CN104884197A - A polycrystalline super hard construction and a method of making same - Google Patents
A polycrystalline super hard construction and a method of making same Download PDFInfo
- Publication number
- CN104884197A CN104884197A CN201380068303.0A CN201380068303A CN104884197A CN 104884197 A CN104884197 A CN 104884197A CN 201380068303 A CN201380068303 A CN 201380068303A CN 104884197 A CN104884197 A CN 104884197A
- Authority
- CN
- China
- Prior art keywords
- diamond
- polycrystalline
- pcd
- main body
- area
- Prior art date
- Legal status (The legal status 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 status listed.)
- Pending
Links
- 238000010276 construction Methods 0.000 title claims abstract description 59
- 238000004519 manufacturing process Methods 0.000 title claims description 24
- 239000000463 material Substances 0.000 claims abstract description 319
- 239000010432 diamond Substances 0.000 claims abstract description 262
- 229910003460 diamond Inorganic materials 0.000 claims abstract description 261
- 239000002904 solvent Substances 0.000 claims abstract description 68
- 239000002245 particle Substances 0.000 claims description 238
- 238000000034 method Methods 0.000 claims description 116
- 239000000758 substrate Substances 0.000 claims description 101
- 239000003054 catalyst Substances 0.000 claims description 87
- 238000005245 sintering Methods 0.000 claims description 72
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 52
- 239000010941 cobalt Substances 0.000 claims description 49
- 229910017052 cobalt Inorganic materials 0.000 claims description 49
- 230000008569 process Effects 0.000 claims description 37
- 238000005516 engineering process Methods 0.000 claims description 30
- 229910052751 metal Inorganic materials 0.000 claims description 28
- 239000002184 metal Substances 0.000 claims description 28
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 26
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 26
- 238000004458 analytical method Methods 0.000 claims description 26
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 18
- 230000015572 biosynthetic process Effects 0.000 claims description 15
- 238000010191 image analysis Methods 0.000 claims description 14
- 229910052759 nickel Inorganic materials 0.000 claims description 14
- 238000006555 catalytic reaction Methods 0.000 claims description 12
- 238000011282 treatment Methods 0.000 claims description 12
- 230000008859 change Effects 0.000 claims description 11
- 229910002804 graphite Inorganic materials 0.000 claims description 11
- 239000010439 graphite Substances 0.000 claims description 11
- 229910052742 iron Inorganic materials 0.000 claims description 9
- 239000000956 alloy Substances 0.000 claims description 8
- 229910045601 alloy Inorganic materials 0.000 claims description 8
- 239000004575 stone Substances 0.000 claims description 8
- 150000002739 metals Chemical class 0.000 claims description 4
- 230000036961 partial effect Effects 0.000 claims description 4
- 238000012545 processing Methods 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 238000003786 synthesis reaction Methods 0.000 claims description 3
- 150000004767 nitrides Chemical class 0.000 claims description 2
- 230000000737 periodic effect Effects 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims 2
- 230000001186 cumulative effect Effects 0.000 claims 1
- 238000010008 shearing Methods 0.000 claims 1
- 239000000853 adhesive Substances 0.000 description 125
- 230000001070 adhesive effect Effects 0.000 description 125
- 238000002386 leaching Methods 0.000 description 51
- 235000013495 cobalt Nutrition 0.000 description 49
- 239000000203 mixture Substances 0.000 description 45
- 239000012071 phase Substances 0.000 description 39
- 238000005520 cutting process Methods 0.000 description 32
- 238000009826 distribution Methods 0.000 description 29
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 description 28
- 239000010410 layer Substances 0.000 description 26
- 238000004220 aggregation Methods 0.000 description 25
- 230000002776 aggregation Effects 0.000 description 25
- 239000011230 binding agent Substances 0.000 description 23
- 238000005498 polishing Methods 0.000 description 21
- 239000000843 powder Substances 0.000 description 21
- 229910009043 WC-Co Inorganic materials 0.000 description 19
- 229910052799 carbon Inorganic materials 0.000 description 19
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- 229910001573 adamantine Inorganic materials 0.000 description 17
- 238000001878 scanning electron micrograph Methods 0.000 description 17
- ORILYTVJVMAKLC-UHFFFAOYSA-N adamantane Chemical compound C1C(C2)CC3CC1CC2C3 ORILYTVJVMAKLC-UHFFFAOYSA-N 0.000 description 16
- 239000000654 additive Substances 0.000 description 15
- 230000000996 additive effect Effects 0.000 description 15
- 239000002131 composite material Substances 0.000 description 13
- 230000003247 decreasing effect Effects 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 11
- 239000011159 matrix material Substances 0.000 description 11
- 230000002829 reductive effect Effects 0.000 description 11
- 238000012856 packing Methods 0.000 description 10
- 239000002002 slurry Substances 0.000 description 10
- 239000000126 substance Substances 0.000 description 9
- 229910052721 tungsten Inorganic materials 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 239000011651 chromium Substances 0.000 description 8
- 239000008187 granular material Substances 0.000 description 8
- 239000003978 infusion fluid Substances 0.000 description 8
- 239000002243 precursor Substances 0.000 description 8
- 230000009467 reduction Effects 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 239000010937 tungsten Substances 0.000 description 8
- 229910052804 chromium Inorganic materials 0.000 description 7
- 230000007613 environmental effect Effects 0.000 description 7
- 238000003384 imaging method Methods 0.000 description 7
- 238000005259 measurement Methods 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 208000037656 Respiratory Sounds Diseases 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000010949 copper Substances 0.000 description 6
- 230000001965 increasing effect Effects 0.000 description 6
- 238000007711 solidification Methods 0.000 description 6
- 230000008023 solidification Effects 0.000 description 6
- 230000031068 symbiosis, encompassing mutualism through parasitism Effects 0.000 description 6
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 238000000151 deposition Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000012634 fragment Substances 0.000 description 5
- 150000007522 mineralic acids Chemical class 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 239000011435 rock Substances 0.000 description 5
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 4
- 230000002411 adverse Effects 0.000 description 4
- 230000002902 bimodal effect Effects 0.000 description 4
- 230000015556 catabolic process Effects 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 238000012937 correction Methods 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 230000006872 improvement Effects 0.000 description 4
- 230000000670 limiting effect Effects 0.000 description 4
- 239000011812 mixed powder Substances 0.000 description 4
- 229910052709 silver Inorganic materials 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 3
- 238000005266 casting Methods 0.000 description 3
- 238000005229 chemical vapour deposition Methods 0.000 description 3
- 229910021446 cobalt carbonate Inorganic materials 0.000 description 3
- ZOTKGJBKKKVBJZ-UHFFFAOYSA-L cobalt(2+);carbonate Chemical compound [Co+2].[O-]C([O-])=O ZOTKGJBKKKVBJZ-UHFFFAOYSA-L 0.000 description 3
- 239000004567 concrete Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 239000000428 dust Substances 0.000 description 3
- 230000002708 enhancing effect Effects 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 238000012423 maintenance Methods 0.000 description 3
- 229910052758 niobium Inorganic materials 0.000 description 3
- 239000010955 niobium Substances 0.000 description 3
- 238000005240 physical vapour deposition Methods 0.000 description 3
- 239000013557 residual solvent Substances 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- 238000010972 statistical evaluation Methods 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- 229910052720 vanadium Inorganic materials 0.000 description 3
- 229910000809 Alumel Inorganic materials 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 239000006061 abrasive grain Substances 0.000 description 2
- 210000000988 bone and bone Anatomy 0.000 description 2
- 150000001875 compounds Chemical group 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 230000004927 fusion Effects 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 2
- 230000000149 penetrating effect Effects 0.000 description 2
- 230000002093 peripheral effect Effects 0.000 description 2
- -1 pottery Substances 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 229910052702 rhenium Inorganic materials 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 238000007619 statistical method Methods 0.000 description 2
- 229910052715 tantalum Inorganic materials 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- INZDTEICWPZYJM-UHFFFAOYSA-N 1-(chloromethyl)-4-[4-(chloromethyl)phenyl]benzene Chemical compound C1=CC(CCl)=CC=C1C1=CC=C(CCl)C=C1 INZDTEICWPZYJM-UHFFFAOYSA-N 0.000 description 1
- QIJNJJZPYXGIQM-UHFFFAOYSA-N 1lambda4,2lambda4-dimolybdacyclopropa-1,2,3-triene Chemical compound [Mo]=C=[Mo] QIJNJJZPYXGIQM-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 239000004831 Hot glue Substances 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229910039444 MoC Inorganic materials 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910018487 Ni—Cr Inorganic materials 0.000 description 1
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000000441 X-ray spectroscopy Methods 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 239000003082 abrasive agent Substances 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000011260 aqueous acid Substances 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000027455 binding Effects 0.000 description 1
- 238000009739 binding Methods 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- UFGZSIPAQKLCGR-UHFFFAOYSA-N chromium carbide Chemical compound [Cr]#C[Cr]C#[Cr] UFGZSIPAQKLCGR-UHFFFAOYSA-N 0.000 description 1
- VNNRSPGTAMTISX-UHFFFAOYSA-N chromium nickel Chemical compound [Cr].[Ni] VNNRSPGTAMTISX-UHFFFAOYSA-N 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000001427 coherent effect Effects 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 238000000866 electrolytic etching Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- ZZUFCTLCJUWOSV-UHFFFAOYSA-N furosemide Chemical compound C1=C(Cl)C(S(=O)(=O)N)=CC(C(O)=O)=C1NCC1=CC=CO1 ZZUFCTLCJUWOSV-UHFFFAOYSA-N 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000007431 microscopic evaluation Methods 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 238000000879 optical micrograph Methods 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000011378 shotcrete Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 230000000153 supplemental effect Effects 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 238000007751 thermal spraying Methods 0.000 description 1
- 229910003470 tongbaite Inorganic materials 0.000 description 1
- 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 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 238000009849 vacuum degassing Methods 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- E—FIXED CONSTRUCTIONS
- E21—EARTH DRILLING; MINING
- E21B—EARTH DRILLING, e.g. DEEP DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
- E21B10/00—Drill bits
- E21B10/46—Drill bits characterised by wear resisting parts, e.g. diamond inserts
- E21B10/56—Button-type inserts
- E21B10/567—Button-type inserts with preformed cutting elements mounted on a distinct support, e.g. polycrystalline inserts
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F7/00—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression
- B22F7/06—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of composite workpieces or articles from parts, e.g. to form tipped tools
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B24—GRINDING; POLISHING
- B24D—TOOLS FOR GRINDING, BUFFING OR SHARPENING
- B24D18/00—Manufacture of grinding tools or other grinding devices, e.g. wheels, not otherwise provided for
- B24D18/0009—Manufacture of grinding tools or other grinding devices, e.g. wheels, not otherwise provided for using moulds or presses
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B24—GRINDING; POLISHING
- B24D—TOOLS FOR GRINDING, BUFFING OR SHARPENING
- B24D3/00—Physical features of abrasive bodies, or sheets, e.g. abrasive surfaces of special nature; Abrasive bodies or sheets characterised by their constituents
- B24D3/02—Physical features of abrasive bodies, or sheets, e.g. abrasive surfaces of special nature; Abrasive bodies or sheets characterised by their constituents the constituent being used as bonding agent
- B24D3/04—Physical features of abrasive bodies, or sheets, e.g. abrasive surfaces of special nature; Abrasive bodies or sheets characterised by their constituents the constituent being used as bonding agent and being essentially inorganic
- B24D3/06—Physical features of abrasive bodies, or sheets, e.g. abrasive surfaces of special nature; Abrasive bodies or sheets characterised by their constituents the constituent being used as bonding agent and being essentially inorganic metallic or mixture of metals with ceramic materials, e.g. hard metals, "cermets", cements
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
- C04B41/91—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics involving the removal of part of the materials of the treated articles, e.g. etching
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C26/00—Alloys containing diamond or cubic or wurtzitic boron nitride, fullerenes or carbon nanotubes
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/02—Local etching
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/10—Etching compositions
- C23F1/14—Aqueous compositions
- C23F1/16—Acidic compositions
- C23F1/28—Acidic compositions for etching iron group metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F5/00—Manufacture of workpieces or articles from metallic powder characterised by the special shape of the product
- B22F2005/001—Cutting tools, earth boring or grinding tool other than table ware
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Mining & Mineral Resources (AREA)
- Organic Chemistry (AREA)
- Ceramic Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Metallurgy (AREA)
- Environmental & Geological Engineering (AREA)
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Abstract
A polycrystalline super hard construction comprising a body of polycrystalline diamond (PCD) material and a plurality of interstitial regions between inter-bonded diamond grains forming the polycrystalline diamond material; the body of PCD material comprises a working surface positioned along an outside portion of the body; a first region substantially free of a solvent/catalysing material; and a second region remote from the working surface that includes solvent/catalysing material in a plurality of the interstitial regions. The first region extends to a depth of at least about 800 microns from the working surface into the body of polycrystalline diamond material.
Description
Technical field
The present invention relates to the polycrystalline superhard construction comprising polycrystalline diamond (PCD) body of material and the method manufacturing heat-staple polycrystalline diamond stone construction.
Background technology
Tool insert for machining can comprise with other instruments polycrystalline diamond (PCD) layer being attached to cemented carbide substrate.PCD is the example of superhard material, is also referred to as superabrasive materials in the form.
The parts comprising PCD can be used for various cutting, machined, hole or break hard or grinding-material into pieces as rock, metal, pottery, composite and containing in the instrument of wood material.PCD comprises the diamond particles of a large amount of symbiosis substantially, and described diamond particles forms the bone body (skeletal mass) in the gap limited between diamond particles.PCD material typically comprise account for its volume at least about 80% diamond and can stand to be greater than about 5GPa by making the aggregation of diamond particles under the existence of sintering aid, typically about 5.5GPa hyperpressure and at least about 1200 DEG C, typically the temperature of about 1440 DEG C manufactures, and described sintering aid is also referred to as adamantine catalyst material.Can be understood as adamantine catalyst material is the material that can promote the direct symbiosis of diamond particles under thermodynamically more stable than the graphite pressure and temperature condition of diamond.
Typically comprise any VIII element for adamantine catalyst material and Usual examples be cobalt, iron, nickel and comprise some alloys of alloy of these elements any.PCD can be formed in cobalt-cemented tungsten carbide substrate, and this substrate can provide the source of Co catalysts material for PCD.
During the main body sintering of PCD material, the component of sintering-carbide substrate liquefies as the cobalt when cobalt-cemented tungsten carbide substrate and moves fast the gap area (sweep) to diamond particles from the region of contiguous a large amount of diamond particles.In this example, cobalt serves as catalyst to promote the formation of bonded diamond particles.Selectively, Metal-solvent catalyst can mix with diamond particles before diamond particles and substrate stand HPHT process.Gap in PCD material can be full of catalyst material at least in part.That therefore the diamond lattic structure of symbiosis comprises original diamond particle and new precipitation or regrow diamond phase, this diamond combines (bridge) primary granule.In final sintering structure, catalyst/solvent material can remain at least some gap be present between sintered diamond particles usually.
The known problem coexisted with this conventional P CD briquet is that they subject to thermal degradation when when cutting and/or be exposed at high temperature during wearing and tearing program.Someone thiss is presumably because, at least partly owing to there is residual solvent/catalyst material in microstructural gap, this at high temperature has adverse effect to the performance of PCD briquet due to the difference existed between the thermal expansion character and the thermal expansion character of intergranular bond diamond of interstitial solvent Metal catalyst materials.Known this different thermal expansion can occur at the temperature of about 400 DEG C, and is considered to the generation that can cause fracture in diamond and diamond bond, and finally causes forming crack and fragment in PCD structure.Cracked in PCD table or break and may reduce the mechanical performance of cutting element or cause the inefficacy of cutting element in boring or cutting operation, thus cause PCD structure to be not suitable for further use.
Known is also be considered to a kind of form relevant with the adhesion of solvent metal catalyst to diamond crystal with the existence of the solvent metal catalyst in gap area with the another kind of form of the thermal degradation that conventional P CD material coexists.Particularly, at high temperature, diamond particles can carry out chemical breakdown or reverse conversion (back-conversion) with solvent/catalyst.At extreme temperatures, solvent metal catalyst is considered to cause in a diamond less desirable catalysis phse conversion so that part diamond particles can be converted into carbon monoxide, carbon dioxide, graphite or its combination, thus reduces the mechanical performance of PCD material and the practical application of PCD material is restricted to about 750 DEG C.
Attempt in conventional PCD materials, solve this less desirable thermal degradation form to be well known in the art.Usually, these trials all concentrate in the formation of PCD main body of the heat endurance compared with conventional P CD material with improvement.The known technology that a kind of production has the PCD main body of the heat endurance of improvement comprises, after formation PCD main body, such as use Chemical Leaching to remove all or part of solvent catalysis agent material.Removing catalyst/adhesive from diamond lattice structure makes polycrystalline diamond layer more heat-resisting.
Due to the adverse environment of cutting element typical operation, expect to have the cutting element of the cutting lay of the wearability of improvement, intensity and fracture toughness.But when PCD material manufactured place is more wear-resisting, such as, by removing residual catalyst material from the gap in diamond substrate, PCD material typically becomes more frangible and easily breaks and be therefore easy to infringement or reduce resistance to rupture.
Therefore need to overcome or substantially improve the problems referred to above to provide the resistance to fracture with enhancing and the PCD material of peeling off.
Summary of the invention
From first aspect, the invention provides the polycrystalline superhard construction comprising polycrystalline diamond (PCD) body of material and the multiple gap areas between the diamond particles of mutual bonding forming polycrystalline diamond abrasive compact; This PCD material main body comprises:
Along the working surface that the Outboard Sections of main body is located;
Be substantially free of the first area of solvent/catalysis material; And
Away from the second area of working surface, it comprises solvent/catalysis material in multiple gap area;
Wherein, first area extends into the degree of depth at least about 800 μm polycrystalline diamond abrasive compact main body from working surface.
From second aspect, the invention provides the method for the manufacture of heat-staple polycrystalline diamond stone construction, it comprises the following step:
Pack processing is containing the polycrystalline diamond stone construction of polycrystalline diamond main body, the diamond particles that this polycrystalline diamond main body comprises multiple mutual bonding and the gap area be arranged on therebetween, thus remove solvent/catalyst material from the first area of diamond body and allow solvent/catalyst material to be retained in the second area of diamond body;
Comprise further, during treatment step, control the degree of depth of first area so that its working surface from diamond body extends the degree of depth at least about 800 μm.
Accompanying drawing explanation
Mode by means of only example is also described various embodiments with reference to accompanying drawing by the present invention in more detail, wherein:
Fig. 1 is the microstructure schematic diagram of PCD material main body;
Fig. 2 is the schematic diagram of the PCD briquet comprising the PCD structure being bonded to substrate;
Fig. 3 a to 3c is the cross sectional representation of a part of PCD structure that Fig. 2 of the embodiment of progressively wearing and tearing in application is shown by basis;
Fig. 4 is the side schematic view of the example components comprising the first structure and the second structure;
Fig. 5 is the schematic diagram circulated for the manufacture of the exemplary partial pressure and temperature of superhard construction;
Fig. 6 to Figure 10 is the schematic diagram of the exemplary partial pressure and temperature circulation for the manufacture of PCD structure;
Figure 11 a to 11b is the procedural image of the micrograph (shown in egative film) of the polishing portion of the embodiment of the PCD material main body of different diamond density;
Figure 12 tests figure for the polishing scratch area of Cutting Length in (vertical borer test) at the vertical boring mill of an embodiment; And
Figure 13 in the vertical boring mill test of another embodiment for the figure of the polishing scratch area of Cutting Length.
Detailed description of the invention
With reference to Fig. 1, PCD material main body 10 comprises the bone body in the directly diamond particles 12 of bonding and the gap 14 between diamond particles 12 mutually, and packing material or adhesive material can be filled at least in part in this gap 14.Packing material can comprise such as cobalt, nickel or iron or alternately can comprise other non-diamond phase additive one or more, such as, as titanium, tungsten, niobium, tantalum, zirconium, molybdenum, chromium or vanadium, the content of one or more above-mentioned substances in packing material can be such as, 1% of the weight of packing material is about when using Ti, when using V, in packing material, the content of V is about 2% of the weight of packing material, and when using W, in packing material, the content of W is about 20% of the weight of packing material.
Publication number is the method that the PCT application of WO2008/096314 discloses coated diamond particles, so that polycrystalline ultrahard abrasive element or composite can be formed, comprise the adamantine polycrystalline ultrahard abrasive element in matrix, described polycrystalline ultrahard abrasive element is selected from material, and described material is from comprising VN, VC, HfC, NbC, TaC, Mo
2select in the group of C, WC.Publication number is that the PCT application of WO2011/141898 also discloses PCD and formation comprises additive if the method for the PCD of vanadium carbide is especially to improve wearability.
Wish the constraint not being subject to any particular theory simultaneously, the combination of the metallic addition in packing material can be considered in use have the effect of the energy being better dispersed in PCD material the crackle producing and spread, cause the polishing machine of the improvement of PCD material and the impact resistance of enhancing and resistance to fracture, and therefore extend working life in some applications.
According to some embodiments, the sintered body of the PCD material of manufacture have diamond with adamantine bonding and have comprise catalyst/solvent with by the microstructure of WC and other non-diamond phase carbide as together with VC or the second-phase of the WC (tungsten carbide) replacing other non-diamond phase carbide to disperse as VC.PCD material main body can be formed according to standardized method, such as, as at publication number for the use HpHT condition described in the PCT application of WO2011/141898 produces sintering PCD table.
Fig. 2 and Fig. 3 a to 3c shows the embodiment of the polycrystalline compound structure 20 of the tool insert use as the drill bit (not shown) for earth's crust probing (boring into the earth).Polycrystalline composite compact or structure 20 comprise the main body 22 of superhard material as PCD material, and at interface 24, entirety is bonded to substrate 30.Substrate 30 can be become as cemented carbide material by hard material and can be such as cemented tungsten carbide, sintering ramet, sintering titanium carbide, sintering molybdenum carbide or its mixture.Binder metal for this carbide can be such as nickel, cobalt, iron or the alloy containing one or more these metals.Typically, this adhesive can exist with the quantity of 10-20% quality, but this can be low to moderate the quality or less of 6%.Some binder metal may infiltrate polycrystalline diamond abrasive compact main body 22 during formation briquet 20.
Superhard material can be such as polycrystalline diamond (PCD).
Cutting element 20 in use can be installed to little main body (bit body) as in drag bit body (not shown).The upper surface of the exposure of the superhard material 22 relative with substrate 30 forms working surface 34, and this working surface 34 in use performs the surface of cutting along the edge 36 on this surface.
Substrate 30 can be such as generally columniform and have peripheral surface and peripheral upper edges.
The exposed surface of cutter elements 20 comprises the working surface 34 in use also served as above.Inclined-plane 44 the side of working surface 34 and cutting edge 36 and cutter or cylinder (barrel) 42 at least partially between extend, cutting edge 36 is edge limited by inclined-plane 44 and side 42.
The working surface of cutter or " above " 34 are surface or multiple surface, and when cutter is used to from main body cutting material, cut material fragment flows from this surface or multiple surface, before 34 flowings guiding the fragment of new formation.This surface 34 is commonly called upper surface or the working surface of cutter.In the present invention, " fragment " is the fragment of the main body in use removed from the working surface of main body by cutter.
In the present invention, " side " 42 of cutter crosses usually be considered to side or the cylinder of cutter by the surface of the cutter on surface that the body of material of Tool in Cutting produces or multiple surface.Side 42 can provide the gap apart from main body and can comprise multiple side.
In the present invention, " cutting edge " 36 is in use intended to perform cutter body.
In the present invention, " polishing scratch " is in use because the wearing and tearing of cutter are by removing the surface of the cutter of a large amount of cutting material formation.Side can comprise polishing scratch.When in use tool wear, material can remove gradually from nearest cutting edge, thus constantly redefine when polishing scratch is formed cutting edge, above with position and the shape of side.In the present invention, be appreciated that term " cutting edge " refer to as above function limitations in Tool Wear Process until any concrete stage of tool failure or multiple stage include but not limited to be in substantially does not wear and tear or the cutting edge of reality of cutter of unused state.
With reference to Fig. 3 a to 3c, inclined-plane 44 is formed in the structure of closing on cutting edge 36 and side 42.34 be therefore connected to side 42 by the inclined-plane 44 extending to 34 above from cutting edge 36 above, and to be arranged in the plane of the plane extended perpendicular to the cutter longitudinal axis be the plane of predetermined angle theta.In certain embodiments, this chamfering can reach about 45 °.The vertical height on inclined-plane 44 such as can between 350 μm and 450 μm, as about 400 μm.
Fig. 3 a to 3c uses that the technology that is described below in detail is processed schematically illustrates figure with the PCD removing residual solvent/catalyst from the clearance space between diamond particles structure 20.Degree of depth D the PCD layer 22 at the interface 24 of the substrate 30 be substantially removed from working surface 34 towards solvent/catalyst is called as the leaching degree of depth (leach depth).According to embodiment, this degree of depth D is at least about 800 μm.In certain embodiments, this degree of depth is between about 800 μm and about 1400 μm, in other embodiments, this degree of depth is between about 850 μm and about 1400 μm, in other embodiments, this degree of depth is between about 800 μm to about 1200 μm or 1300 μm, and in other embodiments, this degree of depth is greater than 1000 μm.
The primary importance of cutting edge when first make contact 36 in Fig. 3 a is first time uses.When tool wear, the wearing and tearing on cutter be the position represented by dotted line 45 to the second dotted line 46 movement shown in, as shown in Fig. 3 a to 3c, with the movement of the cutting edge represented by reference number 36a and 36b.Fig. 3 b with represent cutting starting point the first dotted line 45 and represent that second dotted line 46 worn and torn gradually of superhard material shows the first stage.
Fig. 3 c show extra use after cutter further wearing and tearing and shown the progress of polishing scratch by PCD material.Therefore wearing and tearing are only carried out in the leaching region of PCD.
Do not wish to be subject to theoretical constraint simultaneously, can expect that crackle has the tendency along the interface diffusion between the leaching region of PCD and non-leaching region in PCD.Usually, once wearing and tearing arrive the top on inclined-plane 44, this may cause peeling off, but, as shown in Figure 3 c, when now polishing scratch remains on the leaching region of PCD, unlikely generation is peeled off, because polishing scratch not yet arrives the interface between the leaching region of PCD and non-leaching region, crackle tends to propagate along this interface initially peel off.
The cutter of Fig. 1 to Fig. 3 c such as can as described belowly manufacture.
In the present invention, " green compact " are the main bodys of the parts comprising particle to be sintered and kept together by particle, as adhesive, and such as organic bond.
The embodiment of superhard construction can comprise the particle of superhard material by preparation and adhesive such as the method for the green compact of organic bond manufactures.These green compact also can comprise the catalyst material of the sintering for promoting superhard particles.Green compact can by combining particle with adhesive and making them be formed as having the main body of the overall shape substantially identical with sintering main body and dry adhesive to manufacture.At least some adhesive material can be removed by such as burning.Green compact can be formed by comprising compacting process, injection or additive method such as the methods such as casting, extruding, deposition modeling.Green compact can be made up of the assembly comprising particle and binding agent, and such as, this assembly can the form of sheet, block or dish exist, and green compact itself can be made up of multiple green compact.
An embodiment for the manufacture of the method for green compact comprises provides flow casting molding sheet material, each sheet material such as comprises multiple diamond particles together with adhesives, as water base organic bond, and by the top of sheet-stacking at top of each other and supporter.Comprise there is varying particle size distribution, the different sheet materials of diamond particles of diamond content or additive can by stacking to realize required structure selectively.Sheet material can be manufactured by method as known in the art, and as extruding or flow casting molding method, the suspension wherein comprising diamond particles and adhesive material is laid on the surface and is allowed to drying.Also the additive method of manufacture diamond-support sheet can be used, as being numbered 5,766,394 and 6,446, described in the United States Patent (USP) of 740.Alternative for diamond coated-supporting layer comprises gunite, as thermal spraying.
Green compact for superhard construction can be placed on substrate, and if cemented carbide substrate is to form pre-sintered components, as known in the art, this substrate can be sealed in the container for hyperpressure stove.This substrate can for the source promoting the sintering of superhard particles to provide catalyst material.In certain embodiments, superhard particles can be diamond particles and substrate can be cobalt-cemented tungsten carbide, and the cobalt in substrate is the source of the catalyst for sintered diamond particles.Pre-sintered components can comprise the additional source of catalyst material.
In a version, the method can comprise and to be loaded into by the container comprising pre-sintered components in forcing press and to make green compact stand hyperpressure and temperature, and under this hyperpressure and temperature, superhard material is thermodynamically stable, to sinter superhard particles.In certain embodiments, green compact comprise diamond particles and the pressure that assembly stands is at least about 5GPa and temperature is at least about 1300 DEG C.
The version of the method can comprise with such as at publication number for manufacturing diamond composite structure for the manufacture of the method for superhard enhancing hard metal material disclosed in the PCT application of WO2009/128034.Comprise diamond particles and metal binder material such as the mixture of powders of cobalt to prepare by these particles are combined and mixed by these particles.Effective powder preparation technology can be used for mixed-powder, as humidity or the multi-faceted mixing of drying, planetary ball mill and high shear mixing homogenizer.In certain embodiments, the average-size of diamond particles can be at least about 50 μm and diamond particles can by by powder mixing or manual being stirred in powder together and being combined with other particle in some cases.In a version of the method, the precursor material being suitable for being converted into adhesive material subsequently in mixture of powders, can be comprised, and in a version of the method, metal binder material can be introduced into be suitable for the mode penetrated in green compact.Mixture of powders can be placed in punch die or mould and to be compacted to form green compact, such as, by uniaxial compression or other compression method, as isostatic cool pressing system (CIP).The sintering process that green compact can stand to be known in the art is to form sintered article.In a version, the method can comprise and the container comprising pre-sintered components is loaded into forcing press neutralization and makes green compact stand hyperpressure and temperature, and under this hyperpressure and temperature, superhard material is thermodynamically stable, to sinter superhard particles.
After sintering, and if polycrystalline superhard construction can be ground in main body that target size needs to be included in produced polycrystalline superhard material have the 45 ° of inclined-planes being highly approximately 0.4mm.
Sintered article can stand process subsequently under the heat-staple pressure and temperature of diamond, some or all non-diamond carbons are converted back diamond and produces diamond composite structure.Can use the hyperpressure stove be well known in the art of diamond synthesized body and for the second sintering process, this pressure can be at least about 5.5GPa, this temperature can be at least about 1250 DEG C.
The further embodiment of superhard construction can be manufactured by a kind of method, the method comprises for diamond composite structure provides PCD structure and front body structure, each structure is formed as complementary separately shape, is assembled to PCD structure and diamond composite structure to form non-coupling assembling in cemented carbide substrate, and makes non-coupling assembling stand the pressure at least about 5.5GPa and the temperature at least about 1250 DEG C constructs to form PCD.Front body structure can comprise carbide particle and diamond or non-diamond carbon material, as graphite, and comprises the adhesive material of metal as cobalt.Front body structure can be contain the mixture of powders of diamond or the particle of non-diamond carbon and the particle of carbide material and the green compact of compressing powder mixture formation by compressed package.
The present invention can be further detailed by following non-limiting example.
Particle such as the diamond particles in starting mixt before sintering or the particle of superhard material can be such as bimodal, that is, charging comprises the mixture of the coarse grain grade of diamond particles and the particulate grade of diamond particles.In certain embodiments, coarse grain grade can have such as about 10 μm to the averaged particles/particle size within the scope of 60 μm." averaged particles or particle size " means that single particle/particle has a size range, and this size range has the averaged particles/particle size of expression " average ".Averaged particles/the particle size of particulate grade is less than the size of coarse grain grade, such as, between about 1/10 to 6/10 of the size of coarse grain grade, and in certain embodiments such as can about 0.1 μm to 20 μm between scope.
In certain embodiments, brait grade can in the scope of about 50% to about 97% for the weight ratio of fine diamond grade, and the weight ratio of fine diamond grade can be from about 3% to about 50%.In other embodiments, coarse grain grade for the weight ratio of particulate grade by the scope of about 70:30 to about 90:10.
In other embodiments, coarse grain grade can in the scope of such as about 60:40 to about 80:20 for the weight ratio of particulate grade.
In certain embodiments, the particle size distribution of coarse grain grade and particulate grade is overlapping and in certain embodiments, and between the single-grade of composition multimodal distribution, the component of the different size of briquet is spaced apart an order of magnitude.
Described embodiment comprises at least one wide bimodal size particle size distribution between the coarse grain grade and particulate grade of superhard material, but some embodiments can comprise three or an even four or more size pattern, this size pattern such as can one, the interval order of magnitude dimensionally, such as, average particle size particle size be 20 μm, 2 μm, the mixing of the particle size of 200nm and 20nm.
Can be pulverized compared with king kong stone granulate and similar method as sprayed by known method, the size of diamond particles/particle being become particulate grade, coarse grain grade or other size in-between.
Be in the embodiment of polycrystalline diamond abrasive compact at superhard material, the diamond particles for the formation of polycrystalline diamond abrasive compact can be natural or Prof. Du Yucang.
In certain embodiments, binder catalyst/solvent can comprise cobalt or some other iron family element, as iron or nickel or its alloy.The carbide of the group IV-VI metal in the periodic table of elements, nitride, boride and oxide are other examples of the non-diamond materials that be introduced in sintered mixture.In certain embodiments, binder/catalyst/sintering aid can be Co.
Cemented metal carbide substrate on composition can be conventional and, thus, can comprise any IVB race, VB race or group vib metal, it is pressed and sinters under the existence of the adhesive of cobalt, nickel or iron or its alloy.In certain embodiments, metal carbides are tungsten carbides.
In certain embodiments, the main body of such as diamond and carbide material adds that sintering aid/binder/catalyst is applied in powder form, and sinters in single UHP/HT process simultaneously.The mixture of diamond particles and a large amount of carbide to be positioned in HP/HT reaction tank assembly and to carry out HP/HT process.The HP/HT treatment conditions selected are enough to the intergranular bonding realized between the adjacent particle of abrasive particle, and the combination of optional sintering particle and cemented metal carbide support.In one embodiment, these treatment conditions generally include and apply to be about 3-120 minute at least about the temperature of 1200 DEG C and the hyperpressure that exceedes about 5GPa.
In another embodiment, in the sintering process of superhard polycrystalline material, presintering substrate in a separate step before can being to combine in HP/HT forcing press.
In another embodiment, the main body of substrate and polycrystalline superhard material all carries out preformed.Such as, the bimodal charging of superhard particles/particle with optional be also powder type carbonate adhesive-catalyst mix together with, and this mixture is packed into the container of suitable shape, then stands extremely high pressure and temperature in a press.Typically, this pressure is at least 5GPa, and temperature is at least about 1200 DEG C.Then the preform of polycrystalline superhard material is positioned over the appropriate location on the upper surface of preformed carbide substrate (containing binder catalyst), and assembly is positioned in the container of suitable shape.Then make assembly stand high temperature and high pressure in a press, the rank of temperature and pressure is still respectively at least about 1200 DEG C and 5GPa.In the process, solvent/catalyst to move to the main body of superhard material from substrate and serves as adhesive-catalyst to realize the symbiosis in layer, and for polycrystalline superhard material layer is bonded to substrate.Sintering process is also for being bonded to substrate by the main body of superhard polycrystalline material.
The much lower sintered-carbide grade of cobalt content is as the practical application of the substrate for PCD insert in following truth, and namely in sintering process, some Co need to enter PCD layer with the formation of catalysis PCD from substrate migration.It for this reason, the base material comprising lower Co content manufactures PCD more difficult, although may be desired.
An embodiment of superhard construction can obtain by the following method, comprise: cemented carbide substrate is provided, make a large amount of diamond particles that the surface contact of described substrate is assembled, that substantially do not bond to form pre-sintered components, pre-sintered components is encapsulated in the container for super-pressure stove, this pre-sintered components is made to stand the pressure at least about 5.5GPa and the temperature at least about 1250 DEG C, and sintered diamond particle is to form PCD composite compact element, this element comprise to completely form in cemented carbide substrate and with the PCD structure of its combination.In some embodiments of the invention, pre-sintered components can stand at least about 6GPa, at least about 6.5GPa, at least about 7GPa or even at least about the pressure of 7.5GPa.
The hardness of cemented tungsten carbide substrate by standing super-pressure especially by this substrate and high temperature strengthens under the thermodynamically stable pressure and temperature of diamond.The amplitude that hardness strengthens can be depending on pressure and temperature condition.Particularly, hardness strengthens and can increase higher pressure.When not wishing the constraint by particular theory, it is relevant that this is considered in compacting sintering process, to enter PCD with Co from basement migrate, because the degree that hardness strengthens directly depends on the minimizing of Co content in substrate.
In cemented carbide substrate containing enough for adamantine solvent/catalyst, and PCD structure is intactly formed in suprabasil embodiment in ultra-high pressure sintering process, solvent/catalyst material can be included in or be introduced in the aggregation from the diamond particles of the material source being different from cemented carbide substrate.This solvent/catalyst material can comprise the cobalt only penetrated into before ultra-high pressure sintering step and in ultra-high pressure sintering process from substrate the aggregation of diamond particles.But, in cobalt or the lower embodiment of other solvent/catalyst material content in the substrate, particularly when its lower than cemented carbide material about 11 % by weight time, then may need to provide other source to guarantee the good sintering of aggregation, to form PCD.
Can be introduced in the aggregation of diamond particles by various method for adamantine solvent/catalyst, comprise solvent/catalyst material and the diamond particles of mixed-powder form, in the deposited on silicon solvent/catalyst material of diamond particles, or the part penetrating solvent/catalyst material from the material source being different from substrate before the sintering step or as sintering step enters aggregation.The method deposited on the surface of diamond particles as cobalt for adamantine solvent/catalyst is well known in the art, and it comprises chemical vapour deposition (CVD) (CVD), physical vapour deposition (PVD) (PVD), sputter coating, electrochemical method, chemical coating method and ald (ALD).It should be understood that the merits and demerits of often kind of method depends on the character of sintering aid material and coated structure to be deposited, and the characteristic of particle.
In an embodiment of the inventive method, by following methods, cobalt is deposited on the surface of diamond particles: first depositing precursor materials, then precursor material is converted into the material of containing element metallic cobalt.Such as, in a first step, following reaction can be used to be deposited on the surface of diamond particles by cobalt carbonate:
Co(NO
3)
2+Na
2CO
3→CoCO
3+2NaNO
3
Can be realized by the method described in the PCT patent of publication number WO2006/032982 for adamantine cobalt or the carbonate of other solvent/catalyst or the deposition of other precursor.Then such as by pyrolysis as described below, cobalt carbonate is converted into cobalt and water:
CoCO
3→CoO+CO
2
CoO+H
2→Co+H
2O
In another embodiment of method of the present invention, the precursor of cobalt powder or cobalt, as cobalt carbonate, can mix with diamond particles.When the precursor using solvent/catalyst as cobalt, material described in heat treatment may be necessary, with before sintering aggregation, carry out reacting the solvent/catalyst material with generting element form.
In certain embodiments, cemented carbide substrate can be formed by the tungsten carbide particle be bonded together by adhesive material, and this adhesive material comprises the alloy of Co, Ni and Cr.This tungsten carbide particle can be formed as account for substrate at least 70 % by weight and at the most 95 % by weight.Adhesive material can comprise the Cr between the Ni, about 0.1 to 10 % by weight between about 10-50 % by weight, and all the other percentage by weights comprise Co.In certain embodiments, the Size Distribution of the tungsten carbide particle in cemented carbide substrate has following characteristics:
-be less than the particle diameter of the carbide particle of 17% for being equal to or less than about 0.3 μm;
The particle diameter of the tungsten carbide particle between-Yue 20-28% is between about 0.3-0.5 μm;
The particle diameter of the tungsten carbide particle between-Yue 42-56% is between about 0.5-1 μm;
-be less than the particle diameter of the tungsten carbide particle of about 12% for being greater than 1 μm; And
The average grain diameter of-tungsten carbide particle is about 0.6 ± 0.2 μm.
In certain embodiments, adhesive comprises the carbon between tungsten between about 2-20 % by weight and about 0.1-2 % by weight in addition.
The basalis adjacent with the interface of polycrystalline diamond abrasive compact main body can have the thickness of such as about 100 μm, and can comprise tungsten carbide particle and adhesive phase.The feature of this layer can be the following elements composition having and measured by energy dispersion X-ray microscopic analysis (EDX):
Cobalt between-Yue 0.5-2.0 % by weight;
Nickel between-Yue 0.05-0.5 % by weight;
Chromium between-Yue 0.05-0.2 % by weight; And
-tungsten and carbon.
In another embodiment, comprise at element composition in the above-mentioned layer of the chromium between nickel between cobalt between about 0.5-2.0 % by weight, about 0.05-0.5 % by weight and about 0.05-0.2 % by weight, remainder is tungsten and carbon.
Basalis can comprise free carbon further.
The magnetic characteristic of cemented carbide material can be relevant with composition characteristic to important structure.For measuring the concentration that the modal technology of carbon content in sintered-carbide is the indirect tungsten in proportional dissolving in indirect inspection adhesive: the carbon content of dissolving in adhesive is higher, then the tungsten concentration of dissolving in adhesive is lower.In adhesive, W content can by measurement magnetic moment σ or magnetic saturation M
sdetermine, M
s=4 π σ, these values and W content have contrary relation (Roebuck (1996), " Magnetic moment (saturation) measurements on cementedcarbide materials ", Int.J.Refractory Met., Vol.14, pp.419-424.).Following formula can be used for magnetic saturation M
sassociate with the concentration of W with C in adhesive:
M
s∝ [C]/[W] x % by weight Co x 201.9, unit is μ T.m
3/ kg
Adhesive cobalt content in cemented carbide material is measured by various method as known in the art, comprise indirect method as the magnetic characteristic of cemented carbide material or the more direct method by energy dispersion X-ray spectroscopy (EDX), or the method for Chemical Leaching based on Co.
Carbide particle such as the average grain diameter of WC particle such as can by checking the optical microscope image of the cross section of the cemented carbide material main body of microphoto or the metallurgical preparation using SEM (SEM) to obtain, and application average linear interception (mean linearintercept) technology is determined.Alternatively, the average-size of WC particle is estimated indirectly by the magnetic coercive force measuring cemented carbide material, described magnetic coercive force represents the mean free path of the particle in the middle of Co, uses simple formula well known in the art can calculate WC particle diameter by this magnetic coercive force.This formula has quantized the inverse relationship between the magnetic coercive force of Co-sintering WC cemented carbide material and the mean free path of Co, thus determines average WC particle diameter.Magnetic coercive force and MFP have inverse relationship.
In the present invention, composite " mean free path " (MFP) as sintered-carbide is the measuring of average distance between the gathering carbide particle that sinters in adhesive material.The mean free path feature of cemented carbide material can use the microphoto of the polishing portion of this material to measure.Such as, this microphoto can have the magnifying power of about 1000 times.This MFP can to reach the standard grade and distance between each crosspoint of crystal boundary is determined at uniform grid by measuring.Matrix (matrix) line segment Lm is sued for peace, and particle (grain) line segment Lg is sued for peace.The mean matrix line segment length adopting diaxon is " mean free path ".The mixture of multiple distributions of tungsten carbide particle size may cause MFP value for the extensive distribution of same matrix content.Below this is explained in more detail.
In Co adhesive, the concentration of W depends on C content.Such as, under low C content, W concentration is obviously higher.In the Co adhesive of Co-sintering WC (WC-Co) material, W concentration and C content can be determined by magnetic saturation angle value.Cemented tungsten carbide is magnetic moment or the magnetic saturation that the magnetic saturation 4 π σ of the hard metal of an one example or magnetic moment σ are defined as per unit weight.The magnetic moment σ of pure Co is that cubic meter every kilogram (μ T.m is multiplied by 16.1 micro-teslas
3/ kg), and the saturation induction of pure Co, being also referred to as magnetic saturation 4 π σ, is 201.9 μ T.m
3/ kg.
In certain embodiments, cemented carbide substrate can have at least about 100Oe and the average magnetic coercive force of maximum about 145Oe, and about at least about 89% at the most about 97% the magnetic moment of specific magnetic saturation degree of pure Co.
MFP characteristic in desired substrate can be realized by several method as known in the art.Such as, lower MFP value can realize by using lower metal binder content.The actual lower limit of about 3 % by weight cobalts is applicable to sintered-carbide and conventional liquid phase sintering.Stand such as pressure in cemented carbide substrate to exceed in the super-pressure of about 5GPa and an embodiment of high temperature (such as exceeding about 1400 DEG C), the metal-to-metal adhesive of lower content can be realized as cobalt.Such as, when cobalt content is about 3 % by weight and the average-size of WC particle is about 0.5 μm, MFP will be about 0.1 μm, and when the average-size of WC particle is about 2 μm, MFP will be about 0.35 μm, and when the average-size of WC particle is about 3 μm, MFP will be about 0.7 μm.These average particle size particle size correspond to the pass the natural pulverizing process producing particle logarithm normal distribution and the single powder rank obtained.Higher matrix (adhesive) content can cause higher MFP value.
According to the details of powder-processed and mixing, change particle diameter by mixing different powder ranks and change the full spectrum MFP value that distribution can realize substrate.Definite value must rule of thumb be determined.
In certain embodiments, substrate comprises Co, Ni and Cr.
For the adhesive material of substrate can comprise in solid solution at least about 0.1 % by weight at the most about 5 % by weight V, Ta, Ti, Mo, Zr, Nb and Hf in one or more.
In other embodiments, polycrystalline diamond (PCD) composite compact element can comprise at least about 0.01 % by weight and at the most about 2 % by weight Re, Ru, Rh, Pd, Re, Os, Ir and Pt in one or more.
The sintered-carbide main body of some embodiments can have the tungsten-carbide powder of average equivalent circular diameter (equivalent circle diameter) (ECD) size within the scope of about 0.2 μm to about 0.6 μm and formed by providing, ECD Size Distribution has further feature, and the carbide particle being namely less than 45% has the average-size being less than 0.3 μm; The carbide particle of 30% to 40% has at least 0.3 μm and the average-size of 0.5 μm at the most; The carbide particle of 18% to 25% has and is greater than 0.5 μm and the average-size of 1 μm at the most; The carbide particle being less than 3% has the average-size being greater than 1 μm.By tungsten-carbide powder with comprise Co, the adhesive material of Ni and Cr or chromium carbide grinds, and the total carbon equivalent be included in mixed-powder is such as relative to about 6% of tungsten carbide.Then by mixed-powder compacting to form green compact, and green compact are carried out sinter to produce sintered-carbide main body.
Green compact can sinter at least 65 minutes at the temperature of the highest 1440 DEG C and the time of maximum 85 minutes at such as at least 1400 DEG C.
In certain embodiments, the total carbon equivalent (ETC) be included in cemented carbide material is about 6.12% relative to tungsten carbide.
In certain embodiments, the Size Distribution of tungsten-carbide powder can have the feature of the standard deviation of 0.4 μm average ECD and 0.1 μm.
With reference to following example, embodiment is explained in more detail, these examples only for illustration of and be not to limit the scope of the invention.
Embodiment 1
The sub-micron cobalt powder being enough to the amount obtaining 2 quality % in final diamond matrix is carried out first carrying out depolymerization (de-agglomerated) in 1 hour with WC abrasive media in the methyl alcohol slurry of ball mill.Then be that the particulate grade (fraction) of the diamond dust of 2 μm joins in described slurry to obtain the amount of 10 quality % in final mixture by average grain diameter.Introduce extra abrasive media and add other methyl alcohol to obtain applicable slurry; Gains are ground one hour again.Then the adamantine coarse grain grade of average grain diameter about 20 μm is added with the amount obtaining 88 quality % in final mixture.Again other methyl alcohol and abrasive media are supplemented to slurry, and then grind 2 hours.Slurry is removed from ball milling and drying, to obtain diamond powder mixture.
Then diamond powder mixture is put into suitable HpHT container, make it adjacent with tungsten carbide substrate and sinter at the temperature of the pressure of about 6.8GPa and about 1500 DEG C.
Embodiment 2
The sub-micron cobalt powder being enough to the amount obtaining 2.4 quality % in final diamond matrix is carried out first carrying out depolymerization in 1 hour with WC abrasive media in the methyl alcohol slurry of ball mill.Then be that the particulate grade of the diamond dust of 2 μm joins in described slurry with the amount obtaining 29.3 quality % in final mixture by average grain diameter.Introduce extra abrasive media and add methyl alcohol further to obtain applicable slurry; Gains are ground one hour again.Then the adamantine coarse grain grade of average grain diameter about 20 μm is added into thus in final mixture, obtains the amount of 68.3 quality %.Again other methyl alcohol and abrasive media are supplemented to slurry, and then grind 2 hours.Slurry is removed from ball mill and drying, to obtain diamond powder mixture.
Then diamond powder mixture is put into suitable HPHT container, make it adjacent with tungsten carbide substrate and sinter at the temperature of the pressure of about 6.8GPa and about 1500 DEG C.
The diamond content of sintered diamond structure is greater than 90 volume %, and the most coarse grain grade of this distribution is greater than 60 % by weight and is preferably greater than 70 % by weight.
In polycrystalline diamond abrasive compact, independent diamond particles/particle is bonded on adjacent particle/particle by Buddha's warrior attendant stone bridge or diamond neck (neck) to a great extent.This independent diamond particles/particle keeps its uniformity (identity), or usually has different orientations.Average grain/the particle size of these independent diamond particles/particles can utilize image analysis technology to measure.SEM collects image and uses standard image analysis technology to analyze.From these images, representational diamond particles/particle size distribution can be extracted.
Usually, the main body of polycrystalline diamond abrasive compact will produce and be bonded in cemented carbide substrate in HPHT process.In this process, arrange adhesive phase and diamond particles, it is favourable for being uniformly distributed mutually to make adhesive and having small scale.
The uniformity of sintering structure or uniformity are by carrying out statistical evaluation to define to the great amount of images collected.The distribution of binder phase is easily distinguished with the distribution of diamond phase by using electron microscope, then can measure the distribution of adhesive phase by the method similar with method disclosed in EP0974566.The method can carry out statistical evaluation to the average thickness of the binder phase by microstructural line drawn arbitrarily along several.To those skilled in the art, this adhesive thickness measured value is also referred to as " mean free path ".For entirety composition or binder content and the similar bi-material of average diamond particle diameter, the less material of average thickness will evenly, because this means diamond mutually in the distribution of " more small scale " of adhesive.In addition, the standard deviation of this measurement is less, and structure is more even.Large standard deviation shows that adhesive thickness alters a great deal in microstructure, and namely this structure is uneven, and comprises multiple different structure type.
Binding agent and the diamond mean free path measured value of the various samples formed according to each embodiment is obtained below in the mode listed.Unless otherwise indicated herein, the mean free path size in PCD material main body to refer on the surface of the main body comprising PCD material or by the cross section of this main body being measured and not carrying out the size of three-dimensional correction.Such as, obtain measured value by the graphical analysis carried out on a polished surface, and in data described in this article, do not carry out Sa Ertekefu (Saltykov) correction.
In the mean value or other statistical parameter measured by graphical analysis of measuring amount, use several images of the different piece of surface or cross section (hereinafter referred to sample) to improve reliability and the accuracy of statistics.Can be such as between 10 to 30 for measuring the picture number of a given amount or parameter.If the sample analyzed is uniform, the situation for PCD depends on magnifying power, can think that 10 to 20 width images represent this sample enough fully.
In order between clear identification particle and alternate boundary, the resolution ratio of image needs enough high, for described measured value, employs the image-region of 1280 × 960 pixels herein.The image for graphical analysis is obtained by the mode of the scanning electron micrograph (SEM) captured by use back scattered electron signal.Select backscattered mode to provide the high-contrast based on different atomicity, and reduce the susceptibility (compared with secondary electron imaging pattern) of effects on surface damage.
1. use line EDM to cut the exemplar of PCD sintered body and polishing.Use SEM with at least 10 width back-scattered electron image of 1000 times of multiplication factor shooting sample surfaces.
2. original image is converted to gray level image.By guaranteeing that diamond peak brightness appears at the contrast level setting image between 10 to 20 in tonal gradation histogram.
3. automatic threshold characteristic is used for binary image, especially for the clear resolution ratio obtaining diamond and adhesive phase.
4. use from Soft Imaging
the software of the trade name analySIS Pro of GmbH (trade mark of Olympus Soft ImagingSolutions GmbH), and any particle getting rid of contact image border from analyze.This needs suitably to select image magnification ratio:
If a. too low, the resolution ratio of fine particle reduces.
If b. too Gao Ze:
I. the efficiency that coarse granule is separated reduces.
Ii. a large amount of coarse granules is excised by the border of image, analyzes these less particles thus.
Iii must analyze more images thus to obtain the result having statistical significance.
5. each particle represents eventually through the quantity of the contiguous pixels forming it.
6.AnalySIS software program carry out detect and analysis chart picture in each particle.This process is repeated automatically to multiple image.
7. use tonal gradation to analyze ten width SEM images, to determine binder pool mutually different from other in sample.Then by selecting only to identify binder pool and the maximum getting rid of the binder pool content of other phases all (no matter grey or white) determines the threshold value of SEM.Once determine this threshold value, this threshold value is used to carry out binaryzation SEM image.
8. be superimposed upon on the width of whole binary image by line thick for pixel, every root line at a distance of 5 pixels (having enough representativenesses to guarantee to measure) on angle of statistics.Be excluded mutually outside these are measured by the adhesive that image boundary is excised.
9. to measure and the analyzed material of distance-often kind recorded between the binder pool along superposition line at least carries out 10000 times measures.The intermediate value of record (report) non-diamond phase average free path and diamond phase average free path.
Also record the mean free path measured value at Q1 and Q3 for both diamond phase and non-diamond phase.
Q1 is commonly referred to the first quartile (also referred to as lower quartile), and below this numerical value, show the data of the bottom of 25%.Q3 is commonly referred to the 3rd quartile (also referred to as upper quartile), and has the data of 75% under it, and the data of front 25% thereon.
Thus, determine that embodiment has:
1.5 > α >=0.50 and β <0.60,
Wherein
α is non-diamond phase MFP intermediate value/(Q3-Q1), which show the measured value of " uniform adhesive pool size "; And
β=diamond MFP intermediate value/(Q3-Q1), which show the measured value of " wide particle diameter distribution ".
In certain embodiments, determine 1.5 > α >=0.60, or 1.5 > α >=0.80, or 1.5 > α >=0.83.
In certain embodiments, β <0.60, or <0.50, or <0.47, or <0.4.
The additive method comprising the PCD briquet 20 of PCD material main body 22 produced as shown in figs. 1-3 c is described with reference to Fig. 4-10.As shown in Figure 4, the configuration of PCD structure (the second structure) 200 contiguous cemented carbide substrate (the first structure) 300, the thin layer or the film 400 that comprise the adhesive material of Co connect the major opposed surfaces of PCD structure 200 and substrate 300 with composition assembly for super-pressure, high temperature compacting (not shown) in housing 100.The CTE of the PCD material comprised in PCD structure 200 is about 2.5 × 10
-6/ DEG C to about 4 × 10
-6/ DEG C scope in, the CTE of the cobalt-cemented tungsten carbide material comprised in substrate 300 is about 5.4 × 10
-6/ DEG C to about 6 × 10
-6/ DEG C scope in (CTE value is applicable to 25 DEG C).In this example, substrate 300 and PCD structure 200 are containing the adhesive material comprising Co.According to estimates, the Young's modulus of PCD material be about 900GPa to about 1400GPa, this depends on the grade of PCD, the Young's modulus of substrate be about 500GPa to about 650GPa, this depends on content and the composition of adhesive material to a great extent.
Fig. 5 shows the signal phasor of carbon at pressure p axle and temperature T axle, and line D-G represents the thermodynamical equilibrium between diamond and graphite allotrope, diamond more thermal-stable in the D of region, graphite more thermal-stable in the region G of chart.The temperature that line S-L graphically illustrates adhesive material fusing at a variety of pressures or solidifies, this temperature is tended to increase along with the increase of pressure.Note, this temperature is likely different from the temperature of pure adhesive material, because the existence of carbon and/or this temperature of the expected reduction of WC that some dissolve in diamond, because the fusing point that there are expected reduction cobalt and other metals of carbon in solution.The assembly described with reference to Fig. 4 may be in first pressure P 1 of about 7.5GPa to about 8GPa and under about 1450 DEG C of conditions to about 1800 DEG C of temperature, form PCD material by the aggregation sintering the diamond particles that contiguous substrate is arranged.On the one hand under sintering pressure and sintering temperature, form PCD in situ and the assembly that makes on the other hand stands do not have substantial interruption between the first pressure P 1; The method more related aspect in stage I and the relation between the reduction of the pressure and temperature in stage II subsequently.When sintering temperature, Co adhesive material will melt and be expected to promote that the direct symbiosis sintering of diamond particles is to form PCD material, and the diamond comprised in PCD material is thermodynamically basic more than graphite stable under sintering temperature and sintering pressure.
With further reference to Fig. 5, the pressure and temperature of assembly can be reduced to the ambient level in stage I, II and III.In concrete example, in the stage I, pressure is reduced to second pressure P 2 of about 5.5GPa to about 6GPa from the first pressure P 1, temperature is reduced to about 1350 DEG C to about 1500 DEG C simultaneously, to guarantee to maintain pressure-temperature conditions, so that diamond is than graphite thermodynamically more stable and adhesive material maintenance fully fusing.Then, in the stage II, temperature can be reduced within the scope of about 1100 DEG C to about 1200 DEG C, pressure be maintained in the diamond stable region D of online more than D-G, with solidification adhesive material simultaneously; In the stage III, by various method, pressure and temperature can be reduced to ambient level.Then, PCD structure can remove from press equipment.Note, the stage I, II and III only for key-drawing 6, and may not distinguished between these stages in practice clearly.Such as, do not maintain the substance of pressure and temperature condition at the end of a stage during, these stages can enter another stage reposefully.Or some stages or all stage can be different and at the end of a stage, pressure and temperature condition can continue for some time.
In some instances, the pre-sintered components such as manufacturing PCD structure can be produced and is arranged on the original position of the first following pressure P 1.A container can be provided, can the aggregation comprising multiple diamond particles and substrate be assembled in this container, the shape (considering distortion possible in sintering step) of the PCD structure that the interior shape of this container is normally expected.This aggregation can comprise significantly loose diamond particles or the diamond containing, for example graininess, plate-like, disk or sheet-like precursor structure.Aggregation also can comprise for adamantine catalyst material or the precursor material for catalyst material, and this aggregation can mix with diamond particles and/or be deposited on the surface of diamond particles.The average-size of diamond particles can be at least about 0.1 μm and/or about 75 μm at the most, and can be single mode or multi-modal substantially.Aggregation also can comprise the additive for reducing irregular diamond or grain growth, or aggregation also can essentially no catalyst material or additive.Selectively or alternatively, another source such as cobalt of catalyst material or matrix (matrix) material can be provided, as the adhesive material in cemented carbide substrate.Can be put in container by the aggregation of sufficient amount, then substrate can advance against this aggregation with near-end and insert in container.The pre-sintered components comprising aggregation and substrate can be loaded into and comprises in the metal shell of container, the organic bond be included in aggregation to burn through heat-treated and be sealed in be suitable for super-pressure compacting housing (it can be called as container) in.Housing can be placed in applicable ultra high pressure machine equipment and to stand sintering pressure with sintering temperature to form the assembly comprising the PCD structure of contiguous substrate be connected by the film of the hot-melt adhesive comprising cobalt.In such as these examples, can think that sintering pressure is the first pressure P 1.
In exemplary arrangement, can prepare and be provided in the first pressure P as described below the pre-sintered components manufacturing PCD structure for 1 time in press equipment.PCD structure can carry out presintering in aforesaid super-pressure, high-temperature technology.PCD structure can containing the adhesive material comprising cobalt, and this adhesive material is arranged in the gap area between the diamond particles being included in PCD material.As for PCD material, PCD structure can have the region of at least one basic adhesive-free material.Such as, can process in acid PCD structure with the surface from least contiguous PCD structure or the gap of the volume (or the change between these possibilities) that substantially runs through whole PCD structure remove adhesive material, leaving at least one can containing region that is porose or hole.In some instances, generation hole thus the packing material that can comprise or not comprise adhesive material can be full of.PCD structure can be placed in substrate, and pre-structured (pre-construction) assembly of generation can load in the housing being suitable for super-pressure compacting.Housing can be placed in suitable ultra high pressure machine equipment and (under the condition in the region D at Fig. 5) stands the first pressure P 1 under adhesive material is in liquid temperature.
The illustrative methods constructed for the manufacture of exemplary PCD is described below with reference to Fig. 6-10.In each figure, illustrate only a part for pressure and temperature circulation, this part starts from the first respective pressure P 1, be included in PCD material in structure at this pressure to start to be formed by sintering, and temperature be fully reduced to adhesive material is solidified reduce from the second pressure P 2 with pressure after terminate.
In some instances, can the providing package pre-sintered components of aggregation of diamond particles of placing containing the surface that multiple vicinity comprises the substrate of cobalt-cemented tungsten carbide.The average-size of diamond particles is in the scope of about 0.1 to about 40 μm.Pre-sintered components can be compressed in the container for ultra high pressure machine equipment, be mounted with this container in the apparatus.Can at ambient temperature by vessel pressurization at least about the pressure of 6.5GPa and the temperature be heated within the scope of about 1500 to about 1600 DEG C, this temperature is far longer than the fusing point (under described pressure) of the cobalt-based adhesive material comprised in the substrate and causes cobalt material to melt.At such a temperature, pre-sintered components can be in about 7.5 to the first pressure P 1 (at least partly due to the increase of temperature, P1 can slightly higher than 7GPa) within the scope of about 10GPa.Described first pressure P 1 and described temperature can maintain substantially at least about 1 minute, or keep the long enough time to be sintered together (in these examples, sintering pressure is substantially P1) by diamond particles.Then, pressure can be decreased to from the first pressure P 1 the second pressure P 2 that scope is about 5.5 to about 8.5GPa.Under the second pressure, because temperature is decreased to the setting temperature of adhesive material, adhesive material starts to solidify.
If temperature still keeps being greater than cobalt-based adhesive material by temperature when solidifying completely, then the temperature of pre-sintered components can reduce with pressure simultaneously.When pressure reduces from P2, also temperature can be reduced by the line of solidification of cobalt-based adhesive material, cause solidifying of adhesive material.In these concrete examples, pressure significantly continues to reduce from the first pressure P 1, when not having essence to pause, and the pressure solidified by the second pressure P 2 and by adhesive material.The reduction speed of temperature and/or pressure can be change or both one of or both reduction speed can be constant substantially, at least until cobalt-based adhesive material solidifies.This temperature also can significantly continue to reduce, at least until it is enough low that this temperature is fully solidified for all cobalt-based adhesive materials.Then, this temperature and pressure can be reduced to environmental condition, and container removes from ultra high pressure machine equipment and constructs and removes from this container.This structure can comprise the sintering PCD structure being connected to substrate and being formed, and this PCD structure is connected in substrate in the identical general step forming PCD material by sintering multiple diamond particles simultaneously.The thin layer being rich in cobalt will be present in PCD structure and by between the substrate together of these anatomical connectivity.
In the particular exemplary process shown in Fig. 6, the first pressure P 1 is about 7.6GPa, and in the temperature of the first pressure in the scope of about 1500 DEG C to about 1600 DEG C, the second exemplary pressure P 2 is about 6.8GPa.
In the particular exemplary process shown in Fig. 7, the first pressure P 1 is about 7.7GPa, and in the temperature of the first pressure in the scope of about 1500 DEG C to about 1600 DEG C, the second exemplary pressure P 2 is about 6.9GPa.
In the particular exemplary process shown in Fig. 8, the first pressure P 1 is about 7.8GPa, and in the temperature of the first pressure in the scope of about 1500 DEG C to about 1600 DEG C, the second exemplary pressure P 2 is about 6.9GPa.
In the particular exemplary process shown in Fig. 9, the first pressure P 1 is about 7.9GPa, and in the temperature of the first pressure in the scope of about 1500 DEG C to about 1600 DEG C, the second exemplary pressure P 2 is about 5.5GPa.
In the particular exemplary process shown in Figure 10, the first pressure P 1 is about 9.9GPa, is about 2000 DEG C in the temperature of the first pressure, and the second exemplary pressure P 2 can be about 8.1GPa.
Note, the line S-L in Fig. 6-10 shows fusing and the setting temperature of cobalt-based adhesive material under the existence of carbon, and line S-L uses data available to estimate based on calculating.In practice, not exclusively rely on the evaluation on S-L but repeatedly test to find that for the fusing of special adhesive material and setting temperature and use pressure be desirable.
The method circulated for measuring pressure and temperature as illustrated in figures 6-10 uses the fusion temperature knowledge of so-called K-type thermocouple and copper (Cu) and silver (Ag) to measure." the gold under 60 kilobar pressure is called by P.W.Mirwald and G.C.Kennedy at one section when the data up to the fusing point of Cu and Ag of use K-type thermocouple measurement during 60 kilobar, the fusion curve-reinvestigate of silver and copper " (" The melting curve of gold, silver and copper to60-Kbar pressure – a reinvestigation ", published on 10 November 1979 inthe Journal of Geophysical Research volume 84, number B12, pages 6750to 6756, by The American Geophysical Union) article disclosed in.K-type thermocouple also can be called as " chromel-alumel " thermocouple, and in " chromel-alumel " thermocouple, " nickel chromium triangle " component comprises the nickel of 90% and the chromium of 10%, " nickel aluminium " component comprise 95% nickel, the manganese of 2%, the aluminium of 2% and 1% silicon.The method comprises inserts the main body be substantially made up of Cu and the main body insertion of the joint of the 2nd K-type thermocouple be substantially made up of Ag by the joint of a K-type thermocouple, and two main bodys is placed in a reservoir close to pre-sintered components.Record runs through the reading from two thermocouples of the circulation of pressure and temperature at least partially, and processes this reading, and according to publish data, this reading is converted into pressure and temperature value.
Various ultra high pressure machine can be used, comprise belt, the many anvils of tetrahedron, the many anvils of cube, fertile gram type or annular pressure machine.The volume of superhard construction to be manufactured and the desired pressure and temperature for sintering superhard material are likely depended in the selection of press types.Such as, tetrahedral and cubical forcing press may be suitable in the PCD material at least about 7GPa or the fired under pressure viable commercial volume at least about 7.7GPa.
Some illustrative methods can comprise make PCD be configured at least about 500 DEG C, at least about 600 DEG C or at least about the temperature of 650 DEG C stand heat treatment at least about 5 minutes, at least about 15 minutes or at least about 30 minutes.In certain embodiments, temperature can be about 850 DEG C at the most, about 800 DEG C or about 750 DEG C at the most at the most.In certain embodiments, PCD structure can be made to stand to be heat-treated to many about 120 minutes or about 60 minutes at the most.In one embodiment, PCD structure can be made in a vacuum through heat-treated.Such as, application number is 6,517, the treated forms U.S. patents disclosing a kind of preform elements of 902, and this preform elements has the PCD table face (facing table) of the substrate with cobalt binder, PCD being bonded to cemented tungsten carbide.In six side's solid matter crystal structures, substrate comprises the boundary zone of the cobalt binder with at least 30% volume.
When not wishing by particular theory constraint, the possibility that the method reduces to cause superhard construction to be broken due to the residual stress in structure or frequency reduction.
Other non-limiting examples will be described in more detail below.
Embodiment 3
PCD insert for boring rock (rock-boring) drill bit can as described belowly manufacture.
Preparation comprises the pre-sintered components of the aggregation of multiple diamond particles of the near-end being arranged on substantial cylindrical cemented carbide substrate.Aggregation comprises multiple wafer being included in the diamond particles of dispersion in organic binder material, and the average-size of diamond particles is at least about 15 μm and about 30 μm at the most.Substrate comprises the WC particle be bonded together by the adhesive material containing Co of about 90 % by weight.Pre-sintered components to be installed in metal shell and the organic bond comprised in the wafer that heated to burn, and chlamydate pre-sintered components is compressed in container, for super-pressure, high temperature many anvils press equipment.
Pre-sintered components stands the pressure of about 7.7GPa and the temperature of about 1550 DEG C to make diamond particles direct sintering each other, and then forms the PCD material layer by being connected to the near-end of substrate from the film comprising the adhesive material of the fusing of cobalt of substrate.This pressure is decreased to about 5.5GPa, and this temperature is decreased to about 1450 DEG C, and the maintenance package diamond be contained in PCD is the condition that thermodynamically stable (relative to graphite, a kind of allotrope of softer carbon) and adhesive material are in liquid phase.Then, this temperature is decreased to about 1000 DEG C and also forms with solidification adhesive material the structure that the adhesive material comprised by solidifying is bonded to the PCD layer of substrate, and then, this pressure and temperature is decreased to environmental condition.
Stand 660 DEG C of heat treatments under general context pressure in the described air being configured in basic anaerobic about 2 hours, be then cooled to environment temperature.After heat treatment, PCD layer is without obvious crackle.
Described structure is processed by grinding and polishing, thinks that boring rock drill bit provides insert.
In order to compare, reference configuration is as described below to be manufactured.Pre-sintered components is prepared with reference to above-mentioned exemplary pre-sintered components.Pre-sintered components stands the pressure of about 7.7GPa and the temperature of about 1550 DEG C to make diamond particles direct sintering each other, and then forms the PCD material layer by being connected to the near-end of substrate from the film comprising the adhesive material of the fusing of cobalt of substrate.This temperature is decreased to about 1000 DEG C and also forms with solidification adhesive material the structure that the adhesive material comprised by solidifying is bonded to the PCD layer of substrate, and then, this pressure and temperature is decreased to environmental condition.Stand 660 DEG C of heat treatments under general context pressure in the described air being configured in basic anaerobic about 2 hours, be then cooled to environment temperature.After heat treatment, at the obvious severe crack of the Bian Shangyou of PCD layer.
Embodiment 4
PCD insert for boring rock drill bit can as described belowly manufacture.
Preparation comprises the pre-sintered components with the PCD structure of general disc shaped of the near-end being arranged on substantial cylindrical cemented carbide substrate.Sinter in the previous steps of the aggregation of multiple diamond particles simultaneously and manufactured PCD structure including under the super-pressure being less than about 7GPa and high temperature (at such a temperature, diamond is than graphite Thermodynamically stable more).Substrate comprises the WC particle be bonded together by the adhesive material comprising Co of about 90 % by weight.Pre-sintered components to be installed in metal shell and the organic bond comprised in the wafer that heated to burn, and chlamydate pre-sintered components is compressed in container, for super-pressure, high temperature many anvils press equipment.
Pre-sintered components stands the temperature of the pressure of about 7.7GPa and about 1550 DEG C to change the microstructure of PCD structure.This pressure is decreased to about 5.5GPa, and this temperature is decreased to about 1450 DEG C, and the maintenance package diamond be contained in PCD is the condition that thermodynamically stable (relative to graphite, a kind of allotrope of softer carbon) and adhesive material are in liquid phase.Then, this temperature is decreased to about 1000 DEG C and also forms with solidification adhesive material the structure that the adhesive material comprised by solidifying is bonded to the PCD layer of substrate, and then, this pressure and temperature is decreased to environmental condition.
Stand 660 DEG C of heat treatments under general context pressure in the described air being configured in basic anaerobic about 2 hours, be then cooled to environment temperature.After heat treatment, PCD layer is without obvious crackle.
Described structure is processed by grinding and polishing, thinks that boring rock drill bit provides insert.
As used in this article, the thickness of the some parts of PCD structure 22,200 or substrate 30,300 or PCD structure or substrate is basically perpendicular to the thickness measured at interface 24.In certain embodiments, PCD structure or PCD material main body 22,200 can have general thin slice, disk or discoid shape, or are general layered form.In certain embodiments, the thickness of PCD structure 22,200 can be at least about 0.3mm, at least about 0.5mm, at least about 0.7mm, at least about 1mm, at least about 1.3mm or at least about 2mm.In one embodiment, the thickness of PCD structure 22,200 can within the scope of about 2mm to about 3mm.
In certain embodiments, substrate 30,300 shapes can with thin slice, disk or column (post), and can be generally columniform.Substrate 30,300 axial widths can with the axial width being such as at least equal to or greater than PCD material main body 22,200, and on thickness can be such as at least about 1mm, at least about 2.5mm, at least about 3mm, at least about 5mm or even at least about 10mm.In one embodiment, substrate 30, the thickness of 300 can be at least 2cm.
PCD structure 22,200 opposite side that such as only side is connected to substrate 30,300, PCD structure can be not joined to substrate 30,300.
In certain embodiments, the full-size of PCD material main body 22,200 is about 6mm or larger, and such as, be in columniform embodiment in shape in PCD material main body, the diameter of main body is about 6mm or larger.
In some versions of described method, before sintering, the condensate (aggregated mass) of diamond particles/particle is generally to have at least about 0.6mm, at least about 1mm, at least about 1.5mm or the surface being even arranged on substrate at least about the form of the layer of the thickness of 2mm.When particle sinters under super-pressure, the thickness of the described body of diamond particles can significantly reduce.
The ultra-hard particles used in this process can be raw material that is natural or synthesis.The mixture of ultra-hard particles can be multimodal, and namely it can comprise the mixture of the diamond particles of different average grain diameter or the grade of particle.Typically, the quantity of grade can be:
The special circumstances of-two grades
-three or more grade.
" averaged particles/particle size " is meant to single particle/particle and has size range, and averaged particles/particle size represents " mean value ".Therefore, the major amount of particle/particle close to average-size, although will the particle/particle of above-mentioned limited quantity and following given size be had.The peak value of distribution of particles will therefore at given size place.The particle size distribution of the grade of often kind of ultra-hard particles/particle typically is the single mode of himself, but may in some cases time multi-modal.In sintered compact, term " averaged particles/particle size " is explained by similar mode.
As shown in Figure 1, there is adhesive phase in addition in the main body of the polycrystalline diamond abrasive compact of an embodiment manufacture.This adhesive material is preferably the catalyst/solvent for used super hard abrasive particle.Well-known in the art for adamantine catalyst/solvent.In adamantine situation, adhesive is preferably cobalt, nickel, iron or the alloy containing one or more these metals.This adhesive or introduce by penetrating into abrasive grain daughter in sintering processes process, or is introduced as the mixture in abrasive grain daughter in particulate form.Infiltration from the pad provided or adhesive metal layer or can occur from carbide supported thing.Typically, the combination of mixing and permeating method can be used.
In high pressure, high-temperature process, catalyst/solvent material is melted by compacted zone and moves, and serves as catalyst/solvent and causes ultra-hard particles to be combined with each other.Once make, therefore PCD structure comprises the coherent matrix of superhard (diamond) particle be combined with each other, thus forms the ultrahard polycrystalline composite as above with many gaps or pond (pool) comprising adhesive material.Substantially, therefore final PCD structure comprises two-phase complex, and wherein super hard abrasive diamond comprises a phase, and adhesive (non-diamond phase) comprises another phase.
In one form, typically be adamantine superhard form mutually by volume 80% to 95%, solvent/catalyst material form remaining 5% to 20%.
Adhesive phase is mainly limited by the size and dimension of diamond particles with the Relative distribution being full of the space of this phase or the quantity in pond.
Adhesive (non-diamond) can contribute to the impact resistance improving more fragile abrasive material phase mutually, but when the more weak and less wearability level of adhesive mutually typically representative structure, high quantity can be easy to adversely affect wearability.In addition, when adhesive is also a kind of active solvent/catalyst material mutually, its existence increased in the structure can endanger the heat endurance of briquet.
To be the diamond intensity showing the boundary between diamond particles shown in egative film be Figure 11 a and 11b 0 (Figure 11 a) and diamond intensity be the example of the finished SEM image of the polishing part of the PCD material of 15 (Figure 11 b).These boundary lines are provided by image analysis software and in Figure 11 a and 11b, are shown as the surface area in single non-diamond phase (gap) region of contrary (i.e. field of illumination) for measuring whole non-diamond (as adhesive) surface area and be shown as dark area in the cross section of the main body by PCD material in actual SEM image.In order to the result of carrying out analysis below and will realize, by the cross section of the main body of PCD material can any direction by the main body of PCD material.To Description Image analytical technology in more detail below.
As non-limiting example, in order to observe, the cross section shown in Figure 11 a and 11b can be exposed by the cross section of cutting PCD composite compact in the mode of Linear cut (wire EDM).Prepare for being observed as SEM (SEM) by microscope, can polished cross-sections, and take a series of microphotograph image.Each image can be analyzed by image analysis software, to determine whole adhesive area and the single adhesive area between diamond particles.The value of whole adhesive area and single adhesive area by SEM photographs to a large amount of collection images carry out statistical evaluation and determine.
The selected accuracy of magnifying power on the data obtained for microstructure analysis has significant impact.Imaging under lower magnifying power provides the chance typically sampling larger particles or feature in microstructure; but when fail fully to differentiate under such magnifying power comparatively granule or feature time, the imaging under lower magnifying power may be tended to fail to represent comparatively granule or feature.Otherwise comparatively high power allows high-resolution and therefore can measure small scale features, but the border of its image is intersected and can not fully measure thus when sampling larger feature.Obviously, for the magnifying power that any quantitative microstructure analysis choice of technology is suitable is important.Therefore well-formedness is determined by the size of the feature as characteristic.Magnifying power for various measured value selection described herein will be discussed in more detail below.
Except otherwise herein provided, otherwise the size that the size of whole adhesive area in PCD material main body and single adhesive area refers on the surface of the main body comprising PCD material or by it cross section is measured, and do not carry out three-dimensional correction.Such as, obtain measured value by the graphical analysis carried out on a polished surface, and in data described in this article, do not carry out Sa Ertekefu (Saltykov) correction.
In the mean value or other statistical parameter measured by graphical analysis of measuring amount, use several images of the different piece of surface or cross section (hereinafter referred to sample) to improve reliability and the accuracy of statistics.Can be such as between 10 to 30 for measuring the picture number of a given amount or parameter.If the sample analyzed is uniform, the situation for PCD depends on magnifying power, can think that 10 to 20 width images represent this sample enough fully.
For will be clear that the object made from alternate boundary between particle, the resolution ratio of image needs enough high, for described measured value, employs the image-region of 1280 × 960 pixels herein.
In statistical analysis, be chosen at 15 width images of the zones of different on the surface of the main body comprising PCD material, and carry out statistical analysis on each image.
The image for graphical analysis is obtained by the mode of the scanning electron micrograph (SEM) captured by use back scattered electron signal.Select backscattered mode to provide the high-contrast based on different atomicity, and reduce the susceptibility (compared with secondary electron imaging pattern) of effects on surface damage.
It is important that many factors is considered to picture catching.These factors are:
-SEM voltage, in order to the object of measured value as herein described, SEM voltages keep constant at about 15kV;
-operating distance, it also keeps constant and at about 8mm;
-image definition;
-sample quality of finish;
-image comparison level, it is selected to provide the clear interval of micro-structural feature;
-magnifying power (should change according to different diamond particle size and as described below);
-choose the quantity of image
Consider above-mentioned condition, the image analysis software of use can differently diamonds separated and adhesive phase, and the direction at the edge with sample being about 45 ° gathers backscatter image.
The mode that interested feature can fully should be differentiated and describe by the pixel by available quantity to the magnifying power used in graphical analysis is selected.In PCD graphical analysis, measure the various features of different size and distribution simultaneously, and use independent magnifying power to be unpractiaca to each interested feature.
When lacking reference measurement result, determine that to the optimum magnification of each characteristic measurements be difficult.It may change with the difference of operator.Therefore, a kind of program is proposed to the selection of magnifying power.
Measure the size of the diamond particles of the statistically effective quantity in microstructure and obtain mean value.
Relevant particle in the present invention or particle, unless otherwise stated or implied, otherwise term " size " refers to the length of the particle using image analysis technology to observe from the side or in cross-section.
Determine the quantity of the pixel describing this average length, and determine that the scope of pixel value is to determine magnifying power.
In image analysis technology, original image is converted to gray level image.By guaranteeing that diamond peak brightness appears at the contrast level setting image between 15 to 20 in tonal gradation histogram.
As mentioned above, multiple images of the different piece in surface or cross section are chosen to improve reliability and the accuracy of statistics.For the measured value in whole non-diamond phase (as adhesive) region, the quantity of image is larger, and the result perceived is more accurate.Such as, the every width image of 15 width image has 1000 measured values, chooses about 15000 measured values.
The step that image analysis program is taked can roughly be summarized as follows:
1. original image is converted to gray level image.By guaranteeing that diamond peak brightness appears at the contrast level setting image between 10 to 20 in tonal gradation histogram.
2. automatic threshold characteristic is used for binary image, especially for the clear resolution ratio obtaining diamond and adhesive phase.
3. adhesive is interested principal phase in present analysis.
4. use from Soft Imaging
the software of the trade name analySIS Pro of GmbH (trade mark of Olympus Soft ImagingSolutions GmbH), and any particle getting rid of contact image border from analyze.This needs suitably to select image magnification ratio:
If a. too low, the resolution ratio of fine particle reduces.
If b. too Gao Ze:
I. the efficiency that coarse granule is separated reduces.
Ii. a large amount of coarse granules is excised by the border of image, analyzes these less particles thus.
Iii. more images must be analyzed thus to obtain the result having statistical significance.
5. each particle represents eventually through the quantity of the contiguous pixels forming it.
6.AnalySIS software program carry out detect and analysis chart picture in each particle.This process is repeated automatically to multiple image.
7. can be exported in a large number.Further subsequent treatment can be carried out to this output, such as Using statistics Epidemiological Analysis software and/or carry out further signature analysis, such as described below for determining the analysis for the mean value of total adhesive area of all images and the mean value of single adhesive area.
If use suitable threshold values, except tiny error during expected rounding, image analysis technology unlikely introduces other mistakes accuracy of measured value being had to actual influence in the measurement further.In existing analysis, when being tending towards normal according to the distribution of central-limit theorem (Central LimitationTheorem) mean value along with the increase of sample size, use the assembly average of whole adhesive area and single adhesive area, the no matter mean value distribution of taking from, except when estimator of parent distribution is not when (parent distribution) moment, (moment) existed.In statistical engineering, all practicality distributions all define the moment, and therefore central-limit theorem is applicable to this situation.Therefore, Using statistics mean value is deemed appropriate.
Use above-mentioned standard image analysis tools to determine use electron microscope easily with region or the pond of superhard single non-diamond (as adhesive or the catalyst/solvent) phase distinguished mutually.By determining the area (according to square micron) of the whole non-diamond phase in analyzed cross sectional image to the area summation of the single binder pool in analyzed whole microstructure image region.
Then, statistics assessment is carried out to the set distribution of these data, then determines arithmetic mean of instantaneous value.Thus, the mean value of the whole binder pool area in analyzed microstructural surface is estimated.
Microstructure Parameter can change from a region of abrasive compact slightly to another region, and depend on formation condition, this it is expected to.Therefore, microstructure imaging is carried out to sample the major part of the superhard composite portion of briquet typically.
Other non-limiting examples of present description.Manufacture following three groups of samples: have the average diamond grain size of about 13 μm and multimodal (three peaks) diamond powder mixture of 1 % by weight cobalt, this mixture preparing q.s thinks that every increment product provide about 2g mixture.Then, the mixture of every increment product is poured into or is placed in niobium internal container with additive method.About 13 % by weight cobalt contents the cemented carbide substrate with non-planar interface are placed in each internal container on mixture of powders.Titanium lid be placed in turn this structure and seal with above the assembly producing container (canister).This container carries out pretreatment at about 1050 DEG C by vacuum degassing, and be divided into three groups, described three groups namely sinter at three different super-pressure and temperature conditions in diamond stable region under about 5.5Gpa (the 1st group), 6.8GPa (the 2nd group) and 7.7GPa (the 3rd group).Particularly, this container is being enough to the PCD structure carrying out sintering to produce PCD table (table) and the well-bound substrate with fully sintering at the temperature melting cobalt.The technology that above-mentioned composition graphs 3 to 9 describes can be applicable to the sintering of container under 7.7GPa (the 3rd group).The superhard construction produced does not stand the synthesis of any later stage and leaches process.
Then, use above-mentioned technology to carry out graphical analysis in these superhard construction each, particularly, determine that above-mentioned suitable magnifying power is to determine the average cross-section adhesive area of average whole adhesive area in polished cross-sections and each sample.
Synthetic for different diamond particle size can be tested repeatedly, and table 1 lists experimental result.
table 1
| Particle size | Whole adhesive area | Adhesive area | Magnifying power | |
| μm | ％ | μm 2 | ||
| Mean value | Standard deviation | 0.01 | ||
| 13.4600 | 2.2750 | 8.0699 | 0.4446 | 1000x |
| 12.5755 | 3.1707 | 8.0223 | 0.2802 | 1000x |
| 10.8800 | 1.8440 | 6.4004 | 0.2638 | 1000x |
| 3.9700 | 0.7990 | 10.3135 | 0.1528 | 3000x |
Can determine from above-mentioned experiment, for the whole non-diamond phase area (such as adhesive area) within the scope of about 0-12%, what the full-size realizing the PCD material main body as used image analysis technology to determine was about 6mm or larger is less than about 0.7 μm
2the single non-diamond area of association be possible, the magnifying power of this technology application about 1000 times also analyzes the image-region of 1280 × 960 pixels.The thickness of PCD material main body can be such as about 0.3mm or larger in these embodiments.
In addition, in certain embodiments, for within the scope of about 0-12% as be less than 12% or be less than 10% or be less than 8% whole non-diamond phase area (such as adhesive area), what the full-size of PCD material main body realized as used image analysis technology to determine was about 6mm or larger is less than about 0.7 μm
2or be less than about 0.5 μm
2or be less than about 0.4 μm
2or be less than about 0.34 μm
2the single non-diamond area of association be possible, the magnifying power of this technology application about 1000 times also analyzes the image-region of 1280 × 960 pixels.The thickness of PCD material main body can be such as about 0.3mm or larger in these embodiments.
In order to promote the heat endurance improving sintering structure, the region of catalysis material from the polycrystal layer of its exposed surface contiguous is removed, namely relative with substrate working surface.Method as known in the art such as electrolytic etching and Ore Leaching and evaporation technique can be used to carry out removing of catalysis material.
The polycrystalline superabrasive layer 22 leached by the embodiment of the method can but not there is the about 1.5mm thickness to about 3.5mm uniquely.
Have been found that and remove non-adhesive phase from PCD table, being commonly called leaching, is desirable in numerous applications.The existence of the residual solvent/catalyst material in microstructure gap is considered at high temperature have adverse effect to the performance of PCD briquet, because it is said that the existence of solvent/catalyst can cause the heat endurance reducing diamond table at these elevated temperatures in diamond table.Therefore, it is desirable to leach the heat endurance that can improve PCD main body.But, knownly can reduce its fracture toughness between 20% to 30% and intensity from PCD structure leaching solvent/catalyst material.The applicant unexpectedly concludes, contrary with traditional expection, leach the darker leaching degree of depth, especially the degree of depth being leached to PCD main body from working surface is greater than 800 μm, in fact the intensity in the pure mechanical strength of PCD main body in cutting process and in the intensity of reply load can significantly be increased, thus the possibility that delay is peeled off.This can be explained and illustrated by example below.
In Ore Leaching, be considered to be controlled by chemical speed when acid contacts PCD table surperficial at first about the reflection speed leached, controlled by diffusion rate when acid diffuses through the hole of PCD table subsequently.
By convention, HF-HNO
3prove the most effective medium removing tungsten carbide (WC) from sintering PCD table.HF-HNO
3problem be it be volatile, and when heating this acid, need particular technology, such as, Dry-gas Sealing Technology.If do not provide this technology, then due to HF (it is poisonous) evaporation and be generally the formation of NO kind of gaseous state, the application of temperature will reduce HF-HNO
3effect, therefore need frequent supplemental acid medium.In addition, in order to make this process commercially feasible, usually need heat to accelerate leaching process.Another problem is HF-HNO
3corrode most of containment vessel, make reaction be difficult to carry out.
HCl and other similar inorganic acids compare HF-HNO
3be easier at high temperature work, and have aggressiveness to catalyst/solvent especially cobalt (Co).HCl such as can remove most of catalyst/solvent from PCD table in reasonable time section, this time depends on temperature, usually at 80 hours, although HCl does not remove WC, and the applicant has expected that HCl is not suitable for removing any non-diamond phase additive, as the VC from PCD table individually.
In order to improve surface property and the heat resistance of the main body 22 of PCD material, additive such as the carbide additive as cobalt and PCD at least partially of metal-solvent catalyst at least partially can be removed from the gap 14 of PCD material 22 at least partially.In addition, tungsten and/or tungsten carbide can be removed from the main body 22 of PCD material at least partially.
Chemical Leaching be used for from the main body 22 of PCD material remove metal-solvent catalyst and additive until distance PCD material main body working surface 34 desired by the degree of depth.After leaching, the main body 22 of PCD material comprises first volume (volume) of not containing metal solvent catalyst substantially.But a small amount of catalyst can remain in leaching process to be difficult in the gap of arrival.After leaching, the main body 22 of PCD material also comprises the volume containing metal-solvent catalyst.In certain embodiments, this further volume can away from the exposed surface of the main body 22 of one or more PCD material.
The interstitial material that can comprise the additive of such as metallic solvent/catalyst and one or more carbide additive forms can leach from the gap 14 of the main body 22 of PCD material by making PCD material expose suitable infusion solution.
According to some embodiments, infusion solution can comprise one or more inorganic acids and dust technology.The main body of PCD material can contact this infusion solution in any suitable manner, comprises such as by invading main body 22 a period of time of steeping PCD material at least partially in infusion solution.
According to some embodiments, at the temperature that the main body of PCD material can be seethed with excitement as Ore Leaching mixture at high temperature, contact infusion solution.The degree of depth that PCD material leaches can be increased under the main body of PCD material being exposed to high temperature in leaching process, and reduce the necessary extraction time of the leaching degree of depth desired by arriving.
When the main body of only some PCD material will leach; if main body is still attached to substrate, then substrate can be surrounded to prevent the main body of infusion solution chemical damage PCD material and/or in leaching process, be attached to its some part of substrate by protected seam at least in part.This configuration can provide the Selectively leaching of the main body of PCD material, and this is useful.After leaching, protective layer or cover can be removed.
In addition, in certain embodiments, the speed leached with the main body increasing PCD material at least one that the main body of PCD material and infusion solution can be exposed in electric current, microwave and/or ultrasonic energy at least partially.
The example of suitable inorganic acid can comprise any combination of such as hydrochloric acid, phosphoric acid, sulfuric acid, hydrofluoric acid and/or aforementioned inorganic acid.
In certain embodiments, nitric acid can the amount such as between 2-5 % by weight and/or up to the molar concentration of about 1.3M be present in the leaching mixture of some embodiments.In certain embodiments, one or more inorganic acids can be present in infusion solution up to the molar concentration of about such as 7M.
In certain embodiments, hydrochloric acid and nitre aqueous acid is used PCD table to be leached.Leach about 30 to 300 hours at the temperature that PCD table is seethed with excitement at Ore Leaching mixture, this depends on the desired leaching degree of depth and the composition of PCD material, and after leaching a period of time, using ultrasound ripple removes Residual reactants.
After leaching, by the x-ray analysis of routine, the various piece of PCD table is measured respectively to the leaching degree of depth of PCD table.
Being formed according to said method to test and to be leached to the wearability of the sintering polycrystalline product of the various leaching degree of depth, first exemplary products (example 1) of the average grain diameter comprising 70 % by weight to be the diamond particles of 17 μm and the average grain diameter of 30 % by weight the be bimodal compound of the diamond particles of 1.7 μm sinters under the sintering pressure of 6.8GPa.Sintered products leaches sufficient extraction time (the leaching degree of depth about 40 hours for about 250 μm and the leaching degree of depth for about 1000 μm about 100 hours) to produce, as comparing, there is the leaching product of the leaching degree of depth of distance working surface 256 μm, the another kind of product of the another kind of product with the leaching degree of depth of 572 μm and the leaching degree of depth with 947 μm.
Then, polishing carried out to diamond layer and carry out vertical boring mill test.In this test, the throughput (number of passes) that the area of plane of wearing and tearing pierces workpiece according to cutter elements is measured.Figure 12 vivo describes obtained result.This result provides the instruction of the total polishing scratch area drawn for Cutting Length.
This shows, the PCD briquet formed according to example 1 can realize than obvious larger Cutting Length and less polishing scratch area when being leached to 256 μm in the leaching degree of depth of 572 μm and 947 μm.
Another exemplary group of polycrystalline briquet manufactures according to said method, and form example 2, these briquets by the average particle size particle size of 40 % by weight be the diamond particles of 17 μm, three peak mixtures of the average particle size particle size of 30 % by weight to be the diamond particles of 10 μm and the average particle size particle size of 30 % by weight the be diamond particles of 1.7 μm form.Sintering pressure is 7.1Gpa.
Sintered products leach enough extraction time (from for about 230 hours of the leaching degree of depth of about 700 μm to for about 250 hours of the leaching degree of depth of about 900 μm) to produce, as a comparison, the leaching product of the leaching degree of depth of distance working surface 971 μm and another product with 770 μm of leaching degree of depth.
Then, polishing carried out to diamond layer and carry out vertical boring mill test.Figure 13 vivo describes obtained result.
This shows, the PCD briquet formed according to example 2 can realize than Cutting Length obviously larger when being leached to 770 μm and less polishing scratch area the leaching degree of depth of 971 μm.
When not wishing the constraint being subject to particular theory, the main body can determining to use the PCD material that condition manufacturing machine intensity described herein is larger and more wear-resisting is possible, when using as cutter, this main body can significantly improve the durability of the cutter manufactured according to embodiment more described herein.
Really, especially when leaching the heat endurance being expected to improve PCD main body, knownly its fracture toughness between 20% to 30% and intensity can be reduced from PCD structure leaching solvent/catalyst material.Inventor recognizes, contrary with the expection of routine, when with PCD main body leach the degree of depth be less than 800 μm compared with time, be leached to the darker leaching degree of depth, especially the degree of depth being leached to PCD main body from working surface is greater than 800 μm, in fact the intensity in the pure mechanical strength of PCD main body in working angles and in the intensity of reply load can significantly be increased, thus the possibility that delay is peeled off.This can assist by use polishing scratch being remained on leaching PCD layer, thus suppresses the impact of the crackle along the interface diffusion between the leaching district and non-leaching district of PCD.These contribute to the possibility that reduces to peel off or frequency, and therefore increase the useful working life of PCD structure.
Also have been found that the multimodal distribution of some embodiments can help to realize the diamond symbiosis of very high level (density), and still keep enough percent opening can effectively leach.
Although be described various embodiment with reference to some embodiments, but it will be appreciated by one of skill in the art that, can make various change for element wherein and can be replaced by equivalent, and these embodiments are not intended the specific embodiment disclosed in restriction.
In addition, the present invention is that described method contemplates various arrangement and combination, and the example of described method can also comprise in various combination one or more following non-exhaustive and nonrestrictive in.
The invention provides a kind of method manufacturing superhard construction, described structure comprises:
Be connected to the first structure of the second structure, described first structure comprises first material with the first thermal coefficient of expansion (CTE) and the first Young's modulus, and described second structure comprises second material with the 2nd CTE and the second Young's modulus; A described CTE and described 2nd CTE is obviously different each other, and described first Young's modulus and described second Young's modulus are obviously different each other; At least one in the one the second materials comprises superhard material; Described method comprises:
Formed comprise the first material, the second material and be set to can by the first and second material bindings to together with the assembly of adhesive material, described adhesive material comprises metal; Make described assembly stand adhesive material and be in liquid sufficiently high temperature and superhard material is thermodynamically stable first pressure; Reducing pressure to superhard material is thermodynamically stable second pressure, keeps sufficiently high temperature to be in liquid state to maintain adhesive material; Reduce temperature with solidification adhesive material; And reduce pressure and temperature to environmental condition to provide superhard construction.
In certain embodiments, about 25 DEG C time, the CTE of in the first or second material is at least about 2.5 × 10
-6/ DEG C and at most about 5.0 × 10
-6/ DEG C, another the CTE in the first or second material is at least about 3.5 × 10
-6/ DEG C and at most about 6.5 × 10
-6/ DEG C.
In certain embodiments, the Young's modulus of in the first or second material is at least about 500GPa and maximum about 1300GPa, and another the Young's modulus in the first or second material is at least about 800GPa and maximum about 1600GPa.
The Young's modulus of the first and second materials such as can at least differ about 10%.
In certain embodiments, the CTE of the first and second materials such as can at least differ about 10%.
Described method sinters the aggregation of the particle of multiple superhard material under the existence of sintering catalysis agent material under can also being included in sintering pressure and sintering temperature, to form the second structure.
Described method can comprise contiguous for the aggregation of the particle of superhard material the first vibrational power flow and form pre-sintered components under adhesive material exists; Make pre-sintered components stand sintering pressure and sintering temperature with melt adhesive material sinter the particle of superhard material and form the second structure comprising polycrystalline superhard material, described second structure is connected with the first structure by adhesive material in molten condition.
In certain embodiments, the first pressure is roughly sintering pressure.
The method can also comprise provides the first structure, providing package is containing the second structure of polycrystalline superhard material, contiguous for first structure the second structure is placed and formed (pre-construction) assembly in early stage, and pressure is acted on assembly in early stage, pressure is increased to the first pressure from environmental pressure.
Described method such as can comprise the aggregation of the particle of multiple superhard material is stood sintering pressure and sintering temperature that superhard material sinters to be formed the second material, and pressure and temperature is reduced to environmental condition to provide the second structure; First pressure is obviously greater than sintering pressure.
Second structure can comprise diamond, and adhesive material comprises for adamantine catalyst material.
First and second structures can each self-contained diamond, and adhesive material comprises for adamantine catalyst material.
In certain embodiments, the second pressure and the first pressure at least differ about 0.5GPa.
It is carry out heat treatment further to superhard construction under the metastable treatment temperature of thermodynamics and processing pressure that described method can also be included in superhard material.
Superhard material can comprise diamond, and treatment temperature is at least about 500 DEG C and processing pressure is less than about 1GPa.
Described method can comprise puts the phase of depositing (holding period) pressure is reduced to intermediate pressure from the first pressure, then further by pressure from the low step to the second pressure of middle Pressure Drop.
First pressure such as can be at least about 7GPa, and intermediate pressure such as can be at least about 5.5GPa and be less than about 10GPa, puts the phase of depositing such as can be at least about 1 minute, and the second pressure such as can be at least about 5.5GPa and about 7GPa at most.
The pressure that adhesive material starts to solidify along with the reduction of temperature such as can be substantially equal to the second pressure in certain embodiments.
In other embodiments, the pressure that adhesive material starts to solidify along with the reduction of temperature can be significantly less than the second pressure.
In certain embodiments, the first structure comprises cobalt-cemented tungsten carbide material and the second material comprises PCD material, and the CTE of cemented carbide material is about 4.5 × 10
-6to about 6.5 × 10
-6/ DEG C scope in, the CTE of PCD material is about 3 × 10
-6to about 5 × 10
-6/ DEG C scope in; The Young's modulus of cemented carbide material is in about 500 scopes to about 1000GPa, and the Young's modulus of PCD material is in about 800 scopes to about 1600GPa; First pressure is in about 6 scopes to about 10GPa, and the second pressure is in about 5.5 scopes to about 8GPa.
In certain embodiments, the pressure that the cobalt-based adhesive material be included in cemented carbide material starts to solidify equals the second pressure.
Second pressure such as can in about 6.5 scopes to about 7.5GPa.
In certain embodiments, the second structure comprises PCD material and at the method is included within the scope of about 550 to about 650 DEG C temperature, superhard construction is carried out to the further heat treatment of a treatment cycle within the scope of about 30 to about 90 minutes.
Claims (42)
1. a polycrystalline superhard construction, it comprises polycrystalline diamond (PCD) body of material and the multiple gap areas between the diamond particles of mutual bonding forming described polycrystalline diamond abrasive compact; Described PCD material main body comprises:
Working surface, its Outboard Sections along described main body is located;
First area, it is substantially free of solvent/catalysis material; And
Away from the second area of described working surface, it comprises solvent/catalysis material in described multiple gap area;
Wherein, described first area extends into the degree of depth at least about 800 μm described polycrystalline diamond abrasive compact main body from described working surface.
2. polycrystalline superhard construction as claimed in claim 1, wherein, the most of diamond particles of described main body in the degree of depth apart from described working surface at least 800 μm has substantially not containing the surface of catalysis material, all the other particle contacts catalysis materials.
3. the polycrystalline superhard construction according to any one of the claims, it comprises the substrate along interfacial adhesion to described PCD material main body further.
4. polycrystalline superhard construction as claimed in claim 3, wherein, described interface is plane substantially, or be nonplanar substantially and comprise the one or more parts protruding into PCD material main body described in one or the other or substrate, or from one or more parts that PCD material main body described in one or the other or substrate extend.
5. the polycrystalline superhard construction as described in claim 3 or 4, wherein, described first area and interval, described interface or with the one or more partial separation extended a little along described interface.
6. the polycrystalline superhard construction according to any one of claim 3-5, wherein, described first area is in distance below one or more some place and interval, described interface at described interface:
Be greater than about 20 μm; Or
Between about 50 to about 200 μm.
7. the polycrystalline superhard construction according to any one of the claims, wherein, described first area extends the following degree of depth from described working surface:
At least about 800 μm to about 1000 μm; Or
At least about 800 μm to about 1400 μm; Or
At least about 850 μm to about 1400 μm.
8. the polycrystalline superhard construction according to any one of the claims, wherein, the degree of depth passing through to the described first area of working surface described in small part is somewhat constant; Or the described degree of depth of the described first area passing through to working surface described in small part is change.
9. the polycrystalline superhard construction according to any one of the claims, wherein, described first area passes through substantially whole described working surface and extends; Or described first area extends only through the described working surface extension of part.
10. the polycrystalline superhard construction according to any one of the claims, wherein, described first and/or second area comprise the diamond particles of two or more diamond particle size.
11. polycrystalline superhard construction as claimed in claim 10, wherein, described diamond particles has relevant mean free path; The described solvent/catalyst of the most gap areas in the described second area of at least part of filling has relevant mean free path;
Wherein, the intermediate value of the described mean free path relevant to described solvent/catalyst is more than or equal to 0.5 divided by (Q3-Q1) for described solvent/catalyst, and wherein Q1 is the first quartile and Q3 is the 3rd quartile; And
The intermediate value of the described mean free path relevant to described diamond particles is less than 0.6 divided by (Q3-Q1) for described diamond particles.
12. polycrystalline superhard construction as claimed in claim 11, wherein, the intermediate value of the described mean free path relevant to described solvent/catalyst is more than or equal to 0.6 divided by (Q3-Q1) for described solvent/catalyst.
13. polycrystalline superhard construction as claimed in claim 11, wherein, the intermediate value of the described mean free path relevant to described solvent/catalyst is more than or equal to 0.8 divided by (Q3-Q1) for described solvent/catalyst.
14. polycrystalline superhard construction as claimed in claim 11, wherein, the intermediate value of the described mean free path relevant to described solvent/catalyst is more than or equal to 0.83 divided by (Q3-Q1) for described solvent/catalyst.
15. polycrystalline superhard construction according to any one of claim 11-14, wherein, the intermediate value of the described mean free path relevant to described diamond particles is less than 0.5 divided by (Q3-Q1) for described diamond particles.
16. polycrystalline superhard construction according to any one of claim 11-14, wherein, the intermediate value of the described mean free path relevant to described diamond particles is less than 0.47 divided by (Q3-Q1) for described diamond particles.
17. polycrystalline superhard construction according to any one of claim 11-14, wherein, the intermediate value of the described mean free path relevant to described diamond particles is less than 0.4 divided by (Q3-Q1) for described diamond particles.
18. polycrystalline superhard construction according to any one of the claims, wherein, described diamond particles comprises diamond particles that is natural and/or synthesis.
19. any one of the claims or multinomial as described in polycrystalline superhard construction, wherein, described solvent/catalyst in described second area comprises cobalt, and/or one or more other iron family element, as iron or nickel, or its alloy, and/or the carbide of one or more group IV-VI metals in the periodic table of elements, nitride, boride and oxide.
20. polycrystalline superhard construction according to any one of the claims, wherein, the described solvent/catalyst in described second area is for sintering the described solvent/catalyst of described PCD main body when forming described PCD structure.
21. polycrystalline superhard construction according to any one of the claims, wherein, the described solvent/catalyst of filling described multiple gap area at least partly forms non-diamond phase pond, and each described non-diamond phase pond has independent cross-sectional area,
Wherein, described solvent/catalyst accounts for the percentage of the gross area of the cross section of described polycrystalline diamond abrasive compact main body between about 0 to 12%, and when the image analysis technology being used in the magnifying power of about 1000 and the image-region of 1280 × 960 pixels is analyzed, the mean value of the single cross-sectional area in the described non-diamond phase pond in the analysis chart picture of the cross section through described polycrystalline material main body is less than about 0.7 μm
2.
22. polycrystalline superhard construction as claimed in claim 21, wherein, described solvent/catalyst accounts for the percentage of the gross area of the cross section of described polycrystalline diamond abrasive compact main body between about 0 to 10%, and when the image analysis technology being used in the magnifying power of about 1000 and the image-region of 1280 × 960 pixels is analyzed, the mean value of the single cross-sectional area in the described non-diamond phase pond in the analysis chart picture of the cross section through described polycrystalline material main body is less than about 0.7 μm
2.
23. polycrystalline superhard construction as claimed in claim 21, wherein, described solvent/catalyst accounts for the percentage of the gross area of the cross section of described polycrystalline diamond abrasive compact main body between about 0 to 8%, and when the image analysis technology being used in the magnifying power of about 1000 and the image-region of 1280 × 960 pixels is analyzed, the mean value of the single cross-sectional area in the described non-diamond phase pond in the analysis chart picture of the cross section through described polycrystalline material main body is less than about 0.7 μm
2.
24. polycrystalline superhard construction according to any one of claim 21-23, wherein, when the image analysis technology being used in the magnifying power of about 1000 and the image-region of 1280 × 960 pixels is analyzed, the mean value of the single cross-sectional area in the described non-diamond phase pond in the analysis chart picture of the cross section through described polycrystalline material main body is less than about 0.5 μm
2.
25. polycrystalline superhard construction according to any one of claim 21-23, wherein, when the image analysis technology being used in the magnifying power of about 1000 and the image-region of 1280 × 960 pixels is analyzed, the mean value of the single cross-sectional area in the described non-diamond phase pond in the analysis chart picture of the cross section through described polycrystalline material main body is less than about 0.4 μm
2.
26. polycrystalline superhard construction according to any one of claim 21-23, wherein, when the image analysis technology being used in the magnifying power of about 1000 and the image-region of 1280 × 960 pixels is analyzed, the mean value of the single cross-sectional area in the described non-diamond phase pond in the analysis chart picture of the cross section through described polycrystalline material main body is less than about 0.34 μm
2.
27. polycrystalline superhard construction according to any one of the claims, wherein, the full-size of described polycrystalline diamond abrasive compact main body is about 6mm or larger.
28. polycrystalline superhard construction according to any one of the claims, wherein, the thickness of described polycrystalline diamond abrasive compact main body is about 0.3mm or larger, or about 3mm or larger.
29. polycrystalline superhard construction according to any one of the claims, wherein, described PCD main body comprises the cumulative volume that the accounts for described diamond body diamond at least about the volume between 90% to 95%.
30. 1 kinds of cutters for earth's crust probing, it comprises the polycrystalline superhard construction according to any one of the claims.
31. 1 kinds of rotation shearing machines for earth's crust probing, for drill hammer or for digging up mine or the PCD element of excavator of pitch degraded, it comprises the polycrystalline superhard construction according to any one of claim 1-29.
The assembly of 32. 1 kinds of drill bits or a kind of drill bit for earth's crust probing, it comprises the polycrystalline superhard construction according to any one of claim 1-29.
The method of 33. 1 kinds of heat-staple polycrystalline diamond stone constructions of manufacture, it comprises following steps:
Pack processing is containing the polycrystalline diamond stone construction of polycrystalline diamond main body, the diamond particles that described polycrystalline diamond main body comprises multiple mutual bonding and the gap area be arranged on therebetween, thus remove solvent/catalyst material from the first area of described diamond body, allow described solvent/catalyst material to stay in the second area of described diamond body simultaneously;
Comprise further, during treatment step, control the degree of depth of described first area so that its working surface from described diamond body extends the degree of depth at least about 800 μm.
34. methods as claimed in claim 33, wherein, described PCD structure comprises the substrate along interfacial adhesion to described PCD material main body further, described method be included in described treatment step further before prevent described substrate to be exposed to described treatment step during the step of inorganic agent that uses.
35. methods according to any one of claim 33 or 34, wherein, the treating step comprises the degree of depth controlling described first area in case its working surface from described diamond body extend from described interface or from along described interface in the degree of depth of the one or more partial separation extended a little.
36. methods according to any one of claim 33-35, wherein, the treating step comprises the degree of depth that controls described first area so that it extends to and the degree of depth being greater than about 20 μm at interval, described interface from the working surface of described diamond body.
37. methods as claimed in claim 36, wherein, described first area is in the distance between the one or more somes places and 50 to 200 μm, interval, described interface at described interface.
38. methods according to any one of claim 33-37, wherein, the treating step comprises control described first area the degree of depth so that it extends to the following degree of depth from the working surface of described diamond body:
At least about 800 μm to about 1000 μm; Or
At least about 800 μm to about 1200 μm; Or
At least about 800 μm to about 1400 μm.
39. methods according to any one of claim 33-38, wherein, the treating step comprises the degree of depth controlling to pass through to the described first area of working surface described in small part is somewhat constant; Or the degree of depth controlling to pass through to the described first area of working surface described in small part is change.
40. methods according to any one of claim 33-39, wherein, the treating step comprises and control described process so that described first area passes through substantially whole described working surface and extend; Or described first area extends only through the described working surface extension of part.
41. methods according to any one of claim 33-40, wherein, before described treatment step, form described PCD and construct, described forming step comprises:
A large amount of diamond particles is provided;
Arrange described a large amount of diamond particles to form pre-sintered components; And
At the hyperpressure of about 5.5GPa or higher and described diamond are than the more thermodynamically stable temperature of graphite, described pre-sintered components is processed to be sintered together to form polycrystalline diamond stone construction by the particle of described diamond under the catalyst/solvent material for described diamond particles exists.
42. methods according to any one of claim 33-41, wherein, before described treatment step, described method comprises further described polycrystalline diamond main body is machined to finished size.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US201261722688P | 2012-11-05 | 2012-11-05 | |
| GB1219877.6 | 2012-11-05 | ||
| GB1219877.6A GB2507566A (en) | 2012-11-05 | 2012-11-05 | Tool with a PCD body |
| US61/722,688 | 2012-11-05 | ||
| PCT/EP2013/073007 WO2014068130A1 (en) | 2012-11-05 | 2013-11-05 | A polycrystalline super hard construction and a method of making same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104884197A true CN104884197A (en) | 2015-09-02 |
Family
ID=47429169
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201380068303.0A Pending CN104884197A (en) | 2012-11-05 | 2013-11-05 | A polycrystalline super hard construction and a method of making same |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US20150259987A1 (en) |
| CN (1) | CN104884197A (en) |
| GB (1) | GB2507566A (en) |
| WO (1) | WO2014068130A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111629851A (en) * | 2017-12-31 | 2020-09-04 | 第六元素（英国）有限公司 | Polycrystalline superhard structures and methods of making same |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB201215523D0 (en) * | 2012-08-31 | 2012-10-17 | Element Six Abrasives Sa | Polycrystalline diamond construction and method for making same |
| US11865663B2 (en) * | 2018-05-10 | 2024-01-09 | George Shuai | Optical surface polishing |
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| US10309158B2 (en) * | 2010-12-07 | 2019-06-04 | Us Synthetic Corporation | Method of partially infiltrating an at least partially leached polycrystalline diamond table and resultant polycrystalline diamond compacts |
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| US8727046B2 (en) * | 2011-04-15 | 2014-05-20 | Us Synthetic Corporation | Polycrystalline diamond compacts including at least one transition layer and methods for stress management in polycrsystalline diamond compacts |
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2012
- 2012-11-05 GB GB1219877.6A patent/GB2507566A/en not_active Withdrawn
-
2013
- 2013-11-05 WO PCT/EP2013/073007 patent/WO2014068130A1/en active Application Filing
- 2013-11-05 CN CN201380068303.0A patent/CN104884197A/en active Pending
- 2013-11-05 US US14/440,781 patent/US20150259987A1/en not_active Abandoned
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| US20060266559A1 (en) * | 2005-05-26 | 2006-11-30 | Smith International, Inc. | Polycrystalline diamond materials having improved abrasion resistance, thermal stability and impact resistance |
| CN102333608A (en) * | 2009-02-26 | 2012-01-25 | 美国合成集团公司 | Comprise polycrystalline diamond complex and the application thereof that are substantially free of the tungsten carbide crystal grain that presents exaggerated grain growth through the cemented tungsten carbide substrate |
| CN102438780A (en) * | 2009-02-27 | 2012-05-02 | 六号元素控股有限公司 | A superhead element, a tool comprising same and methods for making such superhard element |
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| Publication number | Publication date |
|---|---|
| US20150259987A1 (en) | 2015-09-17 |
| GB201219877D0 (en) | 2012-12-19 |
| GB2507566A (en) | 2014-05-07 |
| WO2014068130A1 (en) | 2014-05-08 |
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