# US 4,400,213 A · Novel hard compositions and methods of preparation > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 4,400,213 A - Document ID: US4400213A - Status: Granted - Kind: A - Application number: 06/231,085 - Filed: 1981-02-03 - Granted: 1983-08-23 - Earliest claimed: 1981-02-03 - Inventors: Haskell Sheinberg - Web page: https://patentgrep.com/patent/US4400213A ## CPC - C22C 32/0057: {based on B4C} - C22C: ALLOYS (treatment of alloys C21D, C22F) ## Abstract Novel very hard compositions of matter are prepared by using in all embodiments only a minor amount of a particular carbide (or materials which can form the carbide in situ when subjected to heat and pressure); and no strategic cobalt is needed. Under a particular range of conditions, densified compositions of matter of the invention are prepared having hardnesses on the Rockwell A test substantially equal to the hardness of pure tungsten carbide and to two of the hardest commercial cobalt-bonded tungsten carbides. Alternately, other compositions of the invention which have slightly lower hardnesses than those described above in one embodiment also possess the advantage of requiring no tungsten and in another embodiment possess the advantage of having a good fracture toughness value. Photomicrographs show that the shapes of the grains of the alloy mixture with which the minor amount of carbide (or carbide-formers) is mixed are radically altered from large, rounded to small, very angular by the addition of the carbide. Superiority of one of these hard compositions of matter over cobalt-bonded tungsten carbide for ultra-high pressure anvil applications was demonstrated. ## Claims ### Claim 1 A precursor mixture useful for producing a very hard composition without requiring cobalt, said precursor mixture consisting essentially of: (a) a minor amount of a boron carbide component selected from the group consisting of (i) boron carbide and (ii) boron and carbon, both present in amounts effective to form boron carbide in situ; and (b) a major amount of a second mixture consisting of (i) a first amount of a first component selected from the group consisting of tungsten, molybdenum, mixtures thereof and alloys thereof, (ii) a second amount of a second component which is nickel, and (iii) a third amount of a third component selected from the group consisting of iron, copper, and mixtures thereof, wherein said minor amount is an amount corresponding to a weight percent of said precursor mixture within the range from about 1.5 to about 4.0 when said first component is tungsten and within the range from about 5.0 to about 6.3 when said first component is molybdenum, wherein said major amount is a weight percent of about 100 minus said minor amount, wherein said first amount is an amount within the range from about 90 to about 97 weight percent of said major amount when said first component is tungsten, wherein the sum of said second amount and said third amount is within the range from about 3 to about 10 weight percent of said major amount when said first component is tungsten, wherein molybdenum can be substituted for tungsten on a mole-for-mole basis, and wherein said first amount, said second amount, and said third amount are amounts which are effective to result in a composition having an average hardness of at least about 85 Rockwell A when said precursor mixture is subjected to appropriate hot-pressing conditions. ### Claim 2 (depends on 1) A composition according to claim 1 wherein the relative weight ratio of said second amount to said third amount lies within the range from about 3.5 to about 1.5. ### Claim 3 (depends on 2) A composition according to claim 2, wherein said first component is tungsten, wherein said third component is iron, wherein said boron carbide is B.sub.4 C, wherein the sizes of particles of tungsten, nickel, iron, and B.sub.4 C are on the order of microns, and wherein said minor amount is present is an amount corresponding to a weight percent of said precursor mixture within the range from about 2.0 to about 4.0. ### Claim 4 (depends on 3) A composition according to claim 3, wherein said minor amount is an amount corresponding to a weight percent within the range from about 2.5 to about 3.0. ### Claim 5 A precursor mixture useful for producing a very hard composition without requiring cobalt, said precursor mixture consisting essentially of: (a) a minor amount of a boron carbide component selected from the group consisting of (i) boron carbide and (ii) boron and carbon, both present in amounts effective to form boron carbide in situ, wherein said boron carbide is B.sub.4 C; and (b) a major amount of a second mixture consisting of (i) a first amount of a first component which is tungsten, (ii) a second amount of a second component which nickel, and (iii) a third amount of a third component which is iron, wherein said minor amount is an amount corresponding to a weight percent of said precursor mixture within the range from about 2.5 to about 3.0, wherein said major amount is a weight percent of about 100 minus said minor amount, wherein the sizes of particles of tungsten, nickel, iron, and B.sub.4 are on the order of microns, and wherein said tungsten, said nickel, and said iron are present in said second mixture in a weight ratio of 90-95 W:3.5-7 Ni:1.5-3 Fe. ### Claim 6 (depends on 5) A composition according to claim 5, wherein said tungsten, said nickel, and said iron are present in said second mixture in a weight ratio of about 95:3.5:1.5 and wherein said minor amount is an amount corresponding to a weight percent of said precursor mixture within the range from about 2.50 to about 2.83. ### Claim 7 (depends on 1) A composition according to claim 1, wherein said first component is molybdenum, wherein said third component is iron, wherein said boron carbide is B.sub.4 C, wherein the sizes of particles of molybdenum, nickel, iron, and B.sub.4 C are on the order of microns, and wherein said minor amount is an amount corresponding to a weight percent of said precursor mixture within the range from about 5.0 to about 6.3 w/o B.sub.4 C. ### Claim 8 (depends on 7) A composition according to claim 7 wherein said minor amount is an amount corresponding to a weight percent of said precursor mixture within the range from about 5.0 to about 5.9 and wherein said molybdenum is present in a weight percent of about 91. ### Claim 9 A cobalt-free, very hard, densified composition of matter having an angular-shaped grain structure which occupies at least about 40 volume percent of the total volume of said composition, wherein said densified composition is the hot-pressed reaction product of (1) a minor amount of at least one boron carbide component selected from the group consisting of (a) boron carbide and (b) boron and carbon, both B and C present in amounts effective to form said minor amount of boron carbide in situ, (2) nickel, (3) a first component selected from the group consisting of molybdenum, tungsten, mixtures thereof and alloys thereof, and (4) a second component selected from the group consisting of iron, copper, and mixtures thereof, and wherein said densified composition is characterized by having a Rockwell A hardness value of at least about 85. ### Claim 10 (depends on 9) A composition according to claim 9, wherein said minor amount is an amount no greater than about 6.3 weight percent of said hot-pressed reaction product, wherein said nickel, said first component, and said second component make up the balance of said hot-pressed reaction product, wherein said first component is an amount within the range from about 90 to about 97 weight percent of said balance when said first component is tungsten, and wherein molybdenum can be substituted for tungsten on a mole-for-mole basis. ### Claim 11 (depends on 10) A composition according to claim 10, wherein said first component is tungsten, wherein said second component is iron, wherein said boron carbide component is B.sub.4 C, and wherein said minor amount is an amount which corresponds to a weight percent of said composition prior to hot-pressing within the range from about 1.5 to about 4.0. ### Claim 12 (depends on 11) A composition according to claim 11, wherein said minor amount is an amount corresponding to a weight percent of the weight of said composition within the range from about 1.5 to about 3.0. ### Claim 13 (depends on 12) A composition according to claim 12, wherein said minor amount is a weight percent of the weight of said composition within the range from about 2.40 to about 2.85 and where said composition is characterized by having a hardness of at least 90 R.sub.A. ### Claim 14 (depends on 12) A composition according to claim 12 characterized by having a hardness of about 85 R.sub.A and a fracture toughness value of about 12 Megapascal .sqroot.meter, as measured by use of a Fractometer I.RTM. on a short rod. ### Claim 15 (depends on 10) A composition according to claim 10, wherein said first component is molbdenum, wherein said second component is iron, wherein said boron carbide component is B.sub.4 C, and wherein said B.sub.4 C is present in an amount corresponding to a weight percent of said composition prior to hot-pressing within the range from about 5.0 to about 6.3. ### Claim 16 (depends on 10) A composition according to claim 10, wherein the relative weight ratio of said nickel:said second component lies within the range from about 3.5 to about 1.5. ### Claim 17 A cobalt-free, very hard, densified composition of matter having an angular-shaped grain structure which occupies at least about 40 volume percent of the total volume of said composition, wherein said densified composition is the hot-pressed reaction product of (1) a minor amount of at least one boron carbide component selected from the group consisting of (a) boron carbide and (b) boron and carbon, both boron and carbon present in amounts effective to form said minor amount of boron carbide in situ, wherein said boron carbide component is B.sub.4 C, (2) nickel, (3) molybdenum, and (4) iron, wherein said densified composition is characterized by having a Rockwell A hardness value of at least about 85, wherein said molybdenum, said nickel, and said iron are present in said composition in a weight ratio of about 90.9:6.4:2.7 and wherein said B.sub.4 C is present in an amount corresponding to a weight percent of said composition prior to hot-pressing within the range from about 5.0 to about 5.9. ### Claim 18 A method of increasing the hardness of an alloy having a rounded grain shape and being formed from a first component selected from the group consisting of molbdenum, tungsten, mixtures thereof, and alloys thereof, a second component which is nickel, and a third component selected from the group consisting of iron, copper, and mixtures thereof, said method comprising: (a) combining a minor amount of a powdered boron carbide component selected from the group consisting of (i) boron carbide and (ii) boron and carbon with a major amount of a powder of said alloy, so as to obtain a combined mixture; and (b) then subjecting said combined mixture to heat and pressure effective to form a hard, densified composition, wherein said minor amount is a weight percent of said combined mixture within the range from about 1.5 to about 6.3 and wherein said major amount is a weight percent of said combined mixture within the range from about 93.7 to about 98.5. ### Claim 19 (depends on 18) A method according to claim 18, wherein said boron carbide is B.sub.4 C and wherein said minor amount is an amount corresponding to about 1.5 to about 4.0 weight percent of said combined mixture. ### Claim 20 (depends on 18) A method according to claim 18, wherein said tungsten is used to form said alloy in an amount corresponding to a weight percent of said alloy within the range from about 90 to about 97 and wherein said iron and said nickel are used to form said alloy in a combined amount corresponding to a weight percent of said alloy within the range from about 10 to about 3. ### Claim 21 (depends on 18) A method according to claim 18, wherein said alloy consists of molybdenum, nickel, and iron. ### Claim 22 (depends on 21) A method according to claim 21, wherein said boron carbide is B.sub.4 C and wherein said minor amount is an amount corresponding to about 5.0 to about 6.3 weight percent of said combined mixture. ### Claim 23 (depends on 20) A method according to claim 20, wherein the relative weight ratio of said nickel:said second component lies within the range from about 3.5 to about 1.5. ### Claim 24 (depends on 22) A method according to claim 22, wherein the relative weight ratio of said nickel:said second component lies within the range from about 3.5 to about 1.5. ### Claim 25 A method of producing a hard composition, said method comprising: (a) mixing powders so as to obtain a first mixture consisting essentially of (1) a first component selected from the group consisting of tungsten, molybdenum, mixtures thereof and alloys thereof, (2) a second component consisting of nickel, and (3) a third component selected from the group consisting of iron, copper, and mixtures thereof, wherein said first component is an amount within the range from about 90 to about 97 weight percent of said first mixture when said first component is tungsten, wherein the sum of the amounts of said second component and of said third component is within the range from about 3 to about 10 weight percent of said first mixture, and wherein molybdenum can be substituted for tungsten on a mole-for-mole basis; (b) combining about 1.5 to about 6.3 weight percent of powdered boron carbide with about 93.7 to about 98.5 weight percent of said first mixture, so as to obtain a combined mixture; and then (c) applying both heat and pressure to said combined mixture effective to form said hard composition. ### Claim 26 (depends on 23) A method according to claim 23, wherein said heat and said pressure are applied to said combined mixture simultaneously. ### Claim 27 (depends on 25) A method according to claim 25, wherein said pressure is applied to said combined mixture before said heat is applied. ### Claim 28 (depends on 26, 27) A method according to claim 26 or claim 27, wherein said first component is tungsten, wherein said third component is iron, wherein said tungsten, said nickel, and said iron are elemental powders, wherein said boron carbide is B.sub.4 C, and wherein about 1.5 to about 4.0 weight percent of said B.sub.4 C is combined with about 96 to about 98.5 weight percent of said first mixture. ### Claim 29 A method of producing a hard composition, said method comprising: (a) mixing powders so as to obtain a first mixture consisting essentially of (1) tungsten, (2) nickel, and (3) iron, wherein said tungsten, said nickel, and said iron are elemental powders; (b) combining about 1.5 to about 4.0 weight percent of powdered B.sub.4 C with about 96 to about 98.5 weight percent of said first mixture, so as to obtain a combined mixture; and then (c) applying both heat and pressure to said combined mixture effective to form said hard composition, wherein said first mixture consists of about 90 to about 97 weight percent tungsten and about 10 to about 3 weight percent of a mixture of nickel and iron having a weight ratio of nickel:iron within the range from about 3.5 to about 1.5. ### Claim 30 (depends on 29) A method according to claim 29, wherein said B.sub.4 C is present in said combined mixture in an amount corresponding to about 2.5 to about 3.0 weight percent of said combined mixture. ### Claim 31 (depends on 26, 27) A method according to claim 26 or claim 27, wherein said first component is molybdenum, wherein said third component is iron, and wherein said molybdenum, said nickel, and said iron are elemental powders. ### Claim 32 (depends on 31) A method according to claim 31, wherein said B.sub.4 C is present in said combined mixture in an amount corresponding to about 5.0 to about 6.3 weight percent of said combined mixture, and wherein said first mixture consists of about 91 weight percent molybdenum and about 9 weight percent of a mixture of nickel and iron. ### Claim 33 (depends on 32) A method according to claim 32, wherein said B.sub.4 C is present in said combined mixture in an amount corresponding to about 5.0 weight percent. ### Claim 34 (depends on 32) A method according to claim 32, wherein said B.sub.4 C is present in said combined mixture in an amount corresponding to about 5.9 weight percent of said combined mixture and wherein the relative weight ratio of nickel:iron in said first mixture is within the range from about 3.5 to about 1.5. ### Claim 35 (depends on 9) An article of manufacture comprising a composition according to claim 9. ### Claim 36 (depends on 11) An article of manufacture comprising a composition according to claim 11. ### Claim 37 (depends on 13) An article of manufacture comprising a composition according to claim 13. ### Claim 38 (depends on 15) An article of manufacture comprising a composition according to claim 15. ### Claim 39 (depends on 17) An article of manufacture comprising a composition according to claim 17. ### Claim 40 (depends on 2, 3) A hard, densified composition formed by hot-pressing a composition according to claim 2 or claim 3. ### Claim 41 (depends on 5, 6) A hard, densified composition formed by hot-pressing a composition according to claim 5 or claim 6. ### Claim 42 (depends on 7, 8) A hard, densified composition formed by hot-pressing a composition according to claim 7 or claim 8.