WO1981001422A1 - Sintered hard metals - Google Patents
Sintered hard metals Download PDFInfo
- Publication number
- WO1981001422A1 WO1981001422A1 PCT/GB1980/000195 GB8000195W WO8101422A1 WO 1981001422 A1 WO1981001422 A1 WO 1981001422A1 GB 8000195 W GB8000195 W GB 8000195W WO 8101422 A1 WO8101422 A1 WO 8101422A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- carbide
- mixed crystal
- hard metal
- zirconium
- sintered hard
- Prior art date
Links
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 81
- 239000002184 metal Substances 0.000 title claims abstract description 81
- 150000002739 metals Chemical class 0.000 title claims abstract description 38
- 239000013078 crystal Substances 0.000 claims abstract description 57
- 239000000047 product Substances 0.000 claims abstract description 32
- 239000000463 material Substances 0.000 claims abstract description 31
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 26
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 24
- 229910052735 hafnium Inorganic materials 0.000 claims abstract description 21
- -1 hafnium carbides Chemical class 0.000 claims abstract description 20
- 239000000956 alloy Substances 0.000 claims abstract description 17
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 14
- 150000001247 metal acetylides Chemical class 0.000 claims abstract description 10
- 239000010936 titanium Substances 0.000 claims abstract description 8
- 239000010941 cobalt Substances 0.000 claims abstract description 7
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 7
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 6
- 230000000737 periodic effect Effects 0.000 claims abstract description 6
- 239000011230 binding agent Substances 0.000 claims abstract description 5
- 238000001513 hot isostatic pressing Methods 0.000 claims abstract description 5
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 5
- 239000010937 tungsten Substances 0.000 claims abstract description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract 2
- 239000011733 molybdenum Substances 0.000 claims abstract 2
- 229910026551 ZrC Inorganic materials 0.000 claims description 33
- OTCHGXYCWNXDOA-UHFFFAOYSA-N [C].[Zr] Chemical compound [C].[Zr] OTCHGXYCWNXDOA-UHFFFAOYSA-N 0.000 claims description 32
- 239000000203 mixture Substances 0.000 claims description 19
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 claims description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 11
- WHJFNYXPKGDKBB-UHFFFAOYSA-N hafnium;methane Chemical compound C.[Hf] WHJFNYXPKGDKBB-UHFFFAOYSA-N 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 9
- MTPVUVINMAGMJL-UHFFFAOYSA-N trimethyl(1,1,2,2,2-pentafluoroethyl)silane Chemical compound C[Si](C)(C)C(F)(F)C(F)(F)F MTPVUVINMAGMJL-UHFFFAOYSA-N 0.000 claims description 8
- 230000015572 biosynthetic process Effects 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims description 5
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- 229910052593 corundum Inorganic materials 0.000 claims description 2
- 239000012467 final product Substances 0.000 claims description 2
- 239000007769 metal material Substances 0.000 claims description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims 3
- 238000005275 alloying Methods 0.000 claims 2
- 239000011248 coating agent Substances 0.000 claims 1
- 238000000576 coating method Methods 0.000 claims 1
- 229910003468 tantalcarbide Inorganic materials 0.000 abstract description 25
- 239000010955 niobium Substances 0.000 abstract description 9
- 229910052758 niobium Inorganic materials 0.000 abstract description 6
- NFFIWVVINABMKP-UHFFFAOYSA-N methylidynetantalum Chemical compound [Ta]#C NFFIWVVINABMKP-UHFFFAOYSA-N 0.000 abstract description 3
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052719 titanium Inorganic materials 0.000 abstract description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 abstract 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 abstract 1
- 239000006227 byproduct Substances 0.000 abstract 1
- 229910052804 chromium Inorganic materials 0.000 abstract 1
- 239000011651 chromium Substances 0.000 abstract 1
- 229910052720 vanadium Inorganic materials 0.000 abstract 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 abstract 1
- 238000011161 development Methods 0.000 description 7
- 230000018109 developmental process Effects 0.000 description 7
- 238000003754 machining Methods 0.000 description 7
- 238000006467 substitution reaction Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 4
- 238000005245 sintering Methods 0.000 description 4
- 238000007792 addition Methods 0.000 description 3
- 238000011835 investigation Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229910009043 WC-Co Inorganic materials 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910039444 MoC Inorganic materials 0.000 description 1
- 229910019802 NbC Inorganic materials 0.000 description 1
- 229910034327 TiC Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000011363 dried mixture Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000003966 growth inhibitor Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 238000001330 spinodal decomposition reaction Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910000601 superalloy Inorganic materials 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910003470 tongbaite Inorganic materials 0.000 description 1
- 238000001238 wet grinding Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
- C22C29/02—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides
- C22C29/06—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbides, but not containing other metal compounds
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
- C22C29/02—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides
- C22C29/04—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbonitrides
Definitions
- This invention relates to sintered hard metals, which are mixed carbides of metals selected from Groups IV to VI of the Periodic Table of Elements and possibly other metals, in conjunction with metals or alloys of the iron group.
- the extreme hardness and wear resistance of such products make them very suitable for use as tools or tool tips, for use in machine tools, and for dies and components generally, where wear-resistance is essential.
- Modern sintered hard metals such as are used for the machining of materials producing long chips, consist of tungsten carbide, WC, titanium carbide, TiC, tantalum carbide, TaC, or the mixed carbide of tantalum and niobium, (Ta,Nb)C, with cobalt as the customary iron group metal or alloy as a binder.
- the classical cobaltbound tungsten carbide hard metals i.e. WC-Co
- a sintered hard metal contains zirconium and hafnium carbides In mixed crystal form, together with, one or more carbides of metals of Groups IV to VI and a binder comprising one or more metals or alloys of the iron group.
- the mixed crystal material of or comprising ZrC and HfC is present in an amount in the range from 1% to 30% and, most preferably, from 2% to 20%. As indicated previously, these ranges are in percentages by weight.
- the relative proportions of ZrC and HfC in the mixed crystal material incorporated into the products of the invention can vary over very wide limits, though it is preferable for economic reasons for the ZrC to predominate.
- the mixed crystal material comprises ZrC and HfC in proportions by weight in the range from 9:1 to 1:7. Stated in percentage terms, the proportion of ZrC in the ZrC/HfC material present can be as high as 9.0% or as low as 12.5%. The proportion more preferably lies in the range from 90:10 to 50:50, i.e.
- the range of proportions of ZrC to HfC is from 60:40 to 80:20, i.e. the ZrC comprises from 60% to 80% of the total ZrC/HfC content of the sintered hard metal product. It has further surprisingly been found that
- ZrC-HfC-TiC mixed crystal materials produced by high temperature sintering, e.g. treatment for 2 hours at about 2200oC and final eutectic sintering with Co at about 1500oC, decompose spinodally on cooling into two isomorphous mixed crystals.
- This is a typical operation, in accordance with the process of this invention, for preparing the sintered hard metals of the invention.
- the pure pseudobinary ZrC-HfC mixed crystals do not show the miscibility gap and decomposition which take place in the systems comprising TiC-ZrC and TiC-HfC.
- the decomposition of the TiC-ZrC-HfC mixed crystals produces a very fine grain size with increased hardness and a reduced tendency to cratering.
- the mixed crystal material comprises zirconium and hafnium carbides or carbonitrides.
- nitrogen or a substance which is a source of nitrogen under the conditions employed, during the mixed crystal formation.
- any of the hard metal products of the invention can be treated so as to offset this, by subjecting the product to hot isostatic pressing or "hipping".
- the conditions for this treatment can comprise heating at 1380o + 25oC under an argon pressure of 300-400 bar. No appreciable difference in mechanical and physical properties can be found between the nitrogen-containing and nitrogenfree grades but, nevertheless, the nitrogen-containing grades give improved machining performance.
- products made from the hard metals of the invention e.g. throw-away tips, dies or other wearresistant components
- a wear-resistant material e.g. with TiC, TiN,
- the invention additionally provides a process of manufacture of a sintered hard metal, which comprises heating a mixture comprising zirconium and hafnium carbides or zirconium carbide, hafnium carbide and at least one other carbide of a metal of Groups IV to VI of the Periodic Table of the Elements under such conditions as to produce a product containing mixed crystals of zirconium and hafnium carbides and then heating the product, in comminuted form, or the product in comminuted form and at least one other carbide of a metal of Groups IV to VI of the Periodic Table, in conjunction with one or more metals of the iron group under, such conditions as to produce the final product desired.
- rhe invention also consists in a process of manufacture of a sintered hard metal, which comprises heating a first mixture comprising zirconium and hafnium carbides under such conditions that the resultant first product contains zirconium and hafnium carbides in mixed crystal form, forming a second mixture from the first product in comminuted form and one or more metals or alloys of the iron group and heating the second mixture under such conditions that the resultant second product comprises a sintered hard metal acontaining the one or more metals or alloys of the iron group, zirconium and hafnium carbides in mixed crystal form and at least one other hard metal material, the latter being incorporated into either or both of the first and second mixtures.
- the resulting hard metal identical in analysis, was distinctly more fine-grained than that resulting from (a), (0.6-0.8 ⁇ instead of 1-1.2 ⁇ ), and also it was 0.24-0.50 points harder in Rockwell. It was found that the cubic phase had decomposed into two isamorphous cubic phases, one ZrC rich containing some HfC, TiC and WC and the other TiC rich containing some ZrC, HfC and WC.
- This mixed crystal product was wet-milled together with 64 parts WC and 4.5 parts Co.
- the resulting mixture was dried, pressed and sintered under vacuum at 1425o + 25 oC.
- the resulting spinodal decomposition of the cubic mixed crystal was only just discernible under the microscope, but its effect was clearly visible, the extremely fine grain size giving a smaller built-up edge and less cratering.
- TaC-rich ZrC-HfC mixed crystals By the use of HfC-rich ZrC-HfC mixed crystals, larger quantities of TaC (15-25%) may be substituted in WC-TaC and WC-TiC-TaC special hard metals, although a partial exchange only may be indicated by economic grounds.
- a hard metal specification comprising 71% WC, 5% TiC, 8% TaC, 5% ZrC, 4% HfC and 7% Co has proved particularly suitable for the machining of superalloys.
- Small quantities of TaC or TaC-VC are often added as grain growth inhibitors to WC-Co alloys used in the machining of materials giving short chips.
- ZrC-HfC mixed crystals can also be used for this purpose, although, the pseudoternary mixed crystals of 1 part ZrC, 1 part HfC and 2 parts VC have proved still better.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Powder Metallurgy (AREA)
- Ceramic Products (AREA)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB7940140 | 1979-11-20 | ||
| GB7940140A GB2063922A (en) | 1979-11-20 | 1979-11-20 | Sintered hard metals |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO1981001422A1 true WO1981001422A1 (en) | 1981-05-28 |
Family
ID=10509316
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/GB1980/000195 WO1981001422A1 (en) | 1979-11-20 | 1980-11-10 | Sintered hard metals |
Country Status (7)
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4836849A (en) * | 1987-04-30 | 1989-06-06 | Westinghouse Electric Corp. | Oxidation resistant niobium alloy |
| DE3806602A1 (de) * | 1988-03-02 | 1988-07-07 | Krupp Gmbh | Hartmetallkoerper |
| US6057046A (en) * | 1994-05-19 | 2000-05-02 | Sumitomo Electric Industries, Ltd. | Nitrogen-containing sintered alloy containing a hard phase |
| US6716292B2 (en) | 1995-06-07 | 2004-04-06 | Castech, Inc. | Unwrought continuous cast copper-nickel-tin spinodal alloy |
| DE19704242C1 (de) * | 1997-02-05 | 1998-08-27 | Starck H C Gmbh Co Kg | Carbonitrid-Pulver, Verfahren zu ihrer Herstellung sowie deren Verwendung |
| US6797369B2 (en) * | 2001-09-26 | 2004-09-28 | Kyocera Corporation | Cemented carbide and cutting tool |
| CN116103561B (zh) * | 2023-01-17 | 2024-05-31 | 株洲硬质合金集团有限公司 | 一种锰钢基钢结硬质合金的制备方法 |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR1034896A (fr) * | 1950-07-25 | 1953-08-05 | Plansee Metallwerk | Procédé de fabrication de métaux durs frittés |
| GB1117108A (en) * | 1964-09-11 | 1968-06-12 | Corning Glass Works | Fused refractory castings |
| DE2137873A1 (en) * | 1970-11-03 | 1972-05-18 | Teledyne Ind | Carbo-nitride metal alloys - of improved strength and life, for machine tools |
| GB1332451A (en) * | 1969-07-28 | 1973-10-03 | Metro Cutanit Ltd | Cemented carbide materials |
| US3779746A (en) * | 1969-02-26 | 1973-12-18 | Aerojet General Co | Carbide alloys suitable for cutting tools and wear parts |
Family Cites Families (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| USRE22073E (en) | 1942-04-14 | Hard metal tool allot | ||
| USRE22166E (en) | 1942-08-25 | Hard metal alloy | ||
| GB708525A (en) | 1950-07-25 | 1954-05-05 | Metro Cutanit Ltd | Improvements relating to the production of sintered hard metal materials |
| US3455682A (en) * | 1967-07-31 | 1969-07-15 | Du Pont | Isostatic hot pressing of refractory bodies |
| US3779745A (en) * | 1969-02-26 | 1973-12-18 | Aerojet General Co | Carbide alloys suitable for cutting tools and wear parts |
| US3703368A (en) * | 1970-11-03 | 1972-11-21 | Teledyne Ind | Method for making castable carbonitride alloys |
| US3708355A (en) * | 1970-11-03 | 1973-01-02 | Teledyne Ind | Castable carbonitride alloys |
| US3736107A (en) * | 1971-05-26 | 1973-05-29 | Gen Electric | Coated cemented carbide product |
| DE2435989C2 (de) * | 1974-07-26 | 1982-06-24 | Fried. Krupp Gmbh, 4300 Essen | Verfahren zur Herstellung eines verschleißfesten, beschichteten Hartmetallkörpers für Zerspanungszwecke |
| US4049876A (en) * | 1974-10-18 | 1977-09-20 | Sumitomo Electric Industries, Ltd. | Cemented carbonitride alloys |
| US4066451A (en) * | 1976-02-17 | 1978-01-03 | Erwin Rudy | Carbide compositions for wear-resistant facings and method of fabrication |
| AT362943B (de) * | 1977-01-27 | 1981-06-25 | Sandvik Ab | Gesintertes hartmetall |
| US4265662A (en) * | 1977-12-29 | 1981-05-05 | Sumitomo Electric Industries, Ltd. | Hard alloy containing molybdenum and tungsten |
-
1979
- 1979-11-20 GB GB7940140A patent/GB2063922A/en not_active Withdrawn
-
1980
- 1980-11-10 US US06/285,189 patent/US4417922A/en not_active Expired - Fee Related
- 1980-11-10 EP EP80902119A patent/EP0039704A1/en not_active Withdrawn
- 1980-11-10 WO PCT/GB1980/000195 patent/WO1981001422A1/en not_active Application Discontinuation
- 1980-11-10 JP JP50246380A patent/JPS56501569A/ja active Pending
- 1980-11-12 ZA ZA00807000A patent/ZA807000B/xx unknown
- 1980-11-19 IT IT26081/80A patent/IT1134348B/it active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR1034896A (fr) * | 1950-07-25 | 1953-08-05 | Plansee Metallwerk | Procédé de fabrication de métaux durs frittés |
| GB1117108A (en) * | 1964-09-11 | 1968-06-12 | Corning Glass Works | Fused refractory castings |
| US3779746A (en) * | 1969-02-26 | 1973-12-18 | Aerojet General Co | Carbide alloys suitable for cutting tools and wear parts |
| GB1332451A (en) * | 1969-07-28 | 1973-10-03 | Metro Cutanit Ltd | Cemented carbide materials |
| DE2137873A1 (en) * | 1970-11-03 | 1972-05-18 | Teledyne Ind | Carbo-nitride metal alloys - of improved strength and life, for machine tools |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS56501569A (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html) | 1981-10-29 |
| US4417922A (en) | 1983-11-29 |
| GB2063922A (en) | 1981-06-10 |
| EP0039704A1 (en) | 1981-11-18 |
| ZA807000B (en) | 1982-06-30 |
| IT8026081A0 (it) | 1980-11-19 |
| IT1134348B (it) | 1986-08-13 |
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