WO1983000038A1 - Production de particules ultra-dures - Google Patents

Production de particules ultra-dures Download PDF

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Publication number
WO1983000038A1
WO1983000038A1 PCT/US1981/000866 US8100866W WO8300038A1 WO 1983000038 A1 WO1983000038 A1 WO 1983000038A1 US 8100866 W US8100866 W US 8100866W WO 8300038 A1 WO8300038 A1 WO 8300038A1
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WO
WIPO (PCT)
Prior art keywords
ultra
hard particles
group
integer
melt system
Prior art date
Application number
PCT/US1981/000866
Other languages
English (en)
Inventor
Frederic A French
Douglas A French
Original Assignee
French, Frederic, A.
French, Douglas, A.
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 French, Frederic, A., French, Douglas, A. filed Critical French, Frederic, A.
Priority to PCT/US1981/000866 priority Critical patent/WO1983000038A1/fr
Priority to JP56502412A priority patent/JPS58501430A/ja
Priority to EP19810901985 priority patent/EP0081487A4/fr
Publication of WO1983000038A1 publication Critical patent/WO1983000038A1/fr

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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
    • C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30

Definitions

  • This invention relates to the production of ultra-hard particles composed substantially of carbon as the dominant element.
  • MPI promote diamond growth.
  • temperatures in the vicinity of 1300°K. and pressures on the order of 10 ⁇ to 10 ⁇ atmospheres were found to be required.
  • prior techniques employed in the fabrication of synthetic diamonds and other ultra-hard carbonaceous materials are at best cumber ⁇ some and expensive to carry out.
  • the maintenance of any extremes in temperature and pressure requires enormous energy and sophisticated equipment, which in turn detracts from the widespread commercialization of synthetic diamond fabrication.
  • ultra-hard carbonaceous particles can be produced from the reaction of a metal carbide such as aluminum carbide (Al.C.) or beryllium carbide (Be-C) when reacted with halogens and related halocompounds. Care has been exercised to minimize or eliminate the presence of substances which would react parasitically with carbon or the reactants, such as oxygen and oxygenated compounds with oxidizing power.
  • the reactions have tended to produce very hard and strong, covalently bonded lattice structures under highly exothermic conditions at moderate temperatures. The reactions have been accomplished at relatively low temperatures (a few hundred degrees C) and at low pressures (a few atmospheres or less).
  • the aluminum carbide or the beryllium carbide used in the invention must be rela ⁇ tively free of impurities, particularly carbon. If free carbon is present in the metal carbide, graphite nucleation may occur and this greatly diminishes the yield of ultra-hard carbon particles. For this reason, aluminum carbide or beryllium carbide starting materials are selected which possess slightly greater stoichiometric aluminum or beryllium to carbon ratios than are indicated by the formulae A1.C-. or Be 2 C. The physical forms of the aluminum carbide or beryllium carbide are not absolutely critical in carrying out the present invention. However, the various reactions
  • OM?l occur more rapidly with finely divided particles in the 50-500 mesh range.
  • the reaction is carried out in a hot melt system.
  • the melt system is comprised of a molten solution of more than one metal halide wherein the metals are selected from the group consisting of Groups I, II and III of the periodic table and the halides are selected from the group consisting of chlorine, bromine, iodine and fluorine.
  • oxidizing anions such as sulfates, nitrates and carbonates and hydrogen contain ⁇ ing anions such as hydroxides should be avoided in the melt system.
  • the melt system performs several valuable func ⁇ tions in carrying out the present invention. Firstly, it provides for a reaction medium at a temperature substantially below temperatures at which diamond to graphite reversion occurs at a measurable rate. Secondly, it acts as a heat sink.
  • a melt system comprised of lithium chloride (LiCl) combined with aluminum chloride (AlCl ⁇ ) is fluid at a temperature as low as 150 C C.
  • the melt system can be composed of an aluminum halide (A1X.,, where X represents Cl, Br or I although some F may also be present), complexed with one or more metallic halides such as alkaline halides and alkaline earth halides.
  • the predomi- nant melt species are L —i , A1C1.—, and Cl-. If the ratio is high, a solid LiCl phase or Li ⁇ AlCl ⁇ may be present. If the molar ratio of LiCl:AlCl-. is less than 1:1, including as high as approximately 1:2, the pre ⁇ dominant melt species are Li " " " " , A1C1, , and Al-Cl., . Br may be substituted wholly or partially for Cl. Some fluorine, iodide or iodine may be present in free form or in the aluminum-containing anions in either the
  • melt system to function in the present invention, must have solvency capability for aluminum oxide, aluminum oxygen complexes and hydrogen- containing aluminum oxygen complexes.
  • the melt system must also have the ability to wet the metal carbide surface and must have the ability not to destroy the carbon halide reactants or the metal carbide. It must also be substantially anhydrous and substantially free of hydroxyl groups.
  • the present invention can be carried out at pressures betvfeen approximately 0.1 to 100 atmospheres.
  • the reaction should take place at a pressure less than the pressure where diamond would be the stable form of carbon if the reaction was allowed to reach equilibrium, approximately 20,000 atmospheres.
  • the optimum temperature range would depend upon the actual compounds used to make up the melt and as primary reactants. As a general rule, temperatures between approximately 100" to 700°C are to be used in carrying out the reaction noting that the temperature must be high enough to at least maintain the melt system in a liquid state.
  • OMPI Example 1 The melt system is formed by the preparation of a solution of mixed halides which are heated for a suf ⁇ ficient time to insure that substantially all hydrogen and hydrogen chloride have been purged from the system.
  • 24.5 g of anhydrous LiCl was heated in a 500 ml flask at approximately 130-140°C for two days.
  • Approximately 67 g of anhydrous A1C1-. was then added under an argon blanket, the temperature elevated to approximately 250°C and the mixture stirred for 35 minutes at which time very little HC1 was evident.
  • the metal carbide was added.
  • 2.9 g of Al.C as added and held briefly.
  • the halogen-containing reactant can then be added to the solution fay stepwise additions until an excess is present.
  • 1 ml portions of CC1. were added every ten minutes to a total of 10 is followed by further 2 ml additions at ten minute intervals.
  • the temperature was main- tained at approximately 265°C throughout the CCL. additions and the suspension allowed to cool slightly thereafter.
  • Example 2 OMPI Exa ple 2 To the same melt system as developed in Example 1 was added, in addition to the aluminum carbide, approx ⁇ imately 2 g of KBr. CC1. remained as the halogen reactant and was added in a stepwise fashion much, as was done in Example 1. The final ultra-hard carbon ⁇ aceous product was washed and dried, again, as was done in Example 1.
  • Example 3 The melt system was the same as Example 1 while the reactants included aluminum carbide and CBr 4 ⁇ . More specifically, after the l 4 C 3 was added to the hot melt, 1 g of CBr. was added followed by 10 is of CC1 4 in 0.5 ml portions every five minutes. The ultra-hard carbonaceous product was washed as done in Example 1.
  • the melt 'system was prepared as in Example 1 and aluminum carbide was chosen as a first reactant.
  • the remaining reactants included 1 g of CBr 4 and a total of 13.6 g of C-Cl.- added in 1.7 g portions every five minutes.
  • the ultra-hard carbonaceous particles were washed and dried as in Example 1 producing the final product according to the following reaction:
  • Example 2 To the melt system prepared as in Example 1 was added 2.9 g of Al.C, and 2 g of FeS in 18 mg of NaCl as a nucleating agent. These latter ingredients were mixed in the melt system for approximately ten minutes followed by the addition of 1 g of CBr 4 and
  • the melt system was prepared as in Example 1 to which was added 2.9 g of 1 4 C 3 and 20 rag of ten percent FeS in NaCl as a nucleating agent.
  • the fluid reaction mixture was stirred at approximately 240 ⁇ C for 15 minutes after which a total of 24 g of CBr 4 was added in 2 g portions every 5 minutes.
  • the reaction proceeded according to the following equation: A1 4 C 3 + 3CBr > 4AlBr 3 + 6C and the ultra-hard carbonaceous particles were filtered, washed and dried according to the manner employed in Example 1. *
  • Example 7 The melt system was formed by mixing 10 g of powdered KBr, 21 g of LiCl and approximately 67 g of A1C1 3 . The mixture was heated to approximately 240°C and stirred for 1 hour under argon. To the melt system was added 20 mg of HgCl 2 as a possible catalyst to which 2.9 g of Al 4 C 3 was added. After waiting 5 minutes, ' ap -p mroximatelJy 1 ml of C2,C14, was added to the hot melt. The solution was allowed to reflux and, after 10 minutes, 1 g of CBr 4 was added. Then, at 10 minute intervals, 1 ml p ** ⁇ ortions of C2.C14. were added until a total of 9 ml were in the system. The reactants were heated for 45 minutes, filtered, washed and dried as in Example 1. The reaction proceeded according to the following equation:
  • Example 1 The melt system of Example 1 was prepared and to it was added 2.9 g of Al 4 C 3 and 20 g of ten percent
  • the second reactant was made up of 8 ml Br 2 which was added in 0.4 ml portions at 5 minute intervals.
  • the reaction products were filtered, washed and dried as in Example 1 produc- ing a product according to the following equation:
  • Example 9 A melt system was prepared according to Example 1 with the addition of 5 g of KI. To this was added approximately 2.88 g of 1 ., at 250°C which was reacted with CC1 4 added to the system every five minutes in 0.5 * ml amounts totaling 20 additions. The reaction produced ultra-hard particles which were filtered, washed and dried according to the procedure of Example 1.
  • Example 10 A melt system was prepared according to Example 1 with the addition of 5 g of NaF. To the melt system was added approximately 2.88 g of finely ground Al 4 C 3 to which was added CC1 4 in 1 ml amounts every ten minutes totaling 12 additions. The reaction product was filtered, washed and dried according to.Example 1 producing the ultra-hard carbonaceous materials of this invention.
  • Example 11 A melt system comprised of 42 g of LiCl and 134 g of A1C1 3 was prepared as per Example 1 to which 5.76 g of 1 4 C 3 having a -270 mesh size was added. At a starting temperature of approximately 236 ⁇ C, Freon 11 (CC1 3 F) was added in 1 ml amounts every five minutes totaling 23 additions. The reaction product was fil ⁇ tered, washed and dried according to Example 1 produc ⁇ ing the ultra-hard carbonaceous materials of the present invention.
  • Example 12 The melt system of Example 1 was prepared to which approximately 2.88 g of A1 4 C 3 was added having a -270 mesh at 242°C. Chlorine gas was then bubbled into the hot melt system at a rate of 0.05 cubic feet per hour for 1/2 hour. The rate was then increased to 0.1 cubic feet per hour for the next 2-1/2 hours amounting to a total ch ⁇ Orine addition of 10.7 liters. The reac ⁇ tion product was filtered, washed and dried as was shown in Example 1 producing ultra-hard carbonaceous particles according to the present invention.
  • Example 13 A new melt system was prepared by placing 29.2 g of NaCl in a flask which was heated to 180°C under vacuum for 2 hours and which was allowed to stand overnight under full vacuum. With mechanical stirring under an argon blanket, 67 g of A1C1-. was added to complete the melt system. To this melt was added
  • Example 14 A new melt system was prepared by placing 37.3 g of KC1 in a flask which was heated at full vacuum to 180°C for 2 hours. The KC1 was maintained at full vacuum overnight and, under mechanical stirring, 67 g of A1C1-. was then added to complete the melt. Approxi ⁇ mately 2.88 g of Al 4 C 3 was then added, which was reacted with CC1 4 which was in turn added in 1 cc amounts every 10 minutes to a total of 13 additions. As in Example 13, the temperature was maintained above 300°C producing a reaction product which was filtered, washed and dried according to Example 1. The reaction produced ultra-hard carbonaceous particles according to the present invention.
  • Example 2 To the melt system prepared according to Example 1 was added 2.88 g 3 of A14.C3- which was reacted with CC12_F2 congestion at a rate of 0".1 cubic feet per hour. The temperature was maintained between 230°-245°C while the CC1_F 2 was bubbled into the system for 2 hours. At the end of these additions, the reaction product was filtered, washed and dried according to Example 1 yielding ' ultra- hard carbonaceous particles according to the present invention.
  • a melt system according to Example 1 was prepared. At a temperature of approximately 247 ⁇ C, 2.88 g of Al 4 C, was added and reacted with CC1_F_ which was introduced into the hot melt system at a rate of 0.1 cubic feet per hour for 4 hours. The temperature was maintained at approximately 238°C producing a reaction product which was filtered, washed and dried and which was in the nature of ultra-hard carbonaceous particles.
  • Example 17 A melt system according to Example 1 was prepared. To this was added approximately 2.9 g of A1 4 C, and 20 mg of 10 percent FeS in NaCl, which was heated for an additional 15 minutes. A second reactant comprising CHBr 3 was added in 0,5 ml intervals every five minutes to a total of 7.0 ml. The reaction product was fil ⁇ tered, washed and dried producing ultra-hard carbona ⁇ ceous particles according to the following equation: Al 4.C3, + 4CHBr3-, ⁇ ' 4AlBr3_, + 6C + CH4.
  • Example 18 To the melt prepared according to Example 1 was added 1.5 g of 1 4 C 3 and 20 mg of FeS in NaCl. A second reactant comprising CH-I- was added every five minutes in 0.5 ml amounts with refluxing until a total of 5 ml had been added. The product was then washed and dried producing ultra-hard carbonaceous particles according to tfhe following reaction:
  • ultra-hard carbonaceous particles can be produced as the product of a reaction of a metal carbide selected from the group consisting of l 4 C 3 and Be ⁇ C with a member selected from the group consisting of CH n X A Z (4-n)-A' C 2 H n ,X ,Y (6-n' )-A- ' C 2 H n" X A" Y (4-n ⁇ ⁇ -A ⁇ and X 2 wherein X and Y are different halogens selected from the group consisting of chlorine, bromine, iodine and fluorine, and wherein A is an integer from 0 to 4,
  • a * is an integer from 0 to 6 and A" is an integer from 0 to 4, and wherein n is an integer from 0 to 4, n' is an integer from 0 to 6 and n" is an integer from 0 to
  • reaction energy was found to be enormously favorable and more than 100 times as great per carbon atom as the graphite-carbon interconversion energy.
  • the reaction was carried out in a hot melt system comprised of a molten solution of more than one metal halide wherein the metals are seldcted from the group consisting of Group I, Group II and Group III metals of the periodic table and the halides are selected from the group consisting of chlorine, bromine, iodine and fluorine.
  • the present invention also contemplates the use of nucleating agents with lattice constants as close to that of diamond. For example, very fine particles of FeS, Cu, of diamond itself may be employed.
  • the present invention also contemplates the use of a catalyst such as I 2 .
  • OMPI Corundum or carborundum as fine grits or powders yield, at most, short grooves. These abrasives crumble relatively rapidly and the glass slide quickly assumes a frosted appearance. Fine diamond grits and the carbonaceous powders of the present invention behave totally differently and yield long, highly character ⁇ istic, meteoric grooves. Each of the hard carbonaceous products of the above-recited examples displayed at least some tendency to yield these characteristic meteoric grooves when tested.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Carbon And Carbon Compounds (AREA)

Abstract

Production d'une particule ultra-dure composée sensiblement de carbone en tant qu'élément dominant. La particule ultra-dure est le produit de la réaction d'un carbure métallique sélectionné dans le groupe se composant d'Al4C3 et de Be2C avec une substance sélectionnée dans le groupe se composant de CHnXAY(4-n)-A, C2Hn, XA, Y(6-n')-A', C2Hn''XA''Y(4-n'')-A'' et X2 où X et Y sont des halogènes différents sélectionnés dans le groupe se composant de chlore, brome, iode et fluore, et où A est un nombre entier compris entre 0 et 4, A' est un nombre entier compris entre 0 et 6 et A'' est un nombrer entier entre 0 et 4 et où n est un nombre entier compris entre 0 et 4, n' est un nombre entier compris en 0 et 6 et n'' est un nombre entier compris entre 0 et 4, où A, A', A'', n, n' ou n'' représente le même nombre entier dans un organe particulier quelconque sélectionné et où n + A = 4, n' + A' = 6 et n'' + A'' = 4.
PCT/US1981/000866 1981-06-22 1981-06-22 Production de particules ultra-dures WO1983000038A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
PCT/US1981/000866 WO1983000038A1 (fr) 1981-06-22 1981-06-22 Production de particules ultra-dures
JP56502412A JPS58501430A (ja) 1981-06-22 1981-06-22 超硬粒子の製造
EP19810901985 EP0081487A4 (fr) 1981-06-22 1981-06-22 Production de particules ultra-dures.

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Application Number Priority Date Filing Date Title
PCT/US1981/000866 WO1983000038A1 (fr) 1981-06-22 1981-06-22 Production de particules ultra-dures

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4514465A (en) * 1984-05-30 1985-04-30 W. R. Grace & Co., Cryovac Div. Storm window film comprising at least five layers
US4551380A (en) * 1984-05-10 1985-11-05 W. R. Grace & Co., Cryovac Div. Oriented heat-sealable multilayer packaging film
JP2016517388A (ja) * 2013-03-15 2016-06-16 ウエスト バージニア ユニバーシティ リサーチ コーポレーション 純粋な炭素の製造方法、その組成及び方法
US9909222B2 (en) 2014-10-21 2018-03-06 West Virginia University Research Corporation Methods and apparatuses for production of carbon, carbide electrodes, and carbon compositions
US11332833B2 (en) 2016-04-20 2022-05-17 West Virginia Research Corporation Methods, apparatuses, and electrodes for carbide-to-carbon conversion with nanostructured carbide chemical compounds

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2019112237A (ja) * 2016-04-28 2019-07-11 味の素株式会社 グラフェンの製造方法

Citations (7)

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Publication number Priority date Publication date Assignee Title
US3268457A (en) * 1962-04-05 1966-08-23 Armando A Giardini Method of creating electrically semiconducting diamond
US3362788A (en) * 1963-08-26 1968-01-09 Sun Oil Co Preparation of crystalline carbonaceous materials
GB1226231A (fr) * 1968-02-08 1971-03-24
US3711595A (en) * 1971-07-22 1973-01-16 R I Patents Inc Chemical method for producing diamonds and fluorinated diamonds
US4039648A (en) * 1975-12-12 1977-08-02 Aluminum Company Of America Production of aluminum chloride
US4228142A (en) * 1979-08-31 1980-10-14 Holcombe Cressie E Jun Process for producing diamond-like carbon
US4275050A (en) * 1979-11-08 1981-06-23 Tdc-Technology Development Corporation Production of ultra-hard particles

Family Cites Families (1)

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Publication number Priority date Publication date Assignee Title
FR1274206A (fr) * 1960-11-24 1961-10-20 Nilok Chemicals Perfectionnements aux charbons actifs

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3268457A (en) * 1962-04-05 1966-08-23 Armando A Giardini Method of creating electrically semiconducting diamond
US3362788A (en) * 1963-08-26 1968-01-09 Sun Oil Co Preparation of crystalline carbonaceous materials
GB1226231A (fr) * 1968-02-08 1971-03-24
US3711595A (en) * 1971-07-22 1973-01-16 R I Patents Inc Chemical method for producing diamonds and fluorinated diamonds
US4039648A (en) * 1975-12-12 1977-08-02 Aluminum Company Of America Production of aluminum chloride
US4228142A (en) * 1979-08-31 1980-10-14 Holcombe Cressie E Jun Process for producing diamond-like carbon
US4275050A (en) * 1979-11-08 1981-06-23 Tdc-Technology Development Corporation Production of ultra-hard particles

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
High Temperature Science Vol. 10, published 1978, pages 183-195, HOLCOMBE et al *
See also references of EP0081487A4 *

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4551380A (en) * 1984-05-10 1985-11-05 W. R. Grace & Co., Cryovac Div. Oriented heat-sealable multilayer packaging film
US4514465A (en) * 1984-05-30 1985-04-30 W. R. Grace & Co., Cryovac Div. Storm window film comprising at least five layers
JP2018035064A (ja) * 2013-03-15 2018-03-08 ウエスト バージニア ユニバーシティ リサーチ コーポレーション 純粋な炭素の製造方法、その組成及び方法
US9701539B2 (en) 2013-03-15 2017-07-11 West Virginia University Research Corporation Process for pure carbon production
US9764958B2 (en) 2013-03-15 2017-09-19 West Virginia University Research Corporation Process for pure carbon production, compositions, and methods thereof
JP2016517388A (ja) * 2013-03-15 2016-06-16 ウエスト バージニア ユニバーシティ リサーチ コーポレーション 純粋な炭素の製造方法、その組成及び方法
US10035709B2 (en) 2013-03-15 2018-07-31 West Virginia University Research Corporation Process for pure carbon production, compositions, and methods thereof
US10144648B2 (en) 2013-03-15 2018-12-04 West Virginia University Research Corporation Process for pure carbon production
US10494264B2 (en) 2013-03-15 2019-12-03 West Virginia University Research Corporation Process for pure carbon production, compositions, and methods thereof
US10696555B2 (en) 2013-03-15 2020-06-30 West Virginia University Research Corporation Process for pure carbon production
US9909222B2 (en) 2014-10-21 2018-03-06 West Virginia University Research Corporation Methods and apparatuses for production of carbon, carbide electrodes, and carbon compositions
US11306401B2 (en) 2014-10-21 2022-04-19 West Virginia University Research Corporation Methods and apparatuses for production of carbon, carbide electrodes, and carbon compositions
US11332833B2 (en) 2016-04-20 2022-05-17 West Virginia Research Corporation Methods, apparatuses, and electrodes for carbide-to-carbon conversion with nanostructured carbide chemical compounds

Also Published As

Publication number Publication date
EP0081487A4 (fr) 1984-09-06
JPS58501430A (ja) 1983-08-25
EP0081487A1 (fr) 1983-06-22

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