US3871840A - Abrasive particles encapsulated with a metal envelope of allotriomorphic dentrites - Google Patents

Abrasive particles encapsulated with a metal envelope of allotriomorphic dentrites Download PDF

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Publication number
US3871840A
US3871840A US219973A US21997372A US3871840A US 3871840 A US3871840 A US 3871840A US 219973 A US219973 A US 219973A US 21997372 A US21997372 A US 21997372A US 3871840 A US3871840 A US 3871840A
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United States
Prior art keywords
metal
abrasive
tungsten
article
encapsulated
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Expired - Lifetime
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US219973A
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English (en)
Inventor
Arthur G Wilder
Harold C Bridwell
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.)
Norton Christensen Inc
Baker Hughes Oilfield Operations LLC
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Christensen Diamond Products Co
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Priority to US219973A priority Critical patent/US3871840A/en
Priority to JP11019072A priority patent/JPS5337599B2/ja
Priority to FR7241531A priority patent/FR2169573A5/fr
Priority to DE2302574A priority patent/DE2302574C3/de
Application granted granted Critical
Publication of US3871840A publication Critical patent/US3871840A/en
Priority to JP14915477A priority patent/JPS54108994A/ja
Assigned to EASTMAN CHRISTENSEN COMPANY reassignment EASTMAN CHRISTENSEN COMPANY ASSIGNMENT OF ASSIGNORS INTEREST. Assignors: NORTON CHRISTENSEN, INC., NORTON COMPANY
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B24—GRINDING; POLISHING
    • B24D—TOOLS FOR GRINDING, BUFFING OR SHARPENING
    • B24D7/00—Bonded abrasive wheels, or wheels with inserted abrasive blocks, designed for acting otherwise than only by their periphery, e.g. by the front face; Bushings or mountings therefor
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/14—Anti-slip materials; Abrasives
    • C09K3/1436—Composite particles, e.g. coated particles
    • C09K3/1445—Composite particles, e.g. coated particles the coating consisting exclusively of metals

Definitions

  • ABSTRACT Abrasive particles are improved in function by encapsulating them with a metallic envelope; preferably the envelope is made of a pure metal in dendritic crystalline form. Desirably the abrasive substrate is placed in contraction by the envelope which is heat shrunk onto the abrasive substrate. The preferred method is to deposit the metal on the substrate at an elevated temperature by contacting a vapor of the metallic compound with the substrate particle under reducing conditions.
  • the preferred primary abrasive is a diamond, and it is preferably etched before coating.
  • Superior formed abraders may be formed by metal bonding such encapsulated abrasives with a metal matrix which forms a continuous phase in which the abrasive particles may be positioned.
  • the encapsulated abrasive particle may form the primary abrasive together with a secondary abrasive which is not as hard as the primary abrasive and which may or may not be encapsulated with a metal.
  • the primary and secondary abrasive may in one form of the abrader be distributed in the continuous phase metal binder forming the matrix.
  • IZEACTolZ T T is 2 [1% ..I If
  • PATENIEDHARI 3 87 1 ,840
  • abraders have bound abrasive particles into an abrader structure, using a binder such as a resin and, in some cases, metal, which acts as the matrix to hold the abrasive particles in the abrader structure.
  • the metal in the envelope when the encapsulated particle is to be used with the metal matrix acting as a bonding agent, it is desirable that the metal in the envelope have a suitably higher melting point than the metal matrix.
  • the third advantage of the encapsulated abrasive particle of our invention when used together with a metal matrix resides in the increased rate of heat transfer from the abrasive particle resulting from the more intimate contact surface between the envelope and the substrate particle and the envelope and the metal matrix. Heat generated at the abrading surfaces, if not readily transmitted to and absorbed in the metal matrix, acting as a heat mass, will cause a local rise in temperature which may have a deleterious effect upon the life of the abrasive particle.
  • the metallic envelopes which constitute the abrasive particles of our invention employed in the novel abrader structure of our invention differ from the foregoing coatings in composition and crystalline nature.
  • the deposits of our invention are substantially pure metal envelopes, substantially free of intergranular inclusions.
  • aforesaid encapsulated abrasive of our invention by a process of chemical vapor deposition, by subjecting the abrasive particles to contact with a volatile metal compound at an elevated temperature sufficient to maintain the metal compound in vapor form and contact the vapor with a solid substrate under metal deposition conditions.
  • the coefficient of linear expansion of the metal is substantially greater than that of diamond, and their use would also have the advantage of adding a compressive force upon the diamonds to help in overcoming the tensile forces which would tend to fracture the diamond when used in an abrader structure as the abrasive particle.
  • metals may be selected, depending on the stress desired to be imparted.
  • metals listed in Table 2 and the abrasives of Table l metals having a coefficient greater than the substrate coefficient by about 5 to percent or more of the value of the coefficient of the substrate. That is, the coefficient of the metal should be about 1.05 or more, for example, up to about 7 times the coefficient of the substrate.
  • metal encapsulating materials when employing diamonds as a substrate, when we employ carbide-forming metals, we prefer to employ those which have only a limited reaction rate at the temperatures of deposition, as hereinafter described.
  • molybdenum, tungsten, tantalum, titanium, and niobium all of which are carbide formers but are unlike iron which under the conditions of deposition or the production of the abrader may result in excessive attack on the diamond forming carbides or graphite.
  • tungsten, tantalum, niobium (columbium) and molybdenum we prefer to employ diamonds, either the natural or synthetic forms, and prefer to employ tungsten as the encapsulating material, deposited under conditions to produce pure tungsten of the crystal form as described herein.
  • the metal encapsulated abrasive in abrader structures formed by metal bonding the encapsulated abrasive in a metal continuous phase matrix
  • a metal having a significantly lower melting point than the metal sheath of the abrasive substrate we prefer to limit the melting point of the metal matrix to a temperature below about 2,800 F. in order not to expose the diamonds to excessive temperature which may impair the mechanical strength of the diamonds.
  • the coefficient of thermal expansion of the metal matrix used as bonding agent is the coefficient of thermal expansion of the metal matrix used as bonding agent. Since, in general, the low melting metals and materials have high thermal expansion, in the absence of an encapsulating metal which is wetted by the molten metal, the mass of matrix on cooling would tend to pull away from the abrasive material, thus impairing the bond. It is one advantage of the encapsulating metal that the thermal expansion of the metal sheath matches more closely the thermal expansion of the metal matrix and that the interfacial tensions will tend to prevent the pulling away of the metal matrix from the metal sheath. Such metals having melting points so as to be fluid in the formation of the abrader structure, for example at temperatures below about 2,800 F. when employing diamonds are suitable.
  • the metal chosen should be fluid at the temperature at which it is desired to employ the molten metal in forming the composite abrader structure and desirably should have, when solid, ductility as measured in the terms of microhardness of below about 400 kg/mm Desirably, also, it should have a compressive strength above about 90,000 psi. and an impact strength above about 5 foot pounds.
  • the abrasive particle is a tungsten carbide or diamond particle which is attacked by nickel, cobalt or iron or alloys of these metals
  • the encapsulation of the tungsten carbide by a metal envelope of substantially higher melting point according to our invention will prevent the attack which the unencapsulated particle would otherwise suffer under the conditions of fabrication of the abrader structure.
  • unencapsulated cast tungsten carbide is attacked by iron-based or nickel-based alloys.
  • the W C tungsten carbide is attacked or dissolved in the binder, and on freezing precipitates a new phase called eta.
  • This phase is M C type carbide, and in the case of nickel binders will have the composition Ni W C.
  • Eta phase is more brittle than the original particle.
  • the particle is said to be haloed.
  • the haloed portion of particle will have a hardness 'only of about 1,500 kilograms per square millimeter, compared for example to 1,950 to 2,100 kilograms per square millimeter (Knoop) for the core of the particle.
  • a plurality of different abrasive particles are employed.
  • particles of high hardness values for example, diamonds which act on the primary abrasives
  • there is distributed in the continuous phase of the metal matrix binder a secondary abrasive of lower hardness value for example, those shown in Table l.
  • this secondary abrasive particle is to wear away preferentially thus exposing new abrasive faces of the primary abrasive particle.
  • the abrader structures thus formed are deemed selfsharpening. That is, the matrixincluding the secondary abrasive should wear away preferentially and uniformally exposing new primary abrasive cutting surfaces. This tends to reduce the area of the interfacial surfaces between the bonding metal of the matrix and the primary and secondary abrasive particles. Where the bond isweak, the particles are torn out of the metal matrix, causing excessive wear.
  • the intermetallic bond between the metal matrix and the encapsulated primary or secondary abrasive increases the retention of the abrasive particle until its cutting life is ended by wearing away of the particle or breaking away of fragments thereof from the portion of the abrasive particle which has become free of the encapsulation at the abrading surface during the abrading action.
  • the secondary abrasive we may, in order to add mass to the abrader select from the abrasive particles having suitable hardness and other desirable physical properties those having a specific gravity to give mass to the abrader; i.e., those with specific gravities substantially in excess of the abrasive substrate.
  • tungsten carbide or hafnium diboride or those of somewhat lower specific gravity, i.e. 6 or more as set forth in Table 1.
  • encapsulated secondary abrasive of suitable hardness chosen for example from the list of Table l and encapsulate the secondary abrasive with a metal of suitable specific gravity to increase the apparent density of the particle. This will permit the fabrication of an abrader having the required volume percent of secondary abrasive but impart a greater weight to the abrader structure as compared with one of like composition and volume but employing the unencapsulated secondary abrasive particle.
  • halides or the carbonyls of the metals Preferably for convenience of operation, we prefer to employ those compounds having a boiling point at atmospheric pressure below the reaction temperature.
  • encapsulated diamond in place of or in addition to the encapsulated diamond, we may use the other abrasives as described above, preferring among them encapsulated alumina but may also use the other abrasives described above, particularly encapsulated tungsten carbide or silicon carbide as is more fully described below.
  • FIG. 5 is a section taken on 55 of FIG. 2.
  • FIG. 7 is a section through a mold for the core bit shown in FIG. 8.
  • FIGS. 9-14 are photomicrographs of etched sections of metal abrasive particles contained in a metal matrix according to our invention.
  • FIG. 1 illustrated a flow sheet of our preferred process for producing the novel encapsulated abrasive of our invention.
  • the particles to be coated are placed in the reactor 1, whose cap 2 has been removed.
  • the reactor has a perforated bottom to support the particles of selected mesh size.
  • the vacuum pump is started to de-aerate the system.
  • Valve 7 is closed and the system filled with hydrogen from hydrogen storage 11, valve 5 being open.
  • the reactor is heated by the furnace 9 to the reaction temperature, for example, from about 1,000 to about 1,200 F. while purging slowly with hydrogen.
  • the hydrogen flow rate is increased until a fluidized bed is established.
  • Hydrogen prior to introduction into the reactor passes through a conventional palladium catalyst to remove any impurities, such as oxygen in the hydrogen.
  • Vaporized metallic compound is discharged from the vaporizing chamber 10, which may if necessary be heated by furnace 14, together with an inert gas, for example, argon from argon storage 6 into the reactionv chamber.
  • the reaction forms hydrogen halide, which is passed through the bubble traps and is absorbed in the absorber.
  • the volatile compound employed is a fluoride
  • the product formed is a hydrogen fluoride, and we may use sodium fluoride for that absorption.
  • the reaction deposits metal on the substrate and the effluent material, being in the vapor state is discharged, leaving no contaminants on or in the metal.
  • the metal is formed in its pure state.
  • the rate of metal deposition depends on the temperature, and flow rate of the reactants, being the greater the higher the temperature and the greater the flow rate of the hydrogen and volatile metals compound.
  • valves 4 and 5 are closed and argon is continued to pass into the reactor and the metal encapsulated abrasive is allowed to cool to room temperature in the non-oxidizing condition of the argon environment.
  • reaction products and the carrier gases and excess hydrogen enter the upper space termed the disengaging space where they are separated from any entrained particles.
  • the diamond particle is smooth as for example in the case of synthetic diamonds
  • the etching of the diamonds will also have an advantage where the metal envelope is produced by other processes such as electrochemical or electrolytic deposition methods.
  • the product produced by the process of vapor deposition described above is superior and is preferred by us.
  • hydrogen flow is established at a low flow rate of about 100 ml/min and as described above, the temperatures in the reactor 1 having been adjusted to 1,l50 F., as measured by the thermocouples, the hydrogen flow is increased to about l,250-l ,350 ml/min, and the flow of the tungsten fluoride vapor to about ml/min and the argon gas is adjusted. to about 285 ml/min, all as measured by the flow meters as indicated in FIG. 1, the hydrogen being in stoichiometric excess over the tungsten hexafluoride.
  • the thickness of the coat of the tungsten on the diamond depends on the duration of the treatment and suitably for the 40 to 50 mesh diamonds described above, the coat will be 1 mil. thick in about 1 hour. Suitable thickness deposit will run from about 0.1 to about 1.5 mils thick.
  • the substrate surface is completely coated, indicating that the process of vacuum chemical vapor deposition has great throwing power.
  • the metal coated particles may be employed in producing improved abrader structures by any of the techniques previously used with unencapsulated abrasive particles. These include what have become known as surface set, infiltration, hot pressing, and flame metalizing procedures.
  • a surface set oil well drill (see FIGS. 7 and 8) (such as described in the Austin Pat. No. 2,838,284) may be formed in a graphite mold which is formed with sockets positioned in the interior surface of the mold adjacent to the boring surface of the drill to be formed in the mold.
  • a steel shank is positioned in the mold spaced from the interior surfaces of the mold.
  • a matrix composed of a mixture of sized particles of cast tungsten carbide as the secondary abrasive and a powdered metal such as nickel or tungsten. This mixture extends in the mold above the surface on which the diamonds are deposited.
  • the grain size of the tungsten carbide is chosen to give the proper compaction and void volume; for example, in the range of 35 to 75 percent of the total volume, e.g., -30 60 mesh such as described abovefThe mold is vibrated to compact the tungsten carbide particles.
  • tungsten coated diamonds prepared according to the process previously described, having a coating, for example, of about half a mil or more, e.g. l to 1.5 mils.
  • tungsten carbide we may employ as the secondary abrasive any of the other abrasives other than diamonds listed in Table l, or the aforesaid second abrasive particles encapsulated in a metal capsule, as described above, for example, alumina coated with tungsten according to the above procedure.
  • Abrader elements may also be produced by an impregnation technique by mixing the primary and secondary abrasive materials in powder form, vibrating or packing the mixture in a suitable mold, and infiltrating the mixture with a low-melting binder metal alloy as described above.
  • FIGS. 2 and 5 show a suitable graphite mold for use in such techniques for producing saw blade segments to be brazed to a saw blade.
  • the mold is composed of a base 101, the mold proper 102, with an anchor 103, carrying a funnel 104, clamped by clamp bolt 105, and covered with a furnace cap 106.
  • the mold proper consists of circumferentially space mold cavities having substantially smaller circumferential extension than their radial length.
  • the primary abrasive for example, a mix of diamond particles 20 45 or 45 60 mesh screen and powdered tungsten carbide is tamped into the mold 102.
  • the funnel contains a bronze-copper-tinalloy powder through a 200 mesh screen.
  • Example 8 The process of Example 7 and the product then produced may also be carried out by replacing the tungsten carbide with a metal coatedtungsten carbide for example tungsten carbide coated with tungsten metal or other tungsten coated secondary abrasive such as alumina or silicon carbide.
  • a metal coatedtungsten carbide for example tungsten carbide coated with tungsten metal or other tungsten coated secondary abrasive such as alumina or silicon carbide.
  • sections of about 1 /8 inches long, one-eighth inch wide, and about five thirty-seconds inch thick may be formed suitably by introducing about 3,500 stones of mesh size 45 60 grit or about 1.1 carats of diamonds grit. (See FIG.
  • Example 9 The mold employed is shown in FIGS. 4 and 3. The mold is similar to that of FIG. 2 except that no funnel is employed and the nut 105 is now a plug 107 and the funnel 104 is replaced by the cap 108 in place of cap 106. The mold is formed for the insertion of the cap as shown. The mold is placed in a press and heated for example in an induction furnace.
  • a mixture of tungsten metal power, powdered tungsten carbide 35 50 mesh diamond grit which has been coated with a 10 micron tungsten metal envelope as described above is mixed with a 200 mesh bronze-tin alloy and tamped into the mold of FIG. 4.
  • Theconcentration of diamonds in the mix may be suitably about 25 percent.
  • the mold is heated to about 1,600 F. at about 3,000 p.s.i. pressure to produce the saw blade element.
  • tungsten carbide instead of tungsten carbide, we may use tungsten coated tungsten carbide or other metal coated secondary abrasive described above, for example, tungsten coated alumina or silicon carbide.
  • the higher melting metals as binder matrix such as iron, cobalt, nickel or alloys of these metals and heat the hot press mold to temperatures as high as above l,535 F. depending on the melting point of the metal selected to form the binder.
  • FIG. 9 which shows a 0.025 inch tungsten coat on an aluminum oxide particle in the metal matrix at 140 X magnification and having an apparent density of 9.3 grams per cubic centimeter.
  • FIG. 10 shows a similar tungsten coated alumina particle in a metal matrix at 280 X magnification.
  • FIG. 11 shows a tungsten coated diamond particle hot pressed into a metal matrix at 210 X magnification.
  • FIG. 12 shows a portion of the particle at 840 X magnification.
  • FIG. 13 shows mesh silicon carbide particle coated with tungsten hot pressed into a metal matrix at 280 X magnification.
  • FIG. 14 shows tungsten coated A1 0 hot pressed in a metal matrix at 1700 F., polished and etched at 560 X magnification to show the allotriomorphic dendrite crystal structure.
  • An article of manufacture consisting of abrasive particles having a hardness of above about 2000 kg/mm encapsulated with a metal envelope formed of allotriomorphic dendrites.
  • abrasive particles are chosen from the group consisting of diamonds, tungsten carbide, alumina and silicon carbide.
  • the encapsulated metal is chosen from the group consisting of tungsten, tantalum, columbium (niobium) and molybdenum.
  • the abrasive has a coefficient of linear expansion in the range of about 1 X 10 inches per inch per degree Fahrenheit to about 5 X 10" inches per inch per degree Fahrenheit and said metal has a linear coefficient of expansion in the range of from about 2 X 10 to about 10 inches per inch per degree Fahrenheit and in which the linear coefficient of expansion of said metal is in the range of from about 1.05 to about 7 times the linear coefficient of expansion of said unencapsulated particle.
  • abrasive particles are chosen from the group consisting of diamonds, tungsten carbide, alumina and silicon carbide.
  • the encapsulated metal is chosen from the group consisting of tungsten, tantalum, columbium (niobium) and molybdenum.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Composite Materials (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Polishing Bodies And Polishing Tools (AREA)
US219973A 1972-01-24 1972-01-24 Abrasive particles encapsulated with a metal envelope of allotriomorphic dentrites Expired - Lifetime US3871840A (en)

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US219973A US3871840A (en) 1972-01-24 1972-01-24 Abrasive particles encapsulated with a metal envelope of allotriomorphic dentrites
JP11019072A JPS5337599B2 (pt) 1972-01-24 1972-11-02
FR7241531A FR2169573A5 (pt) 1972-01-24 1972-11-22
DE2302574A DE2302574C3 (de) 1972-01-24 1973-01-19 Schleifmittel und Verfahren zu seiner Herstellung
JP14915477A JPS54108994A (en) 1972-01-24 1977-12-12 Polishing instrument

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US4108614A (en) * 1976-04-14 1978-08-22 Robert Dennis Mitchell Zirconium layer for bonding diamond compact to cemented carbide backing
US4110084A (en) * 1977-04-15 1978-08-29 General Electric Company Composite of bonded cubic boron nitride crystals on a silicon carbide substrate
US4142869A (en) * 1973-12-29 1979-03-06 Vereschagin Leonid F Compact-grained diamond material
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DE2302574B2 (de) 1979-10-31
DE2302574C3 (de) 1980-07-10
JPS5337599B2 (pt) 1978-10-09
JPS4886189A (pt) 1973-11-14
JPS54108994A (en) 1979-08-27
FR2169573A5 (pt) 1973-09-07
DE2302574A1 (de) 1973-08-02

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