size and shape depending on the intended application. For example, the aperture size may be designed to accommodate a plurality of crystalline seeds of a given mesh size. However, it is most often desirable to design the apertures such that only one crystalline seed is accommodated by each aperture.
As used herein, “inclusion” refers to formation of carbon or metal deposits instead of diamond at the interface between a growth surface of the diamond and the surrounding material. Inclusions are most often formed by the presence of substantial amounts of carbon at the growth surface of the diamond and/or inadequate control of temperature and pressure conditions during HPHT growth. Similar inclusions and defects can also be formed during cBN synthesis.
As used herein, “euhedral” means idiomorphic or a crystal having an unaltered natural shape containing natural crystallographic faces.
As used herein, “octahedral” refers to a crystal morphology wherein crystallographic faces are dominantly the (111) plane. Octahedral diamond crystals typically have eight triangular faces as shown in FIG. 14 (far right) and FIG. 21B (predominantly octahedral diamonds).
As used herein, “upon” refers to either actual physical contact or sufficient proximity to achieve the desired effect. For example, placing a template upon the growth precursor can allow for a small space between the growth precursor and the template such that particle placement in the desired pattern is still realized. Typical process conditions can allow for actual physical contact.
As used herein, a plurality of items, structural elements, compositional elements, and/or materials may be presented in a common list for convenience. However, these lists should be construed as though each member of the list is individually identified as a separate and unique member. Thus, no individual member of such list should be construed as a de facto equivalent of any other member of the same list solely based on their presentation in a common group without indications to the contrary.
Concentrations, amounts, and other numerical data may be presented herein in a range format. It is to be understood that such range format is used merely for convenience and brevity and should be interpreted flexibly to include not only the numerical values explicitly recited as the limits of the range, but also to include all the individual numerical values or sub-ranges encompassed within that range as if each numerical value and sub-range is explicitly recited.
For example, a numerical range of about 1 to about 4.5 should be interpreted to include not only the explicitly recited limits of 1 to about 4.5, but also to include individual numerals such as 2, 3, 4, and sub-ranges such as 1 to 3, 2 to 4, etc. The same principle applies to ranges reciting only one numerical value, such as “less than about 4.5,” which should be interpreted to include all of the above-recited values and ranges. Further, such an interpretation should apply regardless of the breadth of the range or the characteristic being described.

B. The Invention

Reference will now be made to the drawings in which the various elements of the present invention will be given numeral designations and in which the invention will be discussed. It is to be understood that the following description is only exemplary of the principles of the present invention, and should not be viewed as narrowing the appended claims.
The present invention includes a method for synthesizing superabrasive particles and controlling nucleation and growth during superabrasive particle synthesis. Generally, the methods of the present invention can be used to form either diamond or cBN superabrasive particles from corresponding crystalline seeds. However, it will be understood that the principles of the present invention can also be useful for production of other crystalline particles.
Growth Precursors
Referring now to FIG. 1, a raw material layer 12 can be formed. The raw material layer can be provided as a particulate layer or as a solid plate. In one aspect of the present invention, the raw material layer can be a particulate layer. In one embodiment of the present invention, the raw material layer can be provided as a loose powder. The loose powder can be placed in a mold and optionally pressed using any known pressing technique. For example, the powder can be pressed using cold isostatic pressing at about 200 MPa to achieve a porosity of from about 8% to about 15%, although porosities of less than about 30% are typically satisfactory. Using particulate layers can provide ease of planting crystalline seeds therein and avoid formation of large voids around the crystalline seeds.
The raw material layer can include any materials which are capable of providing raw materials for growth of a desired superabrasive particle. Specifically, a carbon source can be used for diamond growth, while a low pressure-phase boron nitride such as hexagonal boron nitride can be used for cBN growth. Under diamond growth conditions, the carbon source layer can comprise a carbon source material such as graphite, amorphous carbon, diamond powder, and the like. In one aspect of the present invention, the carbon source layer can comprise graphite. Although a variety of carbon source materials can be used, graphite generally provides good crystal growth and improves homogeneity of the grown diamonds. When graphite is used as the carbon source material, preferably the carbon source material comprises at least about 85 wt % graphite. For embodiments wherein the graphite is formed as a particulate layer, suitable graphite powder can typically be from about 1 μm to about 1 mm. In one detailed aspect of the present invention, the graphite can have a degree of graphitization of greater than 0.50. Preferably, the graphite can have a degree of graphitization of from about 0.75 to about 1, and in some cases greater than about 0.80. However, the degree of graphitization is most preferably from about 0.85 to about 1. Experiments have shown that a higher degree of graphitization corresponds to larger crystallite sizes and improved grown diamond quality and uniformity. Diamond is typically formed through puckering and bending of graphene planes in the presence of molten catalyst metal. Therefore, diamond formation can be improved by providing graphite having a high degree of graphitization.
In another aspect of the present invention, a particulate catalyst layer 14 can be formed adjacent the raw material layer 12. The particulate catalyst layer can be formed of metal catalyst powder. The metal catalyst layers of the present invention can be formed as a loose powder, porous compact or other substantially non-sintered mass. Loose powder can be used directly by placing the powder in a suitable mold adjacent to the raw material layer. This loose powder can be optionally pressed using known pressing technologies to form a disk. Alternatively, the metal catalyst powder can be formed into a disk and then subsequently placed adjacent the raw material layer.
In a preferred embodiment, the particulate catalyst layer contains no binder, no oils, and no organic materials. Further, the particulate catalyst layers of the present invention can consist essentially of metal catalyst powder. The presence of organic materials during the growth process can cause undesirable flaws and non-uniformities in the grown superabrasive crystal structures. Providing a particulate catalyst layer allows for crystalline seeds to be easily embedded in the catalyst layer, as described in more detail below. Care should be taken when handling such particulate layers, since the absence of organic binders and the like tends to make the assemblies and disks more brittle than if an organic binder was included. Therefore, in some embodiments of the present invention, it can be desirable to use a solid plate as the raw material layer to provide additional mechanical support to the assembly. In an optional embodiment, raw material layers and catalyst layers can be pressed together to form a convenient supply of two-layer assemblies for use in the methods of the present invention. In one aspect of the present invention, the particulate catalyst layer can have a porosity of less than about 33%.
In one detailed aspect of the present invention, the catalyst layer can comprise a catalyst material which is suitable for growth of the desired superabrasive particle. Catalyst materials suitable for diamond synthesis can include metal catalyst powder comprising any metal or alloy which is a carbon solvent capable of promoting growth of diamond from carbon source materials. Non-limiting examples of suitable metal catalyst materials can include Fe, Ni, Co, Mn, Cr, and alloys thereof. Several common metal catalyst alloys can include Fe—Ni, e.g., INVAR alloys, Fe—Co, Ni—Mn—Co, and the like. Currently preferred metal catalyst materials are Fe—Ni alloys, such as Fe-35Ni, Fe-31Ni-5Co, Fe-30Ni, and other INVAR alloys, with Fe-35Ni being most preferred and more readily available. Generally, suitable Fe—Ni alloys can have a nickel content which varies from about 10 wt % to about 50 wt %. In addition, the catalyst materials under diamond synthesis can include additives which control the growth rate of diamond, i.e. via suppressing carbon diffusion, and also prevent excess nitrogen and/or oxygen from diffusing into the diamond. Suitable additives can include Mg, Ca, Si, Mo, Zr, Ti, V, Nb, Zn, Y, W, Cu, Al, Au, Ag, Pb, B, Ge, In, Sm, and compounds of these materials with C and B.
Similarly, catalyst materials suitable for cBN synthesis can include any catalyst capable of promoting growth of cBN from suitable boron nitride raw materials. Non-limiting examples of suitable catalyst materials for cBN growth include alkali metals, alkali earth metals, and compounds thereof. Several specific examples of such catalyst materials can include lithium, sodium, calcium, magnesium, barium, nitrides of alkali and alkali earth metals such as Li₃N, Ca₃N₂, Mg₃N₂, CaBN₂, and Li₃BN₂. Additionally, the catalyst material can include Al, Fe, Co, Ni, and alloys thereof. The catalyst materials under cBN synthesis can further include very minor amounts of additives which control the growth rate of cBN crystal such as Si, Mo, Zr, Ti, Al, Pt, Pb, Sn, B, C, and compounds of these materials with Si, B, and N.
Dimensions of the particulate catalyst layer 14 can vary considerably. However, the thickness of the layer should allow raw material such as carbon to diffuse toward the crystalline seeds sufficient to allow crystal growth at an interface between the crystalline seeds and the surrounding catalyst material. In one aspect of the present invention, the raw material layer and/or particulate catalyst layer can be formed by cold pressing powder to form a coherent mass which is then sliced into thin layers such as a disk for use in the present invention. The pressed disks can then be stored for later use and can be easily placed in a mold as described above.
Referring now to FIG. 3, in accordance with the present invention, crystalline seeds 20 can be placed in a predetermined pattern on the particulate catalyst layer 14. By placing crystalline seeds in a regular predetermined pattern, growth conditions can be optimized to efficiently use available growth volumes, increase crystal quality, and decrease size distribution of grown superabrasive particles. The crystalline seeds can be any suitable seed material upon which growth can occur for either diamond or cBN. In one aspect of the present invention, the crystalline seeds can be diamond seeds, cBN seeds, or SiC seeds. The synthesis of either diamond or cBN can utilize such crystalline seeds. Frequently, diamonds seeds are the preferred crystalline seeds for diamond synthesis. Further, in some embodiments of cBN synthesis, cBN seeds can be used. Alternatively, the crystalline seeds can be multi-grained such that a plurality of smaller crystals are bonded together to form each crystalline seed. Most often, when placing crystalline seeds in the catalyst layer, the crystalline seeds are preferably uncoated seeds, i.e. they do not include additional metal or other coatings around crystalline seed.
Typically, the crystalline seeds can have a diameter of from about 30 μm to about 500 μm, and preferably from about 55 μm to about 500 μm. However, the present invention is ideally suited to patterned placement and growth of almost any size crystalline seed. Allowing for larger crystalline seeds also reduces the growth time required to produce large superabrasive particles. In particular, diamond seeds suitable for use in the present invention can be larger than typical diamond seeds, i.e. from about 200 μm to about 500 μm, although the above ranges can also be effectively used. Alternatively, the crystalline seeds can have a diameter from about 10 μm to about 50 μm, and in some cases from about 20 μm. The methods of the present invention allow for extended growth times while also avoiding incorporation of inclusions. As a general guideline, typically crystalline seeds can have an average diameter from about 0.05 to about 0.2 times the average diameter of the desired grown superabrasive particles. In one detailed aspect, suitable diamond seeds can be type IIa diamond and may be synthetic or natural diamond. Alternatively, synthetic cBN or SiC seeds can be used. In an additional alternative embodiment, the crystalline seeds can be a mixture of different types of seeds, i.e. two or more of diamond seeds, cBN seeds, and SiC seeds.
Arrangement of crystalline seeds in the predetermined pattern can be accomplished in any number of ways. In one embodiment, the crystalline seeds can be arranged in a predetermined pattern using a template to guide placement of the seeds. FIG. 1 shows a side view of a template 16 which can be placed upon the particulate catalyst layer 14. For improved consistency and accuracy, the template can be optionally aligned using guiding pins or the like.
Suitable templates can be formed of almost any material in which a pattern of apertures can be formed. The apertures 18 can be sized to accommodate a single crystalline seed 20 in each aperture. The apertures are typically circular; however any other practical shape can be used. Typically, the template 16 can be formed of a metal sheet such as stainless steel, nickel, aluminum, or hard plastics. However, other materials such as polymeric, ceramic, or composite materials can also be used to form the template. In one aspect of the present invention, the template can be prepared by forming holes which extend completely through the material as shown in FIGS. 1 and 3. Alternatively, the holes can be formed only partially through the material to form a divot or indentation. In this embodiment, the template can also act as a transfer sheet to place the crystalline seeds on a substrate. In either case, the holes can be formed using any known method such as mechanical or chemical methods. Several examples can include laser drilling, micro-drilling, computer numerically controlled (CNC) drilling, chemical etching, and the like. In one aspect of the present invention, the template can be a sieve.
The predetermined pattern can be almost any pattern which places the crystalline seeds at distances suitable for crystal growth. FIG. 2A illustrates one embodiment where the predetermined pattern can be a regular grid pattern of apertures 18 in a template 16 which can be used to place crystalline seeds at regular intervals in both the x and y directions. Alternatively, the predetermined pattern can be a series of offset rows as shown in FIG. 2B. In yet another alternative embodiment, the apertures 18 can be formed such that varying concentrations of crystalline seeds can be arranged or even varying sizes of crystalline seeds can be placed on the particulate catalyst layer 14 (FIG. 3). For example, predetermined patterns having variations in the size of apertures can be filled by first placing larger crystalline seeds to fill in larger apertures and then filling smaller apertures with smaller mesh crystalline seeds.
The spacing of apertures 18 in a template 16 can vary somewhat. However, the apertures should be formed such that individual crystalline seeds are placed from 400 μm to about 1.5 mm apart. Those skilled in the art will recognize that spacing outside this range can also be used and can depend on the size of the crystalline seeds and the desired final grown superabrasive sizes. It should be noted that these distances are measured from center to center. As additional guidance, the apertures can be formed so as to place crystalline seeds a distance apart which allows each seed sufficient space to receive raw material without competition from neighboring crystals. Depending on the desired final size of the superabrasive particles, the spacing between grown superabrasive particles can range from about 300 μm to about 1000 μm, although distances outside this range can also be used. Typically, the final diameter of the grown superabrasive particles leaves at least a distance of about 0.8 times the final diameter of the grown superabrasive particles between edges of nearby grown superabrasive particles, and preferably from about 1.2 to about 3 times the final diameter. For example, a spacing of from about 800 μm to about 900 μm can be used to grow particles having a diameter of from about 425 μm to about 600 μm (30/40 mesh). In another example, a spacing of about 650 μm can be allowed between grown superabrasive particles having a size of about 45 mesh, while a spacing of about 800 μm can be allowed for larger grown particles of about 35 mesh. In yet another example, a spacing of from about 700 μm to about 1.5 mm can be used to grow 30/40 mesh (600 to 425 μm) grown diamond. Excessively large spacing between apertures can result in significant amounts of wasted space and raw materials, while an aperture spacing which places crystalline seeds too close can result in large numbers of crystals growing together. Those skilled in the art can make appropriate adjustments to spacing in order to compensate for shrinkage during HPHT growth.
In accordance with the present invention, a thin layer of binder can be coated over at least a portion of a surface of the growth precursor prior to placement of crystalline seeds thereon. This can help to prevent seeds from leaving their predetermined positions and further increases ease of handling during manufacture. The use of an adhesive layer can result in a predetermined pattern that is substantially free of vacant positions or misplaced crystalline seeds with respect to the pattern of apertures. The layer of adhesive can be formed using any suitable process such as, but not limited to, spraying, film coating, spin coating, extrusion coating, and the like. Spraying is typically convenient and effective in producing a thin and uniform layer of adhesive.
Suitable binders can include, but are not limited to, organic binders such as acrylic adhesives, wax, polyethylene glycol, polyvinyl alcohol, paraffin, naphthalene, polyvinyl butyral, phenolic resin, wax emulsions, and mixtures thereof. Currently preferred organic binders include acrylic adhesives, polyethylene glycol, and polyvinyl alcohol. In one specific example, an acrylic adhesive spray available from 3M Company can be diluted with a solvent such as acetone and then sprayed on the growth precursor.
The layer of adhesive thus prepared can be of almost any functional thickness. However, as a general guideline the layer of adhesive can have a thickness from about 1 μm to about 50 μm. The thickness of the layer of adhesive can typically correspond to that which is sufficient to hold the crystalline seeds in place. Excessive adhesive can be undesirable. As mentioned herein, it is often desirable to minimize organic content in the growth precursor placed in a HPHT apparatus. Specifically, such materials can interfere with particle growth and can be optionally removed during a subsequent dewaxing step in order to drive off organic materials. The dewaxing step can preferably be performed using a growth precursor which is substantially complete such that all of the crystalline seeds are secured within the growth precursor. Securing can be accomplished by stacking adjacent layers or disks of raw material, catalyst material, and/or inert material adjacent the patterned placement of seeds. In this way, removal of the organic binders will not disturb the predetermined pattern of crystalline seeds.
As shown in FIG. 3, crystalline seeds 20 can be placed into the apertures 18 of the template 16. An excess of crystalline seeds can be spread over the template surface such that each of the apertures is filled with a single crystalline seed. The excess crystalline seeds can be swept away or otherwise removed leaving particles placed on the particulate catalyst layer 14 as shown in FIG. 3. The template can have a thickness which varies depending on the size of the crystalline seeds and the process. Typically, the thickness of the template can be from about 0.6 to about 1.1 times the diameter of the crystalline seeds. Once the crystalline seeds are placed in the apertures of the template, the template can then be removed leaving the crystalline seeds in a predetermined pattern on the particulate catalyst layer. The template can then be reused or discarded depending on its condition. As shown in FIG. 4, a metal plate 22 or other hard surface can be used to press the crystalline seeds 20 at least partially into the particulate catalyst layer 14. Optionally, if the template has a thickness which is less than the diameter of the crystalline seeds, the template can be left in place during pressing in order to control the distance the crystalline seeds are embedded into the catalyst layer and then removed subsequently. In one embodiment of the present invention, the crystalline seeds 20 can be pressed into the catalyst layer such that from about half to about the entire particle is buried into the catalyst layer. In one aspect, crystalline seeds can be pressed completely into the catalyst layer such that each crystalline seed is substantially surrounded by catalyst material.
In accordance with the present invention, any exposed portions of the crystalline seeds 20 can be covered with additional metal catalyst material such that the catalyst material substantially surrounds each crystalline seed to form a growth precursor 24, as shown in FIG. 5. Typically, in this embodiment of the present invention, the thickness of the initial particulate catalyst layer 14 (FIGS. 1, 3 and 4) can be from about 0.5 to about 0.9 times the diameter of the crystalline seeds, and preferably about 0.7. The exposed crystalline seeds can be covered by placing additional catalyst material on the exposed crystalline seeds and then optionally pressing to reduce porosity to less than about 33% to produce the growth precursor 24 shown in FIG. 5.
In one alternative embodiment, the exposed portions of the crystalline seeds can be covered with a metal catalyst plate or foil, although a powder metal catalyst is preferred due to some inherent non-homogeneities in solid plates. The particulate catalyst layer 14 preferably has a thickness which is sufficient to initially completely surround each crystalline seed. During crystal growth, the metal catalyst material continues to wet the surface of the crystalline seed. Therefore, the thickness of the particulate catalyst layer need not be greater than the diameter of the grown superabrasive particles.
During diamond synthesis, the graphite to metal catalyst ratio can determine the availability of raw materials for formation of diamond. Typically, the graphite to metal catalyst ratio can range from about 0.5 to about 2.0 by weight, and preferably from about 0.7 to about 1.5. In one aspect, the catalyst metal can be provided in an amount sufficient to form a layer of molten catalyst metal during growth conditions having a thickness of from about 20% to about 60% of the diameter of the diamond during growth.
Referring now to FIG. 6, additional raw material layers 12 and particulate catalyst layers 14 can be formed to improve efficient use of a high pressure high temperature (HPHT) apparatus cell volume. The thickness of each layer can depend on the diameter of the crystalline seeds 20 and the projected diameter of the final grown superabrasive particles. Additionally, the thickness of the layers will also affect the distance between crystalline seeds in nearby catalyst layers. The predetermined pattern in each particulate catalyst layer can be configured such that upon assembling layers as in FIG. 6, the assembly also exhibits a predetermined pattern across the thickness of the growth precursor 24. The pattern shown in FIG. 6 is an offset pattern; however any suitable arrangement can be used, as long as grown crystals do not impinge on neighboring grown crystals. Typically, the particulate catalyst layers can have a thickness of from about 50 μm to about 500 μm, while the raw material layer can have a thickness of from about 70 μm to about 1 mm. Those skilled in the art will recognize that thicknesses and configurations outside of the identified ranges can also be used.
Typical HPHT reaction cells can have a reaction volume of from about 15 cm³to about 100 cm³. Therefore, it is often practical to include a large number of layers in the growth precursor in order to fully utilize available reaction volume for crystal growth. In one aspect of the present invention, the growth precursor can have from about 3 to about 50 layers. In addition, formation of each layer and placement of crystalline seeds can be preceded or followed by a pressing step in order to reduce porosity and improve the cohesiveness of the growth precursor. Thus, in one preferred embodiment, each layer can be pressed prior to pressing the entire multi-layer growth precursor. Pressing can be preferably accomplished by cold isostatic pressing although other pressing techniques can also be used.
Placement of Crystalline Seeds in a Predetermined Pattern
As mentioned above, the crystalline seeds can be placed in a predetermined pattern using any number of methods. Those of ordinary skill in the art will recognize a variety of ways for locating particles at desired locations on a surface or substrate. A number of techniques have been developed for placing superabrasive particles in a pattern for production of abrasive tools. For example, U.S. Pat. Nos. 2,876,086; 4,680,199; 4,925,457; 5,380,390; and 6,286,498, each of which is incorporated by reference, disclose methods of placing superabrasive particles in a pattern for forming various abrasive tools.
An alternative method for placing crystalline seeds in a predetermined pattern can include providing a transfer sheet having an adhesive layer thereon. The transfer sheet can be any material which is self-supporting and capable of transporting crystalline seeds to a catalyst layer. A template, such as those discussed above, can then be placed upon the adhesive layer. For example, a template can be placed upon a transfer sheet such as an adhesive tape or other adhesive material. Preferably the adhesive layer is sufficiently tacky to hold the crystalline seeds which contact the adhesive while also allowing for easy removal of the template. Non-limiting examples of moderately tacky adhesives suitable for use with a transfer sheet include acrylic adhesives and polymeric adhesive microspheres, e.g., such as those used in POST-IT (trademark of 3M Company) notes. Alternatively, the template can have a surface coated with a smooth and/or non-stick material such as TEFLON or the like, in order to facilitate removal of the template. The apertures of the template can then be filled with crystalline seeds as discussed above. After removing the template, the transfer sheet having patterned placement of crystalline seeds can be contacted with the growth precursor having a layer of adhesive thereon. The transfer sheet can be oriented between the crystalline seeds and the catalyst layer. Depending on the material used, the transfer sheet may decompose during the initial stages of HPHT.
Alternatively, the transfer sheet can be oriented such that the crystalline seeds are between the transfer sheet and the particulate catalyst layer. The transfer sheet can then be removed or left in place. In order to facilitate removal of the transfer sheet without disturbing the crystalline seeds, the particles can be pressed partially into the particulate catalyst layer. Of course, the composition of the adhesive layer can also be adjusted to reduce the tackiness of the adhesive. As a practical matter, it can be desirable to utilize an adhesive on the growth precursor which has a higher tackiness than the adhesive of the transfer sheet such that transfer of the particles from the transfer sheet to the growth precursor is made easier.
Alternatively, the transfer sheet can be a metal catalyst layer such as a foil or disk formed of metal catalyst material used in the particulate catalyst layer. The metal catalyst foil layer can remain in place to help surround the crystalline seeds with metal catalyst material. In such an embodiment, it can be desirable to partially embed the crystalline seeds into the foil in order to avoid the use of organic binders which may adversely affect crystal growth. Regardless of the specific transfer sheet process used, the crystalline seeds can then be at least partially pressed into the particulate catalyst layer.
In yet another alternative embodiment of the present invention, the crystalline seeds can be placed in a predetermined pattern using vacuum chuck. Specifically, a vacuum chuck can be formed having a pattern of apertures therein. The apertures can be configured to hold a single crystalline seed such that pulling a vacuum through the apertures engages a single crystalline seed in each aperture. Thus, the apertures can have an initial portion sized slightly smaller than the crystalline seed and which are connected to a vacuum source. In practice, a vacuum can be pulled through the apertures and the chuck can then be placed in a supply of crystalline seeds. The chuck can then be oriented over the particulate catalyst layer, or optionally a transfer sheet and the vacuum can be reduced sufficient to release the crystalline seeds thus arranging the crystalline seeds in a predetermined pattern corresponding to the pattern of apertures in the chuck. The crystalline seeds can then be pressed at least partially into the catalyst layer in a similar manner as discussed above.
Alternatively, the crystalline seeds can be placed in a predetermined pattern on the raw material layer, rather than the catalyst layer, using any of the above-described methods, i.e. template, sieve, transfer sheet, and the like. It will be understood that any of the methods described above for placement of the crystalline seeds in a predetermined pattern can also be used on the raw material layer. Typically, diamond seeds can be coated with a catalyst metal prior to placement in the raw material layer in order to prevent direct contact of the diamond seeds with raw carbon or graphite. Coating of diamond particles is known in the industry and can be accomplished using any number of available methods. Typically, diamond particles can be coated by a catalyst metal such as Fe, Ni, Co, and alloys thereof. Catalyst coatings of nickel and nickel alloys are particularly preferred. The metal coating can help provide a molten catalyst layer surrounding the diamond seeds during HPHT growth and prevent direct contact with graphite or other carbon raw materials. The coating can have a thickness which varies from about 2 μm to about 50 μm, although thickness above this range can also be used.
In yet another alternative embodiment, the crystalline seeds can be placed in a predetermined pattern by forming polycrystalline seeds from a slurry using a method such as screen printing, other lithographic techniques, or the like. Thus, the crystalline seeds can be polycrystalline or monocrystalline. In accordance with this embodiment, the polycrystalline seeds can be prepared by forming a slurry of diamond particles, catalyst metal powder, an organic binder, and an optional solvent. The slurry can be formed into a plurality of polycrystalline seed precursors and then removing the organic binder and optional solvent to form polycrystalline seeds.
The diamond particles can be almost any functional size. As a general guideline, sizes from about 1 μm to about 15 μm can be useful, and typically from about 2 μm to about 4 μm. The final size of the polycrystalline seed can be about the same as crystalline seeds herein discussed; however, in many cases the seeds can be less than about 10 μm. Additionally, the catalyst metal powder can comprise catalyst material as discussed above in connection with other embodiments, or embodiments which can be used in conjunction with polycrystalline seeds. Typically, the catalyst can comprise from about 5 vol % to about 50 vol % of the polycrystalline seed.
Non-limiting examples of suitable organic binders can include polyethylene glycol (PEG), polyvinyl alcohol, methyl propyl cellulose, carboxy methyl cellulose, hydroxy ethyl cellulose, methyl ethyl cellulose, polyvinyl butyral, acrylic resin, coal tar pitch, long chain fatty materials, sugars, starches, alginates, polystyrene, cellulose acetate, phenolic resins, and mixtures thereof. An optional solvent can be included to adjust the viscosity of the slurry to accommodate a particular printing technique. Suitable solvents can include, but are not limited to, acetone, ethanol, isopropanol, glycols, methanol, trichlorethylene, toluene, and mixtures thereof.
For example, the slurry can be printed onto a surface, e.g., of the growth precursor or particulate growth layer, to form polycrystalline seed precursors. The organic binder and optional solvent can be removed in a drying and/or dewaxing step. For example, a first heating step can be used to remove any solvent, e.g., about 100° C. for about 4 hours, and a second dewaxing step can be used to remove the organic binder, e.g., heating at 600° C. for about 2 hours (usually under a vacuum). The final polycrystalline seeds typically include diamond particles and catalyst metal. Optimal results can be achieved when the final grown superabrasive particles have a size greater than about 10 times that of the polycrystalline seed.
In accordance with the present invention, polycrystalline seeds have been found to produce final grown superabrasive particles having a monocrystalline structure. It appears that the growth conditions of the present invention allow the polycrystalline seeds to merge and form a substantially single crystal. Superabrasive particles formed in this manner tend to allow for microfracturing of the particle during abrasive applications. Typical superabrasive particles tend to either become dull or macrofracture making the remaining particle useless. However, microfractures allow the particle to periodically expose new sharp edges and retain the bulk of the particle for extended useful life.
Mixture Growth Precursors
In yet another alternative embodiment of the present invention, a method for controlling nucleation sites during superabrasive particle synthesis can include forming a particulate crystal growth layer. Generally, a growth precursor can be formed and then heating sufficient to grow superabrasive particles having a preselected morphology. The growth precursor can be formed to include a substantially homogeneous mixture of raw material and catalyst material. Further, the growth precursor can have crystalline seeds in a predetermined pattern at least partially therein. It will be understood that the principles and considerations described above with respect to layered growth precursors can also be used in connection with growth precursors comprising a substantially homogeneous mixture of raw material and catalyst material.
Referring now to FIG. 7, the particulate crystal growth layer 15 can be a substantially homogeneous mixture of particulate raw material and particulate catalyst material. Crystalline seeds 20 can be placed in a predetermined pattern at least partially in the particulate crystal growth layer to form a growth precursor 24 using the same methods discussed above. Additionally, the growth precursor can include a single layer or multiple layers as shown in FIG. 7. The materials, ranges, patterned placement methods, and other aspects discussed above can also be applied to the particulate crystal growth layers comprising a mixture of raw material and catalyst material. In one aspect, the growth precursor can consist essentially of raw material, catalyst material, and crystalline seeds.
As mentioned earlier, an uncoated diamond seed substantially surrounded by graphite can be undesirable. However, surrounding the diamond seeds with a mixture of carbon source material and catalyst allows the catalyst powder to wet the surface of the diamond seeds and coat the surface thereof. This wetting effect is at least partially the result of carbide bonds forming between the diamond and the solvent metal. Diamond may initially dissolve because the catalyst metal is under-saturated with carbon; however, once the catalyst metal is melted, the carbon begins to diffuse into the molten catalyst. The dissolved or suspended carbon will soon adhere to the surface of the diamond seed and allow the seed to grow.
In one currently preferred embodiment, the diamond seeds can be coated with a catalyst material. In some embodiments, the coating can consist essentially of a catalyst material. Typically, the coating can be a catalyst material having a melting temperature within about 5° C. of the melting temperature of the catalyst material used in the particulate catalyst layer. This helps to avoid the metals from melting at significantly different times thus reducing the quality of the final grown diamond. Diamond seeds can be coated with a catalyst material using any known technique. Coating of diamond particles has historically proven difficult, since most catalyst metals cannot be easily coated on diamond to the required thickness, involve significant expense, and/or leave undesirable organic residual materials. Several examples of coating technologies include, without limitation, electroplating, chemical (e.g., electroless) deposition, physical vapor deposition (e.g., sputtering), chemical vapor deposition, fused salt coating, and the like.
In one embodiment, the catalyst metal can be nickel; however, other catalyst metals can be also suitable. FIGS. 8A and 8B show a photomicrograph of nickel coated diamond particles in accordance with one embodiment of the present invention. Nickel coatings typically have a highly irregular surface topography characterized by small protrusions or spikes. This irregular topography has the added benefit of increasing surface area contact between the catalyst coating and catalyst metal in the mixture of the growth precursor. In this way, additional catalyst material can easily diffuse into the catalyst coating during crystal growth in order to maintain a coating of sufficient thickness to prevent direct contact between the diamond and raw material. As diamond growth occurs, the diamond surface area increases, thus having the tendency to decrease the catalyst coating thickness. However, in accordance with the present invention, the catalyst coating thickness can be maintained by adjusting the amount of catalyst material in the growth precursor. The catalyst coating can have a thickness which is sufficient to prevent substantial direct contact between the diamond and raw material. Typically, the catalyst coating can have thickness which is about 0.5 to about 1.3 times the diameter of the particle. For example, a diamond seed having a diameter of 40 μm can be coated to a final diameter of about 100 μm. Thus, the coating thickness in this case is about 30 μm. The larger crystalline seed can also improve the accuracy and speed of placing the seeds in a predetermined pattern. As a practical matter particles smaller than about 50 μm can be difficult to reliably place using a template.
In still another aspect of the present invention, the crystalline seeds can be arranged on a metal catalyst layer such as a foil or disk to form a predetermined pattern of crystalline seeds. The crystalline seeds can be placed on the metal layer in a manner similar to that described above. A substantially homogeneous mixture of catalyst material and raw material can be formed around the crystalline seeds and then consolidated to reduce porosity of the growth precursor. Additional layers can be formed by then placing another metal catalyst layer on the growth precursor and repeating the above steps to produce a multi-layered growth precursor having almost any number of layers. The metal catalyst layer can comprise any catalyst material suitable for growth of the superabrasive particle. Typically, the metal catalyst layer can have a thickness from about 20 μm to about 0.10 mm, although any functional thickness can be used. Generally, the number of layers in a multi-layered precursor can vary depending on the HPHT apparatus to be used. Typically, the height of the precursor is about 80% of the diameter, although this can vary somewhat.
The metal catalyst layer can provide a substantially flat surface which has improved mechanical support for the growth precursor. Additionally, during growth of the superabrasive particles, the layer can provide an initial source of catalyst material for maintenance of the catalyst coating around the growing superabrasive particle. As the superabrasive particle continues to grow, the primary source of additional catalyst material can then be the mixture of catalyst and raw material.
In another optional aspect of the present invention, the growth precursor can be coated along exterior surfaces with a metal coating. Suitable metal materials can include Fe, Ni, Co, and alloys thereof. The exterior metal coating helps to prevent the precursor from adhering or bonding to reaction cell walls of the HPHT apparatus under growth conditions. The coating thickness can be any thickness which is sufficient to provide the above benefit; however, typical thicknesses can range from about 50 μm to about 300 μm. In yet another optional aspect, a layer of separator material can be included adjacent the growth precursor in a reaction cell volume of the HPHT apparatus. A layer of NaCl can typically be used as the separator material; however other materials can also be used.
The growth precursor can then be subjected to a temperature and pressure in which diamond or cBN is thermodynamically stable. As the temperature and pressure are increased to sufficient growth conditions, raw material such as carbon migrates toward the crystalline seeds. The catalyst material surrounding individual crystalline seeds form a catalyst layer substantially surrounding each seed, assuming sufficient catalyst material is present to form such a coating. The catalyst coating facilitates formation of diamond or cBN at the surface of the crystalline seeds. The growth conditions are maintained for a predetermined period of time to achieve a specific size of grown superabrasive particle.
Advantageously, the methods of the present invention enable a high degree of control over the growth conditions of each superabrasive particle. The highly regular placement of seeds and the substantially homogeneous growth precursor compositions allow for precise control of temperature throughout the growth precursor. As a result, the growth of individual superabrasive particles can be nearly uniform throughout the growth precursor. The final collection of superabrasive particles are therefore highly uniform in shape, size, and quality. Typically, the collection of grown superabrasive particles can have a narrow size distribution characterized by a standard deviation of less than about 0.2 of the average size of unsorted and unsized particles, and preferably less than about 0.1 and most preferably less than about 0.05 of the average size. For example, a narrow size distribution having a standard deviation (2 a) within about 0.05 of an average size corresponds to about 95% of the particles falling within about 5% of the average. In many cases, the size distribution can have a standard deviation (3 a) from the average size of less than about 0.2 of the average size and in many cases less than about 0.1, e.g., a single assembly of grown particles having an average size of about 100 μm will have substantially no particles outside the range of about 90 μm to about 110 μm.
The final grown superabrasive particles can be recovered from the growth precursor using any number of known methods. For example, any remaining metal matrix can be removed by dissolving in warm aqua regia and remaining graphite can be removed in hot sulfuric acid. The recovered superabrasive particles can then be further cleaned and/or prepared for commercial use.
Diamond Growth Considerations
In accordance with the present invention, growth precursors can include diamond seeds located at controlled locations such that each seed is subjected to substantially identical growing environments. In this way, each seed can grow to substantially similar sizes and quality. This technology allows for custom dialing of the size and quality so nearly the entire output is uniform for a particular application or customer. Due to this increase in uniformity of growth conditions, a number of advantages can be realized. For example, the crystal morphology can be controlled to produce superabrasive particles having a preselected morphology, e.g., octahedral, cubo-octahedral, etc. The following discussion provides guidance in obtaining specific results using the methods of the present invention, without being bound by any particular theory presented.
Diamond growth can be accomplished by providing dissolved carbon atoms or by puckering layers of graphite which add to an existing diamond crystal face. FIG. 9A shows an octahedral (111) face of diamond in progress of growth. As shown in FIG. 9B the carbon atoms contained in this layer contain one unbonded, or dangling, electron. The octahedral face of diamond can be dominantly formed by puckering of graphite layers, shown in FIG. 9C. If nano-sized flakes of graphite (graphite-like carbon or GLC) are present, these flakes can be readily rearranged to form rhombohedral graphite as shown in FIG. 10A. The rhombohedral graphite can be readily puckered to form diamond-like carbon (DLC) as shown in FIG. 10B. The diamond-like carbon can then add to the octahedral (111) face of diamond as illustrated in FIG. 10C. Additional details on such a method of forming rhomohedral graphite may be found in Applicant's copending application, U.S. patent application Ser. No. 10/900,037, filed Jul. 24, 2004, which is incorporated herein by reference.
Similarly, the cubic (100) face of diamond is shown in FIG. 11A. It is interesting to note that these atomic scale atomic arrangements affect the macroscale crystalline structure, i.e. cubic versus octahedral faces of diamond particles. The carbon atoms on the cubic face of diamond contain atoms having two dangling electrons as shown in FIG. 11B. Thus, carbon atoms can be easily attached to the cubic face such that growth of diamond occurs perpendicular to this face, as shown by FIG. 11C.
Referring now to FIG. 12A, diamond growth mechanisms will be discussed in more detail. FIG. 12A illustrates a growing diamond particle 30 surrounded by a catalyst material 32. A portion of a cubic (100) face 36 of the diamond particle and a portion of an octahedral (111) face 38 are also shown. The catalyst material envelope 32 surrounding the diamond particle is also in contact with a raw material 34 which diffuses through the catalyst envelope. FIG. 12B shows a portion of the cubic face 36 under growth conditions which favor growth on this plane. Specifically, at relatively high temperatures, graphite will dissolve to form atomic carbon solutes. These carbon atoms tend to deposit as diamond on the cubic face of diamond. Growth of the cubic face perpendicular to the face will result in the cubic face becoming smaller such that the growing diamond will become more and more octahedral.
Conversely, as shown in FIG. 12C, if the temperature is relatively low, graphite will disintegrate in the molten catalyst to form graphite-like carbon (GLC) that will be puckered under catalytic action to become diamond-like carbon (DLC). The DLC will add to the octahedral (111) face of diamond. As a result, growth perpendicular to the (111) face will shrink this face and make the diamond crystal more and more cubic. For example, FIG. 13A illustrates diamond growth at low temperature such that DLC preferentially deposits on the octahedral (111) face so the crystal will become more cubic. Conversely, a higher temperature will favor carbon atoms depositing on the cubic face so the diamond crystal will become more octahedral, as shown in FIG. 13B. According to an embodiment of the present invention, the ability to achieve a preselected morphology is greatly increased. For example, in some cases, the grown diamonds from an unsorted single run can have greater than 70%, preferably greater than about 85%, and most preferably greater than about 90% of the grown particles being a desired morphology, e.g., cubic, octahedral, or cubo-octahedral.
The diamond morphology is determined by the relative growth rate perpendicular to (100) and (111) faces. In FIG. 14, the fastest direction of diamond growth (the largest size of the crystal) is measured by α=√3V(111)/V(100), where V is the growth rate in a direction perpendicular to the identified face. FIG. 15 shows a photomicrograph of common premium quality saw grits having euhedral crystal morphology. These premium saw grits are typically cubo-octahedral as can be seen in the figure. The octahedral (111) face has the highest packing density of carbon atoms, relative to other diamond faces. As a result, the separation of octahedral faces from one another is farther such that failures of diamond particles tend to occur along this cleavage plane. As carbon atoms are added to the (111) face, they tend to spread along the face rather than to spread across the plane. On the other hand, if DLC is preferentially deposited, the octahedral plane will grow perpendicular to the (111) face. Additionally, octahedral diamond has a more acute angle than other shapes of diamond. Thus, octahedral diamonds are highly desirable for making single point cutters as well as wire drawing dies.
The temperature effect on diamond morphology allows for adjustment of the temperature based on the diamond itself to carefully control the resulting morphology. Thus, if diamond is too cubic, temperature can be increased by adding electrical heating power to make it more octahedral. On the other hand, lower electrical power can make diamond more cubic. The methods and growth precursors of the present invention allow for increased control and manipulation of these subtle temperature effects on crystal morphology. For example, in order to achieve dominantly octahedral diamonds a temperature from about 1305° C. to about 1320° C. can be used. Similarly, a temperature from about 1250° C. to about 1310° C. can be useful for obtaining cubic or cubo-octahedral diamonds. However, these temperature ranges are merely general guidelines as the actual values can vary depending on the specific catalyst material and raw material used. In accordance with the present invention, the temperature can be controlled to within about 10° C. throughout the growth precursor during crystal growth, typically within about 5° C. and in some cases within about 2° C.
Thus, in accordance with the present invention, synthetic octahedral diamonds can be produced in large quantities having very few inclusions. Further, the synthetic octahedral diamond of the present invention can be formed in relatively large sizes. For example, sizes greater than about 1 μm and often greater than about 10 μm can be easily realized. Generally, useful synthetic octahedral diamond can have a size from about 1 μm to about 10 mm, with sizes from about 20 μm to about 5 mm being preferred.
Referring now to FIG. 16, a graph shows various guidelines and aspects for consideration when using the methods of the present invention. During diamond growth, if the diamond seed is in contact with raw material, diamond is not formed so either graphite or metal will be trapped as inclusions to form highly included diamond. Consequently, it is important that diamond be enveloped in a molten layer of catalyst to allow uninterrupted growth of diamond. For example, diamond surface area is proportional to the square of the diamond size. Additionally, the supply of catalyst is proportional to the size of the growing diamond. As such, the thickness of the catalyst coating can gradually decrease as the diamond becomes larger. Thus, the substantially homogeneous mixtures of the present invention can provide a relatively uniform supply of additional catalyst material which can maintain a sufficiently thick catalyst coating around the growing diamond. Thus, both raw material and catalyst material tend to diffuse toward the growing diamond. Maintaining a substantially continuous catalyst envelope around each growing crystal helps to significantly reduce the number of inclusions in the grown diamonds.
FIG. 17 illustrates the growth of diamond seeds 20 in the presence of the surrounding catalyst material 26 to form a grown diamond 28. Direct contact of diamond seeds directly with the carbon source material can cause an undesirable number of inclusions. Typical growth conditions can vary somewhat; however, the temperature can be from about 1200° C. to about 1400° C. and the pressure can be from about 4 to about 7 GPa. The appropriate temperature can depend on the catalyst material chosen. As a general guideline, the temperature can be from about 10° C. to about 200° C. above a melting point of the catalyst. Growth time can typically be from about 5 minutes to about 2 hours. The patterned placement of crystalline seeds in the present invention also allows for relatively large variations in process conditions. For example, temperature and pressure can deviate from about 1% to about 10%, and in some cases can be from about 3% to about 5%. This allows for less strict control of process conditions than conventional methods, while also maintaining the quality of grown superabrasive particles. Typically, crystal growth in accordance with the present invention can be substantially epitaxial growth such that high quality superabrasive particles having high impact strength are produced. Further, the methods of the present invention can be fully automated and reduce the need for manual evaluation and processing.
In addition to the above considerations, the inclusion level can be further reduced by removing contaminants (e.g. oxygen on the metal, moisture in the graphite) from the reaction cells. One effective way to remove such contaminants is to subject the growth precursor, catalyst materials, and/or raw materials to a high vacuum (e.g. 10⁻¹Pa) at high temperature (e.g. 1100° C.) for an extended period of time (e.g. 2 hours). During this heat treatment, hydrogen can be used to purge the materials to further remove oxygen. Nitrogen can also be used to purge to make the diamond more rich in yellow color. Once these contaminants are substantially removed, the grown diamond can be highly transparent with a minimal level of inclusions. Diamond can also be back-converted to amorphous carbon (an intermediate step toward graphite) by any metal catalyst that is trapped inside of diamond crystal. Typically, this back-conversion can start at temperatures above 700° C. As soon as amorphous carbon is formed around the catalyst inclusion, the resulting volume expansion can cause diamond to microcrack. As a result, impact strength of the diamond can decrease. Thus, diamond with lower inclusion levels can survive better at high temperatures of hot pressing and impact cutting. Diamonds grown in accordance with the present invention possess high impact strength and high thermal stability such that they can be processed at high temperature (e.g. 1000° C.) to make diamond tools and used for aggressive cutting applications. As a general guideline, if molten metal surrounds the seeds from the beginning of the growth process, diamond seed of about 20 microns will tend to dissolve such that the control of nucleation may be lost. On the other hand, if the uncoated seeds are larger than about 50 microns, then a metal catalyst coating can be preferred. Otherwise, graphite may be in contact with the diamond seed before molten catalyst can flow to surround the seed. Without the coating of molten catalyst, graphite can be trapped as inclusions, along with some metal.
In one detailed aspect of the present invention, the crystalline seed can be from about 10% to about 30% of the desired grown diamond particle size. Depending on the growth conditions and the size of the crystalline seed, the grown superabrasive particles can have a particle size from about 100 μm to about 2 mm. Most common superabrasive particles sizes can range from about 18 mesh to about 60 mesh. Even larger superabrasive particles can be grown if larger crystalline seeds are used. Typically, grown superabrasive particles useful in many abrasive and cutting applications can have a particle size from about 210 μm to about 1 mm. One advantage of the present invention is the uniformity of grown superabrasive particle sizes. The predetermined pattern and orientation of layers allows for substantially uniform nucleation and growth of diamond and cBN. Therefore, the grown superabrasive particles of the present invention have a very narrow size distribution and improved quality when compared to particles grown from randomly nucleated and seeded precursors. For example, the size distributions using the present invention are typically less than half the standard deviation of conventional random seeded methods. Typically, the grown superabrasive particles of the present invention also have inclusion levels which are typically not noticeable under unaided visual inspection. Typically, yields of from about 30% to about 90% conversion of carbon to diamond can be expected when using the present invention. Further, the percent of high quality diamond can range from 50% to about 90%, with over 70% being a typical yield. In some embodiments of the present invention, the yield of high quality diamonds can range from about 2 carat/cm³to about 5 carat/cm³, and preferably from about 3.5 carat/cm³to about 4.5 carat/cm³. FIG. 18 shows an assembly of grown diamond particles in accordance with the present invention. In FIG. 18, the diamond particles are substantially uniform in size and exhibit uniform euhedral crystal shapes. In this example, the diamond separation was predetermined at 0.9 mm.

EXAMPLES

The following examples illustrate exemplary embodiments of the invention. However, it is to be understood that the following is only exemplary or illustrative of the application of the principles of the present invention. Numerous modifications and alternative compositions, methods, and systems may be devised by those skilled in the art without departing from the spirit and scope of the present invention. The appended claims are intended to cover such modifications and arrangements. Thus, while the present invention has been described above with particularity, the following examples provide further detail in connection with what is presently deemed to be practical embodiments of the invention.

Example 1

A circular mold having a diameter of 28 mm was filled with powdered natural graphite having an average size of about 20 μm, low resistivity of about 5 μΩ-cm, and a degree of graphitization of 0.8. The graphite was purified to be substantially free of oil, organic binders, ash, or other non-carbon materials. The graphite was cold pressed at 150 MPa to form a particulate compact disk having a thickness of 0.7 mm and a density of 2 g/cm³(12% porosity). High purity INVAR (Fe-35Ni with a mesh size of less than 40 μm) was placed on top of the graphite layer and cold pressed at 300 MPa to form a particulate catalyst layer having a thickness of 0.2 mm and a density of 6 g/cm³(about 20% porosity). A thin layer of adhesive was sprayed onto the particulate catalyst layer. A template similar to that shown in FIG. 2B, having apertures spaced 0.8 mm apart (center-to-center) and apertures 130 μm in diameter was placed on the catalyst layer. The template was covered in uncoated diamond seeds having a mesh size of 120/140 (about 115 μm in diameter) such that the apertures were filled. The excess diamond seeds were then collected for reuse. The template was removed and a metal plate was used to press the diamond seeds into the catalyst layer such that each of the diamond seeds was about two-thirds surrounded by catalyst material. Subsequently, additional INVAR was layered over the diamond seeds. The additional catalyst material was cold pressed at 150 MPa such that the entire catalyst layer had a thickness of 0.3 mm. Seven additional layers of graphite and catalyst material were formed to produce the diamond growth precursor. Each layer was dewaxed under vacuum at about 800° C. to about 1100° C. for two hours to remove the adhesive and other organic matter. Exterior surfaces of the diamond growth precursor were then coated with a 200 μm layer of iron. The diamond growth precursor was then placed in a belt apparatus. The precursor was then subjected to a pressure of about 5.2 GPa and then heated to a temperature of about 1260° C. for about one hour. The layered grown diamond assembly was then cooled and removed from the belt apparatus. The assembly was partially crushed to reveal grown diamonds which were substantially uniform in size and were yellow in color. The average mesh size of the grown diamonds was 30/40. Further, the grown diamonds exhibited superior hardness, superior transparency with fully grown crystallographic faces, and very few viewable inclusions.

Example 2

A circular mold having a diameter of 28 mm was filled with powdered natural graphite having an average size of about 20 μm, low resistivity of about 5 μΩ-cm, and a degree of graphitization of 0.8. The graphite was purified to be substantially free of oil, organic binders, ash, or other non-carbon materials. The graphite was mixed with high purity INVAR (Fe-35Ni with a mesh size of less than 40 μm). The weight ratio of graphite to metal catalyst was 1:1.5. The mixture was then cold pressed at 250 MPa to form a particulate compact disk having a thickness of 0.7 mm and a density of 2 g/cm³(12% porosity). The particulate compact disk was coated with a thin layer of adhesive. A template similar to that shown in FIG. 2B, having apertures spaced 0.8 mm apart (center-to-center) and apertures 130 μm in diameter was placed on the compact disk. The template was covered in uncoated diamond seeds having a mesh size of 120/140 (about 115 μm in diameter) such that the apertures were filled. The excess diamond seeds were then collected for reuse. The template was removed and a metal plate was used to press the diamond seeds into the compact disk such that each of the diamond seeds was about two-thirds surrounded by material. Subsequently, additional graphite and INVAR powders were layered over the diamond seeds. The additional powdered material was cold pressed at 250 MPa such that the entire layer had a thickness of 0.9 mm. Seven additional layers of graphite and catalyst material each having a pattern of diamond seeds were formed to produce the diamond growth precursor. Exterior surfaces of the diamond growth precursor were then coated with a 200 μm layer of iron. The diamond growth precursor was then placed in a belt apparatus. The precursor was subjected to a pressure of about 5.2 GPa and then heated to a temperature of about 1260° C. for about 50 minutes. The layered grown diamond assembly was then cooled and removed from the belt apparatus. The assembly was partially crushed to reveal grown diamonds which were substantially uniform. The average mesh size of the grown diamonds was 30/40. Further, the grown diamonds exhibited superior hardness, superior transparency with fully grown crystallographic faces, and very few viewable inclusions.

Example 3

Graphite disks were prepared by pressing natural graphite powder having a grain size of about 20 microns into disks 37 mm in diameter and 0.8 mm in thickness at about 400 MPa. The porosity of the resulting graphite disks was about 15%. Ni coated diamond seeds (precoated diameter of about 65-75 microns) having a coated diameter of about 105-125 microns were planted into the graphite disks in a grid pattern having a pitch of about 0.8 mm to form seeded graphite disks. The seeded graphite disks were alternated with INVAR (Fe65-Ni35) disks and loaded into a steel container to make a final growth cell of 38.8 mm in diameter and 30 mm in height. One hundred of these growth cells were pressed in a 2500 ton cubic press with a ram size of 600 mm to attain a pressure of about 5.2 GPa and temperature of about 1250° C. The pressure and temperature were maintained for 50 minutes and then the pressure was reduced and the temperature gradually decreased. The pressed growth cells were broken apart to reveal diamonds having 30/40 mesh with good quality and substantially no visible defects. Most of the grown diamonds were grown from the original seeds and appeared in distinct grid patterns corresponding to the original seeded positions. The final diamond yield achieved was 4 carats/cc. This yield was significantly higher than typical commercial diamond synthesis processes providing less than 3 carats/cc.

Example 4

Same as Example 3, except that each layer was made as a mixture of raw material and catalyst material. The disks were made by blending a 1.5 to 1 ratio of INVAR powder (having a grain size of about 40 microns) and graphite powder and then pressing as before to make disks 1 mm in thickness. Ni coated diamond seeds were planted directly into the pressed disks using the same pattern template as before to form seeded disks. The seeded disks were stacked and pressed and heated to grow diamond. The results were substantially the same as Example 3.

Example 5

Same as Example 4, except the diamond seeds are uncoated, i.e. no Ni coating. The grown diamonds had poorer quality with black dots that correspond to the original position of the crystalline seeds. The crystalline seeds had substantially back-converted to carbon. This example highlights the desirability to surround diamond seeds with molten catalyst before growth begins. In this case, graphite will disperse across the molten catalyst envelope and precipitate out as diamond. If the diamond is not fully enclosed by the molten catalyst as in the case of using an uncoated seed in a mixture, the direct graphite-diamond contact will result in highly visible graphitic inclusions.

Example 6

Same as Example 3, except the powder used in the mixture was iron having a grain size of about 6 microns and cobalt having a grain size of about 2 microns in a weight ratio of 2:1. Both nickel coated and uncoated diamond seeds were used. As in other examples, the grown diamonds had a poorer quality when using uncoated diamond seeds.

Example 7

A substantially homogenous mixture of natural graphite (20 microns) and INVAR powder (40 microns) at a 1:1.5 weight ratio were pressed at 350 MPa to form disks of 37 mm in diameter and 1 mm thick. The surface of these disks was sprayed with a thin acrylic binder. A template with holes 130 microns in diameter separated at 800 microns was placed directly on top of the binder. Diamonds (60 microns) that were coated with nickel to a size of about 120 microns were swept across the top surface of the template. Diamonds which enter each aperture are adhered to the binder on the disk. After the removal of the excess diamond and the template, the diamond implanted disks were stacked up to about 30 layers and then were placed in a steel container with one open end. The open cans were then heated to 600° C. for two hours to remove the binder. Subsequently, another steel container was used to cover the open end and the two containers pressed at 30 tons force to become tightly held. The can is then subjected to ultrahigh pressure of 5.2 GPa and 1300° C. for 50 minutes. The result showed grid distribution of diamond crystals of 30/40 mesh with negligible amount of spontaneous nucleation. The clean diamond showed yellow color and with high impact strength.

Example 8

Same as Example 7, except the diamond seeds were first adhered to a flexible tape using the template. The patterned diamond seeds were then transferred to the binder coated disks. The binder on the disk is stronger than the adhesive on the tape such that diamond particles were transferred with ease. The results were substantially the same as in Example 7.

Example 9

Same as Example 1, except the diamond seeds are adhered to a thin nickel layer (37 mm by 0.08 mm thick). The metal layer was much easier to handle during the patterned seeding process than pressed disks. The metal layer was then sandwiched between pressed disks of graphite and INVAR mixture. Yellow diamond crystals formed after the high pressure synthesis similar to Example 7.

Example 10

Uncoated diamond seeds (30 microns) were used adhered on a nickel disk using a template. The resulting grown diamonds had slightly more inclusions than Example 7, but were still yellow with high impact strength.

Example 11

The above examples can be substituted with pure graphite disks that are stacked with INVAR disks. In this case, diamond seeds adhere to the INVAR disk.

Example 12

FIG. 19A is a photomicrograph of a post-growth mass using conventional diamond growth technologies which involve forming a mixture of raw material and catalyst material. The growth conditions for this sample were a pressure of 5.2 GPa and a temperature of 1300° C. for 35 minutes. FIG. 19B is a photomicrograph of unsorted and unsized diamonds as recovered from the mass of FIG. 19A. The recovered diamonds were cubo-octahedral having a wide size distribution and poor quality. The overall diamond yield for this cell was about 2 ct/cc.
In accordance with the present invention, diamond seeds having an average size of 65 μm were coated with nickel to a final diameter of about 125 μm (e.g., see FIGS. 8A and 8B). The coated diamond seeds were arranged in a powdered mixture of graphite and INVAR (65Fe-35Ni) at a ratio of 1:1.5 using a template as described above and a multi-layered configuration similar to that shown in FIG. 17. Two separate multi-layered precursors were prepared in this manner.
FIG. 20A is a photomicrograph of a post-growth mass formed by pressing one of the multi-layered precursors at 5.2 GPa and heating to 1300° C. for 35 minutes.
FIG. 20B is a photomicrograph of unsorted and unsized diamonds recovered from the mass of FIG. 20A. The recovered diamonds were cubo-octahedral having a highly uniform size and quality distribution characterized by very few inclusions and a yellow color. The overall diamond yield for this cell was about 5 ct/cc.
FIG. 21A is a photomicrograph of a post-growth mass formed by pressing one of the multi-layered precursors at 5.2 GPa and heating to 1320° C. for 35 minutes. FIG. 21B is a photomicrograph of unsorted and unsized diamonds recovered from the mass of FIG. 21A. The recovered diamonds were octahedral having a highly uniform size and quality distribution characterized by very few inclusions and a yellow color. The overall diamond yield for this cell was about 5 ct/cc.
Each of FIGS. 19B, 20B and 21B is illustrated at the same enlargement scale. Thus, it can be seen that the average size of the diamonds using the present invention is larger than those using conventional seeding processes, as well as more uniform in crystal morphology and quality.

Example 13

Diamond crystals with faceted morphology or blocky shape having a size from 20-30 microns were coated with nickel via an electroless process to a size of 60-70 microns. Purified natural graphite powder having a grain size of about 20 microns was mixed with INVAR (Fe65-Ni35) powder having a size of about 40 microns at a weight ratio of 1:1. The mixture was pressed at about 200 MPa to form disks of 0.9 mm in thickness of various diameters, e.g. 37 mm, 61 mm, and 85 mm. A screen printer was used to spread the nickel coated diamond seeds over an adhesive pad (manufactured by 3M) of uniform thickness (1, 2, or 3 mils). The adhesive adheres to the screen that contains a predetermined grid of holes 0.9 mm apart. These holes allow coated diamond crystals to be secured on the adhesive pad to form the same predetermined pattern.
After removal of excess diamond crystals, the diamond grid formed on the adhesive pad is removed from the backing layer and glued to the pressed graphite-metal disks. The gluing may be on the back side of the adhesive pad opposite the diamond seeds or on the same side where diamond seeds are attached. Multiple layers (e.g. 40) of graphite-metal disks and patterned diamond seeds were stacked up in a steel container having a wall thickness of about 0.2 mm to form a multilayered precursor assembly. The precursor assembly was heat treated under vacuum (10̂-3 torr) at 1000° C. for 60 minutes with intermittent hydrogen purges. During cooling the stacks were purged under nitrogen gas.
The pretreated stacks were compressed at about 300 MPa to form cells for ultrahigh pressure synthesis of diamond. Subsequently, the pretreated stacks were pressed at 5.2 GPa and heated to 1300° C. for 45 minutes. The grown diamonds were recovered and examined. The diamond seeds grew to about 500 microns (30/40 mesh) with uniform size and similar shape as shown in FIGS. 22 through 26. These diamond crystals were grown with high crystal perfection and mechanical strength. The yield of diamond was over 4 carats per cubic centimeter.
FIG. 23 is a photograph of a post-growth mass having offset patterns of diamond crystals to allow more growing space for each crystal. This pattern was achieved by rotating either the screen during screen printing or rotating the adhesive pad prior to gluing to the disks. This rotational arrangement can be easily automated and can allow tighter packing of diamond seeds in the space of the high pressure cell without interference from the diamond crystals directly above and below adjacent layers.
FIG. 24 is a photomicrograph of the post-growth mass of diamond particles having a predominantly cubic morphology and an average size of about 500 μm as indicated by the bracket.
FIG. 25 is an additional photomicrograph of the post-growth mass showing cubic diamonds prior to recovery. These diamonds show a high degree of uniformity in quality, size and morphology which is uncharacteristic of conventional diamond synthesis processes. FIG. 26 illustrates a collection of unsorted diamonds having a predominantly cubic morphology produced from this example.

Example 14

The same conditions and steps were performed as in Example 13 with INVAR powder being replaced by pure Fe and Ni powder (about 6 microns) at a 2:1 weight ratio. The resulting grown diamond was of substantially the same quality and sizes.

Example 15

The same conditions and steps were performed as in Example 13 except that the heating time is extended to one hour so the diamond size increased to over 600 microns (25/30 mesh). Also, the diamond yield was over 5 carats/cubic centimeter with similar quality as in Example 14.
Thus, there is disclosed an improved method and materials for making and growing superabrasive particles with improved quality and size distributions. The above description and examples are intended only to illustrate certain potential embodiments of this invention. It will be readily understood by those skilled in the art that the present invention is susceptible of a broad utility and applications. Many embodiments and adaptations of the present invention other than those herein described, as well as many variations, modifications and equivalent arrangements will be apparent from or reasonably suggested by the present invention and the forgoing description thereof without departing from the substance or scope of the present invention. Accordingly, while the present invention has been described herein in detail in relation to its preferred embodiment, it is to be understood that this disclosure is only illustrative and exemplary of the present invention and is made merely for purpose of providing a full and enabling disclosure of the invention. The foregoing disclosure is not intended or to be construed to limit the present invention or otherwise to exclude any such other embodiment, adaptations, variations, modifications and equivalent arrangements, the present invention being limited only by the claims appended hereto and the equivalents thereof.

Claims

1. An unsorted collection of superabrasive particles produced by the steps of:

a) forming at least a portion of a growth precursor, said growth precursor including a raw material and a particulate catalyst material;

b) arranging crystalline seeds in a predetermined pattern on a layer of adhesive, said layer of adhesive being coated over at least a portion of a surface of the growth precursor; and

c) heating the growth precursor under temperature and pressure conditions sufficient to grow superabrasive particles having a preselected morphology, wherein said unsorted collection is obtained by recovering the superabrasive particles subsequent to the step of heating and without sizing or sorting of the superabrasive particles.

2. The unsorted collection of claim 1, wherein said superabrasive particles have a narrow size distribution characterized by a standard deviation of less than about 0.05 of an average size.

3. The unsorted collection of claim 1, wherein said superabrasive particles have fewer than 1 wt % inclusions.

4. An unsorted collection of superabrasive particles, comprising a plurality of superabrasive particles having a narrow size distribution characterized by greater than 95% of the superabrasive particles having a size within about 20% of an average size.

5. The unsorted collection of claim 4, wherein greater than about 70% of the superabrasive particles are cubic.

6. The unsorted collection of claim 4, wherein greater than about 70% of the superabrasive particles are octahedral.