EP0111558A1 - Procede de production de particules de diamant presentant une morphologie selectionnee - Google Patents

Procede de production de particules de diamant presentant une morphologie selectionnee

Info

Publication number
EP0111558A1
EP0111558A1 EP83902351A EP83902351A EP0111558A1 EP 0111558 A1 EP0111558 A1 EP 0111558A1 EP 83902351 A EP83902351 A EP 83902351A EP 83902351 A EP83902351 A EP 83902351A EP 0111558 A1 EP0111558 A1 EP 0111558A1
Authority
EP
European Patent Office
Prior art keywords
silicon carbide
particles
diamond
microns
shape
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP83902351A
Other languages
German (de)
English (en)
Other versions
EP0111558A4 (fr
Inventor
Cressie E. Holcombe Jr.
James B. Condon
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
CONDON James B
Original Assignee
CONDON James B
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by CONDON James B filed Critical CONDON James B
Publication of EP0111558A1 publication Critical patent/EP0111558A1/fr
Publication of EP0111558A4 publication Critical patent/EP0111558A4/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/90—Carbides
    • C01B32/914—Carbides of single elements
    • C01B32/956—Silicon carbide
    • C01B32/963—Preparation from compounds containing silicon
    • C01B32/977—Preparation from organic compounds containing silicon
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/25—Diamond
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/25—Diamond
    • C01B32/26—Preparation
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/90—Carbides
    • C01B32/914—Carbides of single elements
    • C01B32/956—Silicon carbide
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/90—Carbides
    • C01B32/914—Carbides of single elements
    • C01B32/956—Silicon carbide
    • C01B32/963—Preparation from compounds containing silicon
    • C01B32/984—Preparation from elemental silicon
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/10—Particle morphology extending in one dimension, e.g. needle-like
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer

Definitions

  • the field of this invention is generally that relating to the preparation of materials useful in grinding and polishing and the like, and more particularly to a process for producing diamond particles for these uses.
  • Man-made diamond particles are produced by several processes known in the art. For example, commercial grade diamond particles have been produced at 130 kilobars and 3000° C. In another process, using nickel or iron as a catalyst, such particles are produced at 27 kilobars and 1400° C. The products of these high temperature processes are generally referred to as General Electric-type diamonds because the General Electric Co. utilizes such processes.
  • An additional process for preparing commercial grade diamond particles involves the shock-wave synthesis of the diamond particles under conditions achieving from 0.3 to 1.5 megabars pressure at about 1000 to 2000° C. This is a process generally utilized by E. I. DuPont and Company and therefore such particles are referred to as DuPont-type diamonds.
  • Still another process for the production of commercial grade diamond particles is that disclosed in our Patent No. 4,228,142, issued October 14, 1980. This patent is incorporated herein by reference.
  • the particles are found to be rather blocky in shape and some appear to be single crystals.
  • Other parti ⁇ cles are polycrystalline.
  • the polycrystalline diamond particles exhibit multi-edges and therefore generally are considered to be a preferred type for polishing and grinding.
  • Diamond particles in the polishing range that are produced by these processes are typically in the range of 0.5 to about 85 microns and these are referred to as micron powder.
  • the size range of diamond particles in the grinding range is typically from 85 to 850 microns and is often referred to as diamond grit.
  • Various sizing techniques are used to separate the particles so that very uniform particle size fractions are available.
  • the smaller sized precision graded particles are utilized for finish grinding, lapping and polishing, while the larger sizes are used in grinding, sawing or drilling applications, often incorporated in or bonded to cutting tools.
  • particles of other specific shapes have advantages for various applications.
  • One such shape or morphology is that of fibers as
  • V. r i? used for strengthening materials Methods are known for the growing of experimental filamentary diamond crystals. Such crystals possess very high strength. These filamentary crystals are grown upon a seed diamond single crystal as a substrate (see, for example, Jl. of Crystal Growth, 2_, p. 380, 1968). Each seed crystal is individually supported, and the filamentary diamond crystal is grown epitaxially in a carbon-containing gas phase. The large scale production of such diamond fibers, is therefore, impractical by these methods.
  • a beginning structure which may be organic, is chosen or fabricated having the shape of the intended diamond particle. Thereafter, this structure is converted to be substantially beta silicon carbide having the desired structure. This silicon carbide is then converted to diamond using the process dis ⁇ closed in our ⁇ . S. Patent No. 4,228,142 or an equivalent low temperature, low pressure process.
  • diamond particles can be prepared by the reaction of a fluorocarbon with silicon carbide in a temperature range of about 800 to 1200° C.
  • a preferred tempera ⁇ ture of about 1000° C provides for the optimum production of the diamond particles.
  • the reaction appears to proceed more readily when the silicon carbide is in the beta phase (cubic close packed) rather than the alpha phase (hexagonal) .
  • the presence of iron or nickel as a promoter is also beneficial.
  • the reaction range may be extended with an attendant increase in reaction velocity (see "Physical and Mechanical Properties of Diamond", H. B. Dyer, Proceedings: Ind. Diamond Conf. , P.I, 1967) .
  • Silicon carbide is available from many sources in the industry. It is used, for example, in many high temperature applications. Also, fibers of SiC are used in the strengthening of aluminum.
  • One conventional method for the production of silicon carbide is through the use of rice hulls. Rice hulls are a unique waste product of agriculture.
  • the rice kernel along with its hulls, contains a high carbon content as well as a high silica (Si0 2 ) content.
  • Si0 2 silica
  • These rice hulls are heated at a temperature of about 1820° C, they are converted to silicon carbide because of this carbon and silicon content.
  • This method of forming silicon carbide from rice hulls is described in U. S. Patent Nos. 3,754,076 and 4,248,844.
  • the resultant product has several forms of morphology including needles, blocky pieces, rough surfaced cylinders and the like.
  • the needles may be separated from the total silicon carbide by a flotation process and then may be used in applications where they provide strengthening to metal matrices, etc.
  • the remaining configurations of the silicon carbide from the needle production are considered waste product but are useful in other applications.
  • Silicon carbide is also conventionally produced using other source ingredients.
  • the silicon portion is derived from such materials as silicon metal, various silicates, silica, silicic acid, silicones, and naturally occurring substances such as diatoma- ceous earth, radiolaria, etc.
  • the carbon sources are typically coke, graphite, charcoal, resins, carbon black, natural carbonaceous materials, etc.
  • SiC particles of various sizes and shapes result and are primarily beta-type. Typical of these other methods are disclosed in U. S. Patent Nos. 4,133,689 and 4,162,167.
  • U. S. Patent No. 3,927,181 describes the preparation of hollow spheres of SiC
  • U. S. Patent No. 3,726,737 describes the preparation of "corrugated paper" SiC.
  • the waste product from the rice hull method of preparing silicon carbon needles or fibers was investigated as an inexpensive source of silicon carbide for the production of diamond particles via metathesis using fluorocarbons according to process of U. S. Patent 4,228,142.
  • An x-ray diffraction analysis of the silicon carbide indicated that the ratio of beta phase to alpha phase silicon carbide was approximately 2:1. Further analysis indicated that the material had approximately 25% carbon, 25% alpha phase silicon carbide and 50% beta phase silicon carbide.
  • the yield efficiency of this reaction was calculated to be 17.4% based on the amount of beta-type silicon carbide in the powder and taking into account the free carbon, iron and alpha silicon carbide, and the amount of the ⁇ tarting beta silicon carbide in the powder.
  • An x-ray diffraction study of the product showed the existence of diamonds and some graphite possibly entrained within the diamond particles during formation. These diamond particles were black, probably due to this graphite.
  • diamond needles may be prepared from needle-like silicon carbide which may be used for the strengthening of various composites in the same manner as the silicon carbide has been used in the past.
  • very porous diamond structures that can be achieved from porous SiC will permit a more complete bonding to any matrix for grinding wheels and the like.
  • Very rough diamond particles can be used in the grinding art, and the very small particles of diamond can be used for polishing applications. This, therefore, makes possible the formation of diamond particles of various sizes and shapes at a relatively low temper ⁇ ature and at normal pressures.
  • any organic material can be heated in an inert atmosphere, such as argon, to give a carbon residue. Since the shape of the organic material is often retained, it is therefore possible to tailor the carbonized particle shape.
  • Solid or hollow starting materials may be used.
  • the body may be dipped in silica gel, ethyl silicates, silicic acid, methyltrichlorosilane (MTS) liquid, sodium silicate or other silica- or silicon -containing material before or after carbonization which would then react with the carbon body to form silicon carbide. If MTS liquid is used, it rapidly reacts with moisture in the air to form a silicon-containing film or crust.
  • MTS methyltrichlorosilane
  • alpha silicon carbide can be converted to the beta phase by heating in a nitrogen atmosphere of about 3MPa (435 psi) at about 2500°C (see Communi ⁇ cations of the Am. Cer. Soc. , C-177,1981). This step of producing the beta silicon carbide would enhance the formation of the diamond particle since, as stated above, the beta silicon carbide reacts more readily to form diamonds.
  • the present invention is not limited to the use of silicon carbide made from naturally occuring materials.
  • a specific shape may be constructed by extrusion, stamping, molding and the like of the necessary Si and C ingredients. The conversion then produces the SiC having the desired shape which may then be converted to diamond having that same shape.
  • methyltrichlorosilane decomposes to beta silicon carbide above 1000° C, it will be possible to produce at least a coating of beta silicon carbide by chemical vapor deposition methods upon almost any shaped particles (mandrels) in a fluidized bed. Then using, for example, the carbon tetrafluoride reaction, diamonds of that shape could be produced. This method would permit the preparation of diamond particles of larger size than may be possible using the complete silicon carbide metathesis reaction process.
  • Diamond particles of a size from a few microns up to several hundred microns can be produced using the above described methods.
  • the starting material i.e. , silicon carbide
  • the product will contain diamond particles having this same wide range of sizes and shapes.
  • a sizing and shape sorting step may be added to separate these specific sizes and/or shapes after the diamonds are formed.
  • a sizing and shape selection may be performed on the initial silicon carbide. In this way, the process is made more efficient in that only those sizes and shapes which are desired are present to react with the gas used for the conversion. In either case, a leaching and density separation step may be necessary to retain only the diamond portion of the reaction products.
  • O more particularly carbon tetrafluoride other gases are believed to be useful in carrying out the present invention.
  • fluorine atoms may be substituted with other halogen atoms to achieve the conversion of silicon carbide to the diamond.
  • halocarbons may be suitable for use with the present invention. These will include a multiple combination of carbon .with fluorine, chlorine, bromine, iodine .and/or hydrogen. Several such gaseous combinations are more readily available at lower costs than the carbon tetrafluoride.
  • halocarbon used in the process should not decompose at temperatures up to that used for the conversion of the silicon carbide to diamond unless the decom ⁇ position yields a halocarbon phase which reacts with silicon carbide to produce the diamond form.
  • Certain forms of solid halocarbons, e.g. Teflon, may also be used when an effective gaseous halocarbon results at the reaction temperature.
  • diamond particles of a wide range of sizes and shapes may be produced.
  • the particular shape is controlled by the shape of the silicon carbide body which is subjected to the metathesis conversion to diamond. Accordingly, a particularly shaped diamond particle is produced by intentionally forming a silicon carbide particle of that particular shape. The diamond is formed by subjecting the silicon carbide particle to a halo-
  • suitable diluent gases helium, argon, nitrogen, hydrogen, etc.
  • inert filler materials such as excess carbon in some form.
  • the resultant diamond particles are then useful according to their size and shape as well as to the external surface of these shapes. They may be tailored to particularly achieve the desired result in the art of strengthening, grinding, polishing, etc.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Carbon And Carbon Compounds (AREA)

Abstract

Procédé de production de particules de diamant possédant des formes et des tailles prédéterminées. Le procédé consiste à former des particules de carbure de silicium, ou des particules convertibles en carbure de silicium, qui sont ensuite soumises à l'action d'un gaz halogéné non décomposable à des températures comprises entre 800 et 1200oC, le carbure de silicium étant converti par une étape de métathèse en particules de diamant correspondantes. Les particules de diamant résultantes présentent des tailles allant de quelques microns à plusieurs centaines de microns et une gamme de forme comprenant des aiguilles, des fibres, des matériaux en vrac ainsi que des particules de diamant poreuses, suivant les formes des particules de carbure de silicium. De préférence, le carbure de silicium devrait avoir la forme de phase béta de manière à accroître le rendement de la réaction. Plusieurs variantes à ce procédé sont décrites pour la préparation initiale des particules de carbure de silicium qui sont utilisées dans la conversion.
EP19830902351 1982-06-07 1983-06-05 Procede de production de particules de diamant presentant une morphologie selectionnee. Withdrawn EP0111558A4 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US38568982A 1982-06-07 1982-06-07
US385689 1982-06-07

Publications (2)

Publication Number Publication Date
EP0111558A1 true EP0111558A1 (fr) 1984-06-27
EP0111558A4 EP0111558A4 (fr) 1984-10-16

Family

ID=23522453

Family Applications (1)

Application Number Title Priority Date Filing Date
EP19830902351 Withdrawn EP0111558A4 (fr) 1982-06-07 1983-06-05 Procede de production de particules de diamant presentant une morphologie selectionnee.

Country Status (4)

Country Link
EP (1) EP0111558A4 (fr)
IL (1) IL68820A0 (fr)
WO (1) WO1983004408A1 (fr)
ZA (1) ZA839325B (fr)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU5725294A (en) * 1992-10-02 1994-04-26 Penn State Research Foundation, The Method for synthesizing solids such as diamond and products produced thereby
US6342195B1 (en) 1993-10-01 2002-01-29 The Penn State Research Foundation Method for synthesizing solids such as diamond and products produced thereby
US9229162B1 (en) * 2006-10-13 2016-01-05 Hrl Laboratories, Llc Three-dimensional ordered diamond cellular structures and method of making the same
US9086229B1 (en) 2006-10-13 2015-07-21 Hrl Laboratories, Llc Optical components from micro-architected trusses
US9546826B1 (en) 2010-01-21 2017-01-17 Hrl Laboratories, Llc Microtruss based thermal heat spreading structures
US9758382B1 (en) 2011-01-31 2017-09-12 Hrl Laboratories, Llc Three-dimensional ordered diamond cellular structures and method of making the same

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3310501A (en) * 1962-12-31 1967-03-21 Gen Electric Preparation of elongated needle-like diamond having electrically conductive properties
US4228142A (en) * 1979-08-31 1980-10-14 Holcombe Cressie E Jun Process for producing diamond-like carbon
JPH0422047A (ja) * 1990-05-15 1992-01-27 Mitsubishi Electric Corp ミリ波発生装置

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
No further documents disclosed *
See also references of WO8304408A1 *

Also Published As

Publication number Publication date
ZA839325B (en) 1986-01-29
WO1983004408A1 (fr) 1983-12-22
EP0111558A4 (fr) 1984-10-16
IL68820A0 (en) 1983-09-30

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