IP Library › Granted Patent US 12,655,068
Granted Patent B2
US 12,655,068 · App. 17/926,973 · Granted Jun 16, 2026

Metal boride ceramic composites and uses thereof

Inventor: Christopher L. Turner (Los Angeles, CA)
Assignee: SuperMetalix, Inc.
C04B35/62695C04B35/495C04B35/58064C04B35/64C04B2235/6562C04B2235/76C04B2235/77C04B2235/96
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Quick Facts
Patent No.
US 12,655,068
App. No.
17/926,973
Granted
Jun 16, 2026
Kind
B2
Abstract

Disclosed herein are compounds, methods, and tools which comprise composite matrices of tungsten tetraborides and ceramics.

Claims (42)

1 . A composite matrix of a formula (W 1-x M x B 4 ) z (Q) n , wherein:

the composite matrix comprises a first component comprising crystalline W 1-x M x B 4 and a second component comprising one or more ceramics Q;

the first component and the second component are uniformly dispersed within the composite matrix;

M is one or more of titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), zirconium (Zr), niobium (Nb), molybdenum (Mo), ruthenium (Ru), hafnium (Hf), tantalum (Ta), rhenium (Re), osmium (Os), iridium (Ir), lithium (Li), yttrium (Y) and aluminum (Al);

x is from 0 to 0.999, wherein if x is 0 then M is absent;

each of the one or more ceramics comprises at least two elements, and at least one of the two elements is B (boron), C (carbon), Si (silicon), N (nitrogen), or O (oxygen);

z is a volume percent from 0.1% to 99.9%;

n is a volume percent from 0.1% to 99.9%;

a sum of n and z is 100%;

Q is not tungsten carbide (WC); and

Palmquist Toughness of the composite matrix is from 1-10 MPam 1/2 .

2 . The composite matrix of claim 1 , wherein W 1-x M x B 4 is a crystalline solid characterized by at least one X-ray diffraction pattern reflection at 2 theta=24.2±0.3.

3 . The composite matrix of claim 1 , wherein x is 0.001 to 0.6.

4 . The composite matrix of claim 1 , wherein M is one or more of Cr, Ta, Mo, or Mn.

5 . The composite matrix of claim 1 , wherein M is Cr; Mn; Mo; Ta and Cr; or Ta and Mo.

6 . The composite matrix of claim 1 , wherein the one or more ceramics comprises at least B, C, Si, or N.

7 . The composite matrix of claim 1 , wherein Q is one or more ceramics selected from TiB 2 , SiC, AlC, TiC, and B 4 C.

8 . The composite matrix of claim 1 , wherein n is from 1% to 50%.

9 . The composite matrix of claim 1 , wherein Vicker's Hardness of the composite matrix is from 18-30 GPa measured at 9.8 N (1 kg force load).

10 . The composite matrix of claim 1 , wherein the composite matrix has a density from 3-8 g/cm 3 .

11 . The composite matrix of claim 1 , wherein n is from 5% to 40%.

12 . A method of preparing a composite matrix of claim 1 , the method comprising:

a) blending together crystalline W 1-x M x B 4 or WB 4 with solid Q to form a mixture; wherein:

M is one or more of titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), zirconium (Zr), niobium (Nb), molybdenum (Mo), ruthenium (Ru), hafnium (Hf), tantalum (Ta), rhenium (Re), osmium (Os), iridium (Ir), lithium (Li), yttrium (Y) and aluminum (Al);

x is from 0.001 to 0.999;

Q is one or more ceramics, wherein each of the one or more ceramics comprises at least two elements, and at least one of the two elements is B (boron), C (carbon), Si (silicon), N (nitrogen), or O (oxygen);

z is a volume percent from 0.1% to 99.9%;

n is a volume percent from 0.1% to 99.9%;

the sum of n and z is 100%; and

wherein Q is not WC,

pressing the mixture to generate a pellet,

heating the pellet to produce the composite matrix, and

Palmquist Toughness of the composite matrix is from 1-10 MPam 1/2 .

13 . The method of claim 12 , wherein the mixture is heated to a temperature between about 1050° C. and about 2200° C., wherein the mixture is heated at a ramp rate of between 100-200° C. per minute.

14 . The method of claim 12 , wherein the mixture is heated by a plasma spark sintering, induction furnace, electromagnetic induction, hot pressing, conventional furnace, or fused deposition modeling.

15 . A tool comprising a surface or body for cutting or abrading, wherein the surface or body comprises a composite matrix of claim 1 .

16 . A method of applying a composite matrix of claim 1 , wherein the method comprises affixing the composite matrix to a tool by laser welding or arc welding.

17 . A method of manufacturing a tool comprising a composite matrix of claim 1 , wherein the tool is manufactured by turning, milling, grinding, drilling, Electrical Discharge Manufacturing (EDM), Electrochemical Machining (ECM), water jet cutting, plasma cutting, or laser machining.

18 . A tool, nozzle, or machine part comprising a composite matrix of claim 1 , wherein a lubricating layer of B 2 O 3 forms on a surface of the composite matrix in presence of moisture.

19 . A method of using a nozzle comprising the composite matrix of claim 1 , comprising:

exposing the nozzle comprising the composite matrix to moisture, thereby forming a lubricating layer of B 2 O 3 on a surface of the composite matrix; and

extruding a semisolid, solution, suspension, or liquid through the nozzle.

Assignments (1)
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Jan 30, 2023
From: TURNER, CHRISTOPHER L.
To: SUPERMETALIX, INC.
Reel/Frame 062528/0175 →
Continuity (2)
Provisional Application 63034651 · Jun 4, 2020
Related Publication 20230202935A1 · Jun 29, 2023
References Cited (122)
US 3507632A · Swoboda et al. · 1970 [cited by applicant]
US 3525610A · Meadows · 1970 [cited by applicant]
US 3535110A · Todd · 1970 [cited by applicant]
US 3647576A · Yamamura et al. · 1972 [cited by applicant]
US 3663017A · Lopez · 1972 [cited by applicant]
US 3668017A · Mandineau et al. · 1972 [cited by applicant]
US 3773903A · Kuratomi · 1973 [cited by applicant]
US 4019873A · Reiter · 1977 [cited by applicant]
US 4235630A · Babu · 1980 [cited by applicant]
US 4268582A · Hale et al. · 1981 [cited by applicant]
US 4365997A · Jachowski et al. · 1982 [cited by applicant]
US 4671822A · Hamashima et al. · 1987 [cited by applicant]
US 4923512A · Timm et al. · 1990 [cited by applicant]
US 4961781A · Morishita et al. · 1990 [cited by applicant]
US 5161696A · Seider · 1992 [cited by applicant]
US 5178647A · Komatsu et al. · 1993 [cited by applicant]
US 5238481A · Takagi et al. · 1993 [cited by applicant]
US 5476531A · Timm et al. · 1995 [cited by applicant]
US 5966585A · Sue · 1999 [cited by applicant]
US 6106957A · Fang · 2000 [cited by applicant]
US 6830738B1 · Lupinetti et al. · 2004 [cited by applicant]
US 8535604B1 · Baker et al. · 2013 [cited by applicant]
US 10125412B2 · Kaner et al. · 2018 [cited by applicant]
US 10731236B2 · Kaner et al. · 2020 [cited by applicant]
US 11033998B2 · Kavanaugh et al. · 2021 [cited by applicant]
US 11174538B2 · Kaner et al. · 2021 [cited by applicant]
US 20020025906A1 · Hagiya et al. · 2002 [cited by applicant]
US 20020054794A1 · Kato et al. · 2002 [cited by applicant]
US 20020088508A1 · Holzl et al. · 2002 [cited by applicant]
US 20030054940A1 · Abe et al. · 2003 [cited by applicant]
US 20070224100A1 · Kaner et al. · 2007 [cited by applicant]
US 20080104091A1 · Chin · 2008 [cited by applicant]
US 20080125323A1 · Nepela · 2008 [cited by applicant]
US 20090186211A1 · Chun et al. · 2009 [cited by applicant]
US 20110262295A1 · Voronov · 2011 [cited by examiner]
US 20120141293A1 · Sato et al. · 2012 [cited by applicant]
US 20140041313A1 · Kaner · 2014 [cited by examiner]
US 20150143953A1 · Chen · 2015 [cited by applicant]
US 20170209983A1 · Kavanaugh et al. · 2017 [cited by applicant]
US 20170260102A1 · Conway et al. · 2017 [cited by applicant]
US 20190135646A1 · Turner et al. · 2019 [cited by applicant]
US 20200048101A1 · Adachi et al. · 2020 [cited by applicant]
CN 1997475A · 2007 [cited by applicant]
CN 105817619A · 2016 [cited by applicant]
CN 106116593A · 2016 [cited by applicant]
EP 2699703B1 · 2017 [cited by applicant]
EP 3408422A1 · 2018 [cited by applicant]
GB 1486964A · 1977 [cited by applicant]
GB 2263704A · 1993 [cited by applicant]
JP S4942763A · 1974 [cited by applicant]
JP H055152A · 1993 [cited by applicant]
JP H09132460A · 1997 [cited by applicant]
JP 2003268479A · 2003 [cited by applicant]
JP 2003306384A · 2003 [cited by applicant]
JP 2008201080A · 2008 [cited by applicant]
JP 2010247212A · 2010 [cited by applicant]
JP 2011252195A · 2011 [cited by applicant]
JP 5632379B2 · 2014 [cited by applicant]
KR 101215656B1 · 2013 [cited by applicant]
WO WO2006001791A1 · 2006 [cited by examiner]
WO WO2013022503A2 · 2013 [cited by applicant]
WO WO2017061477A1 · 2017 [cited by applicant]
WO WO2017132286A1 · 2017 [cited by applicant]
WO WO2019094506A1 · 2019 [cited by applicant]
WO WO2021247981A1 · 2021 [cited by applicant]
WO WO2023091193A2 · 2023 [cited by applicant]
Akopov, Georgiy. “Extrinsic Hardening of Superhard Tungsten Tetraboride Alloys with Group 4 Transition Metals” (Apr. 26, 2016) JACS vol. 138 pp. 5714-5721 (Year: 2016). [cited by applicant]
Ariel et al.: Tungsten-Titanium-Boron Metastable PhaSe Diagram at Room Temperature. Journal of the Less-Common Metals. 20(3):199-206 (1970). [cited by applicant]
European Application No. 21816951.4 Search Report dated Nov. 24, 2023. [cited by applicant]
Examination Report issued in EP Application No. 17744852.9 on Apr. 11, 2023. [cited by applicant]
Extended European Search Report dated Sep. 3, 2020 in corresponding European Application No. 18748255.9. [cited by applicant]
Goto et al.: Preparation of W-B-C System Composites by Arc Melting and their Thermoelectric Properties. Journal of the Japan Society of Powder. pp. 1406-1410 (1995). [cited by applicant]
Intemational Search Report and Written Opinion issued in International Application No. PCT/US2018/059680, on Apr. 11, 2019. [cited by applicant]
Intemational Search Report in International Patent Application No. PCT/US18/16911, dated Apr. 24, 2018. [cited by applicant]
Internal Search Report and Written Opinion of PCT/US2012/034685, mailed Mar. 20, 2013. [cited by applicant]
International Search Report and Written Opinion in International Application No. PCT/US17/14987, dated Apr. 18, 2017. [cited by applicant]
Itoh et al., “Formation process of tungsten borides by solid state reaction between tungsten and amorphous boron”, Journal of Material Science, (Aug. 1, 1987), vol. 22, No. 1, pp. 2811-2815. [cited by applicant]
Kopeliovich, “Graphite molds for continuous casting,” Subs Tech, p. 1 (Jun. 2013). [cited by applicant]
L. G. Bodrova et al., “Theory, Production Technology, and Properties of Powders and Fibers”, Soviet Powder Metallurgy and Metal Ceramics, vol. 13, Jan. 1, 1974, pp. 1-3, XP055138580. [cited by applicant]
Ma et al., “Formation of metastable tungsten tetraboride by reactive hot-pressing”, Ceramics Interantional, (Mar. 14, 2017), vol. 43, No. 12, pp. 8551-8555. [cited by applicant]
Mohammadi et al. “Enhancing the Hardness of Superhard Transition-Metal Borides: Molybdenum-Doped Tungsten Tetraboride”, Chemistry of Materials, Dec. 21, 2015, vol. 28, No. 2, pp. 632-637, XP055607500. [cited by applicant]
Mohammadi et al., Toward inexpensive superhard materials: tungsten tetraboride-based solid solutions. J Am Chem Soc. 134(51):20660-20668 (2012). [cited by applicant]
Mohammadi et al., “Tungsten tetraboride, an inexpensive superhad material,” PNAS, 108(27): pp. 10958-10962 (2011). [Cited in International Search Report in International Patent Application No. PCT/US18/16911, dated Apr.… [cited by applicant]
PCT/US2021/035869 International Search Report and Written Opinion dated Sep. 27, 2021. [cited by applicant]
PCT/US2022/035152 International Search Report and Written Opinion dated Aug. 15, 2023. [cited by applicant]
Q. Gu et al., “Transition Metal Borides: Superhard versus Ultra-incompressible”, Advanced Materials, vol. 20, No. 19, Oct. 2, 2008, pp. 3620-3626, XP055138946. [cited by applicant]
Kaner et al., “Ambient-pressure synthesis and characterization of superhard intermetallic and solid-solution borides”, Abstracts of Papers of the American Chemical Society. vol. 241. 1155 16th St, NW, Washington, DC 200… [cited by applicant]
Standard Test Methods for Vickers Hardness and Knoop Hardness of Metallic Materials. ASTM E92-17, p. 4 (2017). [cited by applicant]
Supplementary Partial European Search Report issued in European Application No. 18 87 5443 on Nov. 11, 2021. [cited by applicant]
U.S. Appl. No. 14/112,903 Notice of Allowance dated Jun. 27, 2018. [cited by applicant]
U.S. Appl. No. 14/112,903 Office Action dated Apr. 12, 2017. [cited by applicant]
U.S. Appl. No. 14/112,903 Office Action dated Feb. 14, 2018. [cited by applicant]
U.S. Appl. No. 14/112,903 Office Action dated Oct. 2, 2017. [cited by applicant]
U.S. Appl. No. 14/112,903 Restriction Requirement dated Aug. 2, 2016. [cited by applicant]
U.S. Appl. No. 14/112,903 Restriction Requirement dated Jan. 9, 2017. [cited by applicant]
U.S. Appl. No. 15/415,553 Corrected Notice of Allowability dated Apr. 26, 2021. [cited by applicant]
U.S. Appl. No. 15/415,553 Notice of Allowance dated Feb. 3, 2021. [cited by applicant]
U.S. Appl. No. 15/415,553 Office Action dated Jun. 24, 2020. [cited by applicant]
U.S. Appl. No. 15/415,553 Office Action dated Mar. 16, 2020. [cited by applicant]
U.S. Appl. No. 15/415,553 Restriction Requirement dated Dec. 2, 2019. [cited by applicant]
U.S. Appl. No. 15/415,553 Restriction Requirement dated Jul. 18, 2019. [cited by applicant]
U.S. Appl. No. 15/888,826 Corrected Notice of Allowability dated Jul. 27, 2021. [cited by applicant]
U.S. Appl. No. 15/888,826 Notice of Allowance dated Jul. 13, 2021. [cited by applicant]
U.S. Appl. No. 15/888,826 Office Action dated Dec. 22, 2020. [cited by applicant]
U.S. Appl. No. 15/888,826 Restriction Requirement dated Jun. 15, 2020. [cited by applicant]
U.S. Appl. No. 16/142,607 Notice of Allowance dated Mar. 25, 2020. [cited by applicant]
U.S. Appl. No. 16/183,346 Notice of Allowance dated Feb. 7, 2023. [cited by applicant]
U.S. Appl. No. 16/183,346 Notice of Allowance dated Mar. 16, 2022. [cited by applicant]
U.S. Appl. No. 16/183,346 Office Action dated Jul. 6, 2022. [cited by applicant]
U.S. Appl. No. 16/183,346 Office Action dated Jun. 24, 2021. [cited by applicant]
U.S. Appl. No. 16/183,346 Office Action dated Sep. 21, 2020. [cited by applicant]
U.S. Appl. No. 16/912,396 Notice of Allowance dated Aug. 30, 2023. [cited by applicant]
U.S. Appl. No. 16/912,396 Restriction Requirement dated Mar. 13, 2023. [cited by applicant]
U.S. Appl. No. 16/912,396 Restriction Requirement dated Oct. 13, 2022. [cited by applicant]
U.S. Appl. No. 17/307,600 Corrected Notice of Allowability dated Jun. 29, 2023. [cited by applicant]
U.S. Appl. No. 17/307,600 Notice of Allowance dated May 1, 2023. [cited by applicant]
U.S. Appl. No. 17/526,726 Office Action dated Sep. 15, 2022. [cited by applicant]
U.S. Appl. No. 18/082,378 Corrected Notice of Allowability dated Sep. 14, 2023. [cited by applicant]
U.S. Appl. No. 18/082,378 Notice of Allowance dated Sep. 5, 2023. [cited by applicant]
U.S. Appl. No. 18/082,378 Office Action dated Apr. 10, 2023. [cited by applicant]
U.S. Appl. No. 18/532,796 Office Action dated Aug. 8, 2024. [cited by applicant]
Yang et al., “Effects of Sn addition on as-cast microstructure, mechanical properties and casting fluidity of ZA84 magnesium alloy,” Materials and Design, vol. 31, pp. 68-75 (Jul. 2009). [cited by applicant]