WO2001077408A1 - Mit multilagen-schichten beschichteter substratkörper und verfahren zu seiner herstellung - Google Patents
Mit multilagen-schichten beschichteter substratkörper und verfahren zu seiner herstellung Download PDFInfo
- Publication number
- WO2001077408A1 WO2001077408A1 PCT/DE2001/000903 DE0100903W WO0177408A1 WO 2001077408 A1 WO2001077408 A1 WO 2001077408A1 DE 0100903 W DE0100903 W DE 0100903W WO 0177408 A1 WO0177408 A1 WO 0177408A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- individual layers
- layer
- substrate body
- individual
- glow discharge
- Prior art date
Links
- 239000000758 substrate Substances 0.000 title claims abstract description 46
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 12
- 238000000034 method Methods 0.000 title claims description 40
- 238000000576 coating method Methods 0.000 claims abstract description 47
- 239000000203 mixture Substances 0.000 claims abstract description 36
- 239000007789 gas Substances 0.000 claims abstract description 35
- 239000011248 coating agent Substances 0.000 claims abstract description 32
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 20
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000000151 deposition Methods 0.000 claims abstract description 11
- 230000008021 deposition Effects 0.000 claims abstract description 11
- 229910052786 argon Inorganic materials 0.000 claims abstract description 8
- 238000005229 chemical vapour deposition Methods 0.000 claims abstract description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000001257 hydrogen Substances 0.000 claims abstract description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 6
- 239000010410 layer Substances 0.000 claims description 173
- 239000000463 material Substances 0.000 claims description 30
- 239000002347 wear-protection layer Substances 0.000 claims description 24
- 229910052751 metal Inorganic materials 0.000 claims description 23
- 239000002184 metal Substances 0.000 claims description 23
- 239000002131 composite material Substances 0.000 claims description 16
- 229910052799 carbon Inorganic materials 0.000 claims description 15
- 229910052719 titanium Inorganic materials 0.000 claims description 15
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 13
- 238000005520 cutting process Methods 0.000 claims description 12
- 150000004767 nitrides Chemical class 0.000 claims description 10
- 230000000737 periodic effect Effects 0.000 claims description 10
- 229910052782 aluminium Inorganic materials 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 9
- 239000000919 ceramic Substances 0.000 claims description 7
- 239000011195 cermet Substances 0.000 claims description 7
- 229910052710 silicon Inorganic materials 0.000 claims description 7
- 229910052726 zirconium Inorganic materials 0.000 claims description 7
- 229910052796 boron Inorganic materials 0.000 claims description 6
- 229910052735 hafnium Inorganic materials 0.000 claims description 6
- 239000002356 single layer Substances 0.000 claims description 5
- 150000002739 metals Chemical class 0.000 claims description 4
- 229910000851 Alloy steel Inorganic materials 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 229910052758 niobium Inorganic materials 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- 229910052720 vanadium Inorganic materials 0.000 claims description 3
- -1 nitride compound Chemical class 0.000 claims description 2
- 229910052715 tantalum Inorganic materials 0.000 claims description 2
- 229910001092 metal group alloy Inorganic materials 0.000 claims 2
- 230000004913 activation Effects 0.000 claims 1
- 238000005268 plasma chemical vapour deposition Methods 0.000 claims 1
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 description 12
- 239000010936 titanium Substances 0.000 description 12
- 238000005240 physical vapour deposition Methods 0.000 description 11
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 8
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 6
- 239000012298 atmosphere Substances 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 230000001427 coherent effect Effects 0.000 description 4
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 4
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 4
- 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 4
- 239000010955 niobium Substances 0.000 description 3
- 229910001928 zirconium oxide Inorganic materials 0.000 description 3
- 108091081062 Repeated sequence (DNA) Proteins 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000001247 metal acetylides Chemical class 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 238000009832 plasma treatment Methods 0.000 description 2
- 239000011241 protective layer Substances 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 229910052580 B4C Inorganic materials 0.000 description 1
- 229910052582 BN Inorganic materials 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 229910010038 TiAl Inorganic materials 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- CKUAXEQHGKSLHN-UHFFFAOYSA-N [C].[N] Chemical class [C].[N] CKUAXEQHGKSLHN-UHFFFAOYSA-N 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- INAHAJYZKVIDIZ-UHFFFAOYSA-N boron carbide Chemical compound B12B3B4C32B41 INAHAJYZKVIDIZ-UHFFFAOYSA-N 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000010891 electric arc Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000007733 ion plating Methods 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 238000000399 optical microscopy Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000005546 reactive sputtering Methods 0.000 description 1
- 230000033764 rhythmic process Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000000992 sputter etching Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
Classifications
-
- 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
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
- C23C16/45523—Pulsed gas flow or change of composition over time
-
- 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
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/50—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges
- C23C16/515—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges using pulsed discharges
-
- 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
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/04—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material
- C23C28/044—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material coatings specially adapted for cutting tools or wear applications
-
- 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
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/40—Coatings including alternating layers following a pattern, a periodic or defined repetition
- C23C28/42—Coatings including alternating layers following a pattern, a periodic or defined repetition characterized by the composition of the alternating layers
Definitions
- the invention relates to a method for producing a wear protection layer consisting of a multiplicity of thin individual layers with a respective layer thickness of 1 to 100 nm with a total thickness of 0.5 to 20 ⁇ m by means of a CVD method, in which the respective ones on a substrate body Individual layers are successively deposited, in particular for the production of a substrate body consisting of a hard metal, cermet, a ceramic or a metal or a steel alloy with a cutting insert coated with a wear protection layer.
- the invention further relates to a composite material, in particular a tool, consisting of a substrate body consisting of a hard metal, a cermet, a ceramic or a metal or a steel alloy and a substrate body deposited thereon and consisting of several individual layers with a thickness between 1 and 100 nm, preferably 5 up to 50 nm, existing wear protection layer.
- a composite material in particular a tool, consisting of a substrate body consisting of a hard metal, a cermet, a ceramic or a metal or a steel alloy and a substrate body deposited thereon and consisting of several individual layers with a thickness between 1 and 100 nm, preferably 5 up to 50 nm, existing wear protection layer.
- a wear-resistant composite body for processing metallic and non-metallic materials which consists of a base body and several differently composed, binder-metal-free hard material layers with a respective thickness of 1 to 50 ⁇ m.
- One of the hard material layers should have a thickness of 3 to 15 ⁇ m and be made up of a large number of thin individual layers each with a thickness of 0.02 to 0.1 ⁇ m, the hard material composition of each individual layer being different from the hard material additive.
- composition of the two neighboring individual layers For example, alternating individual layers consisting of titanium carbide or titanium nitride or titanium carbonitride on the one hand and aluminum oxide or zirconium oxide on the other hand can be provided.
- Both the individual layers or layers firmly adhering to one another on the metallic surface and also finely dispersed hard material / particle mixtures with individual layer thicknesses or particle sizes should have individual layer thicknesses or particle sizes in the range from 0.5 nm to 40 nm. In the case of 0.5 nm thick individual layers or particle sizes, the total number of individual layers or internal phase boundaries is between 100 and 20,000.
- Coherent or partially coherent phase boundaries are provided with respect to the crystal lattice, with the individual layers or layers or the hard material particles by cathode separators - Dust or another PVD method can be applied to the metallic surface or to the substrate, whereby either the surfaces to be coated are moved during the entire coating process relative to at least two atomizing cathodes of different hard material or the coating of the surface or the substrate with the help a cathode consisting of at least two hard materials which form coherent or partially coherent phase boundaries is carried out.
- cathodes made of TiC and T ⁇ B 2 or TiN and T ⁇ B 2 or TiC and TiN and TiB 2 or made of pure metals can be used.
- FIG. 1 A system suitable for such a coating process is shown schematically in FIG. 1.
- an autoclave 10 there are a first target 11 and a made of titanium on diametrically opposite sides second aluminum target 12 arranged.
- layer sequences TiN-AlN can be deposited on substrate bodies 14, which are moved about the axis of rotation 13 by means of a suitable rotating device.
- the substrates 14 can only be coated from one side, namely that side facing the targets 11 and 12.
- planet-like holders according to FIG.
- each substrate body 16 can also be rotated about its own axis, with four targets 11 and 12 of the aforementioned type being used in the case shown in FIG. 2.
- the substrate bodies can be coated on more than one side, but because of the uniform gas atmosphere, which consists, for example, of nitrogen, for example using titanium and aluminum targets only produce TiN-AlN deposits.
- DE 195 03 070 C1 describes a wear protection layer consisting of a large number of individual layers, in which a first individual layer made of a hard metal material which is applied directly to the substrate, and in the further individual layers applied to the first individual layer in a periodically repeated sequence from one metallic hard material and another hard material are deposited.
- the other hard material mentioned is said to be a covalent hard material.
- the individual layers consist of a periodically repeated sequence of a composite of three individual layers, the composite consisting of two individual layers of two different metallic hard materials and one individual layer of the covalent hard material, as a special example a composite of two individual layers of titanium nitride and titanium carbide and a further individual layer is indicated from the covalent hard material boron carbide.
- EP 0 701 982 A1 is concerned with a wear protection layer composed of several individual layers, each of which should have a thickness of 1 nm to 100 nm.
- the individual layers of at least two compounds essentially consist of carbides, nitrides, carbonitrides or oxides of at least one of the elements from the group of the IVB to VIB elements of the periodic table, Al, Si and B.
- Arc discharge can be used.
- a plurality of targets are arranged in a vacuum chamber, past which the substrate bodies arranged on a turntable are rotated.
- CVD coating technology it should be a conventional CVD method for comparison purposes, with which layers 0.5 ⁇ m thick are applied.
- EP 0 592 986 B1 describes a wear-resistant element made of a carrier material and an ultrathin film lambate attached thereon, which has at least one nitride or carbonitride of at least one element which is to be selected from a group which consists of the elements from groups IVB, VB and VIB Periodic table as well as AI and B, where the nitride or carbonitride has a cubic crystal structure and mainly has metal binding properties, as well as at least one compound that has a different crystal structure than the cubic crystal structure at normal temperature and normal pressure and in the state of equilibrium and which is mainly covalent Has binding properties.
- At least one nitride or carbonitride and the last-mentioned compound should be applied alternately, each individual layer having a thickness of 0.2 to 20 nm and the laminate overall having a cubic crystalline X-ray diffraction pattern.
- the laminate coating in question should also be applied using a PVD process. For example, only comparative Individual layers consisting of titanium nitride, aluminum oxide and titanium carbide with a layer thickness of 0.5 ⁇ m and more are mentioned. The same as for EP 0 709 483 A2 treated above also applies to the coating according to EP 0 709 483 A2.
- a wear-resistant coating for a cutting tool consisting of a first 1 ⁇ m thick TiC layer adjoining the surface of the tool and 100 alternating, equally thick layers of the connections TiN and ZrN or a 5 ⁇ m thick coating consisting of three equally thick Layers of (Ti, Zr) (C, N), (TiZr) C and (TiZr) N or by a 5 ⁇ m thick coating of 1500 equally thick, alternating layers of TaB 2 , NbB 2 , MoB 2 or a 5 ⁇ m thick coating of 600 alternating layers of Ta 5 Si 3 Nb 3 Si 3 , which have a tetragonal crystal lattice of the Cr 5 B 3 type, each with a layer thickness ratio of 1: 2, or by a 5 ⁇ m thick coating of 200 alternating layers Layers of the compound TiO, ZrO of cubic lattice with a layer thickness ratio of 1: 3 each are described in DE 35 39 729 C2.
- a PVD process is proposed for applying the coating.
- EP 0 885 984 A2 also describes laminate-like layers with a thickness of 1 to 100 nm, which are to be applied by means of the PVD method.
- WO 98/48072 and WO 98/44163 mention thin individual layers with a maximum thickness of 30 nm or 100 nm, for the application of which the CVD or PVD method is basically named, but in the exemplary embodiments, the PVD- Technology.
- the aforementioned object is achieved on the one hand by means of the method described in claim 1, which is characterized by a CVD method activated by a glow discharge plasma at a pressure of 50 Pa to 1000 Pa and a temperature of at most 750 ° C.
- a CVD method activated by a glow discharge plasma at a pressure of 50 Pa to 1000 Pa and a temperature of at most 750 ° C.
- the entire gas mixture required for the CVD processes can be achieved in a short time, i.e. in seconds to exchange.
- Hard metals, cermets, ceramics or even metallic substrate bodies such as steel base bodies can be used as substrate bodies, in particular for cutting inserts. All the compounds known in principle from the prior art and listed in the documents listed above or the gas mixtures suitable for their deposition are used as hard materials.
- such compounds are carbides, nitrides, carbonitrides of the transition metals titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum and tungsten (elements of the IVB to VIB group of the periodic table).
- aluminum or zirconium oxide, aluminum nitride and boron nitride are addressed in particular as outer wear-resistant individual layers.
- the relative low coating temperatures eliminates the risk of oxidation by oxygen-containing gases, such as is undesirable in a TiN layer, for example.
- a particularly sharp interface between two individual layers of different composition is obtained if the glow discharge plasma which supports the CVD reaction is switched off before the gas change, ie at the end of the coating of a single layer, and is only switched on again after the gas change in the coating reactor.
- the individual layers which follow one another despite the respective process interruptions adhere well to one another, even in those cases in which the substances are not miscible in thermal equilibrium, as is the case, for example, with a multilayer layer composed of A1 2 0 3 and TiN.
- the layer thicknesses are even on all sides when using the CVD process.
- the substrate bodies or the substrate bodies already coated with individual layers do not have to be moved during the coating or further coatings. Due to the unhindered flow around the body to be coated with the process gases introduced into the reactor, the multilayer layer can ideally be formed in a laminar layer and laterally continuously over the entire free surface of the substrate body.
- the object is achieved by the method described in claim 2.
- each of the individual layers is applied by means of a CVD process activated by a glow discharge plasma at a pressure of 50 to 1000 Pa and a temperature of at most 750 ° C.
- a gas or gas mixture of argon, hydrogen and / or nitrogen is introduced into the coating vessel at a pressure of 50 Pa to 1000 Pa at a constant high temperature and a glow discharge is applied to the substrate body or partially coated substrate body by applying a voltage of 200 to 1000 V via a Period of time that is shorter than the duration of the coating of the last individual layer, preferably a maximum of half as long, is maintained.
- the maintenance of the glow discharge in a non-reactive gas atmosphere is already mentioned in DE 44 17 729 AI, but only in connection with the application of relatively thick layers from 200 nm to 400 nm or more.
- the plasma treatment between the individual coating processes causes numerous defects in the previously smooth crystallite surfaces with little growth-active areas. Despite the "weakening" of the previously deposited layer caused by the plasma treatment, there are no adhesion problems when the next layer is applied.
- the structure of the separated individual layers is finer-grained than can be achieved with a CVD process at coating temperatures above 1000 ° C.
- Both the individual layers that each have a different composition from one individual layer to the next individual layer and multilayer coatings in which at least two of the adjacent individual layers have the same composition can be applied using the aforementioned process variants.
- two adjacent individual layers of hard materials can also be applied, which are not miscible, ie alloyable, in thermal equilibrium.
- Preferred hard materials from which the individual layers are made are compounds of at least two components, the first of which contains at least one element from the IVB to VIB group of the periodic table or Al, Si, C or B and the second, different from these, contains at least one element from the group of elements B, C, N, 0 and S.
- individual layers of A1 2 0 3 , Zr0 2 , A1N, BN or B (C, N) on the one hand and nitrides or carbonitrides of the form (C x , N ⁇ _ x ) are alternately arranged at least in part of the wear protection layer deposited with 0 ⁇ x ⁇ 1 of the elements Ti, Zr and Hf on the other hand.
- Multi-layer coatings made of A1 2 0 and TiN may be mentioned here as an example. However, coatings of the type in which individual layers of TiN and Ti (C, N) are deposited in an alternating sequence are preferably also possible.
- At least one intermediate layer with a thickness of 5 to 50 nm, which consists of at least one of the elements or compounds of at least two of the elements C, N, Mo, W, Ti, Al and / or contain Zr0 2 , Si or B as a further phase.
- Intermediate layers of carbon, carbon-nitrogen compounds, metallic layers of only one metal or also TiAl layers as well as layers in which zirconium dioxide, silicon and boron are incorporated as additives are particularly addressed here.
- the methods according to the invention can be used both in such a way that the layer composition of the successive individual layers is repeated periodically or a non-periodic sequence is selected.
- any number of successive individual layers of type A, B, C, A, B, C, ... can be used for periodic deposition as an example of a periodic sequence or Form A, B, C coatings B, A, C, A, C, B, ... can be selected as an example for a non-periodic sequence.
- the individual layers and also any intermediate layers can each be of the same thickness or of different thicknesses.
- the object mentioned at the outset is achieved by a composite material, in particular a cutting tool, consisting of a substrate body consisting of a hard metal, a cermet, a ceramic or a metallic body and a substrate body deposited thereon and consisting of a plurality of individual layers with a thickness between 1 and 100 nm, preferably 5 to 50 nm, existing wear protection layer according to claim 10 solved.
- the individual layers are characterized in that they have been applied by means of a CVD process activated by a glow discharge plasma at a pressure of 50 Pa to 1000 Pa and a maximum temperature of 750 ° C., with two coating processes in preparation for the deposition of the next individual layer either the voltage for generating the glow discharge has been switched off when changing the gas, or a gas or a gas mixture of argon, hydrogen and / or nitrogen is introduced into the coating vessel at a pressure of 50 Pa to 1000 Pa and the glow discharge is applied to the substrate body or partially coated substrate body a voltage of 200 to 1000 V over a period of time that is shorter than the duration of the coating of the last individual layer, preferably a maximum of half as long, has been maintained.
- two or more successive individual layers preferably have different compositions.
- At least two of the individual layers preferably consist of hard material, as have already been mentioned above.
- at least one hard material layer consists of a single Metallcarbonitrid- or metal nitride of composition (M ⁇ M 2) (C x, N y), wherein Mi and M2 are different metals, the preferably come from the group Ti, Zr, Hf, V, Nb and / or Ta and where 0 ⁇ x ⁇ 1 and 0 ⁇ y ⁇ 1.
- M ⁇ M 2 Metallcarbonitrid- or metal nitride of composition
- FIG. 3 shows a partial section through an indexable insert.
- Indexable inserts as exchangeable cutting inserts which are generally known from the prior art, each have diametrically opposed cutting surfaces 7, free surfaces 5 and rounded cutting edges 6 each lying between the free surface and the cutting surface.
- the cutting insert shown in FIG. 3 consists of a substrate body 1, which is covered with a wear protection layer 8, which consists of a plurality of at least two individual layers 2, 3 with different compositions, possibly from an intermediate layer or a further individual layer 4 with different compositions.
- Each of the individual layers is preferably between 5 and 50 nm thick. The entirety of the individual layers results in a wear protection layer thickness that is between 0.5 ⁇ m and 20 ⁇ m.
- a wear protection layer consisting of several individual layers 2, 3 is described on the basis of a specific exemplary embodiment.
- the substrate body 1, which consists for example of a hard metal or cermet, is cleaned in an ultrasound bath before coating.
- a further cleaning is carried out by ion etching in the recipient of the plasma reactor in a hydrogen / argon plasma, for its generation direct current discharges in pulsed succession at process pressures of 100 to 300 Pa were used.
- the heating of the substrate body to the coating temperature is supported by an external heater.
- gas mixtures for the deposition of titanium nitride and aluminum oxide have been introduced in alternating sequence at a temperature of 620 ° C.
- the respective process parameters are shown in Table 1 below:
- V Pulse voltage
- V Pulse voltage
- the glow discharge has been switched off for 2 s in each case.
- a 4.5 ⁇ m thick layer had formed. While the thickness of each individual layer was approximately 47 nm in the previous exemplary embodiment, the individual layer thickness of the coating produced in the second exemplary embodiment could no longer be resolved by means of optical microscopy.
- the average chemical composition of the entire wear protection layer could be determined as follows: 25 atom% Ti, 24 atom% AI, 50 atom% N and 1 atom% Cl.
- the thickness of the individual layers can be determined to be about 5 nm from the value of the total layer thickness.
- the thin individual layers are present as discrete phases made of titanium nitride and aluminum nitride, so that the submicroscopic thickness of the layers is still a continuous layer.
- the hardness of the wear protection layer consisting of titanium nitride and aluminum nitride is 3400 HV0.05.
- the pulsed DC voltage for generating the plasma is generally a square wave voltage with a maximum amplitude between 200 and 900 V and a period between 20 ⁇ s and 20 ms. However, deviations with the formation of non-vertical rising and falling flanks and sloping ceilings are also conceivable.
- the ratio of the pulse length (duration of the voltage signal of a pulse) to the period (pulse length + pulse pause length) is between 0.1 to 6.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Metallurgy (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Plasma & Fusion (AREA)
- Inorganic Chemistry (AREA)
- Chemical Vapour Deposition (AREA)
- Cutting Tools, Boring Holders, And Turrets (AREA)
Abstract
Description
Claims
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP01966772A EP1268878A1 (de) | 2000-04-06 | 2001-03-08 | Mit multilagen-schichten beschichteter substratkörper und verfahren zu seiner herstellung |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE10016958.9 | 2000-04-06 | ||
DE10016958A DE10016958A1 (de) | 2000-04-06 | 2000-04-06 | Verfahren zur Herstellung von Multilagenschichten auf Substratkörpern und Verbundwerkstoff, bestehend aus einem beschichteten Substratkörper |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2001077408A1 true WO2001077408A1 (de) | 2001-10-18 |
Family
ID=7637689
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/DE2001/000903 WO2001077408A1 (de) | 2000-04-06 | 2001-03-08 | Mit multilagen-schichten beschichteter substratkörper und verfahren zu seiner herstellung |
Country Status (4)
Country | Link |
---|---|
US (1) | US20030108752A1 (de) |
EP (1) | EP1268878A1 (de) |
DE (1) | DE10016958A1 (de) |
WO (1) | WO2001077408A1 (de) |
Families Citing this family (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE10212383A1 (de) * | 2002-03-20 | 2003-10-16 | Guehring Joerg | Verschleißschutzschicht für spanabhebende Werkzeuge, insbesondere für rotierende Zerspanwerkzeuge |
US20050112295A1 (en) * | 2003-09-23 | 2005-05-26 | Mikola Grechanyuk | Method to produce microlayer thermostable materials |
SE0402180D0 (sv) * | 2004-09-10 | 2004-09-10 | Sandvik Ab | Deposition of Ti1-xAlxN using Bipolar Pulsed Dual Magnetron Sputtering |
SE528430C2 (sv) * | 2004-11-05 | 2006-11-14 | Seco Tools Ab | Med aluminiumoxid belagt skärverktygsskär samt metod att framställa detta |
SE528432C2 (sv) * | 2004-11-05 | 2006-11-14 | Seco Tools Ab | Med aluminiumoxid belagt skärverktygsskär samt metod för att framställa detta |
US9997338B2 (en) * | 2005-03-24 | 2018-06-12 | Oerlikon Surface Solutions Ag, Pfäffikon | Method for operating a pulsed arc source |
US20070099027A1 (en) * | 2005-10-28 | 2007-05-03 | Anand Krishnamurthy | Wear resistant coatings |
CN102131961B (zh) * | 2008-09-29 | 2012-12-19 | 埃克斯帕斯环球技术公司 | 合金涂覆装置及电解电镀方法 |
US20100255337A1 (en) * | 2008-11-24 | 2010-10-07 | Langhorn Jason B | Multilayer Coatings |
US20100129626A1 (en) * | 2008-11-24 | 2010-05-27 | Langhorn Jason B | Multilayer Coatings |
EP2700460B1 (de) * | 2011-04-20 | 2018-11-07 | Tungaloy Corporation | Beschichtetes schneidwerkzeug |
JP5153968B2 (ja) * | 2011-04-28 | 2013-02-27 | 京セラ株式会社 | 切削工具 |
DE112014001640B4 (de) * | 2013-03-28 | 2022-06-02 | Kennametal Inc. | Mehrschichtig strukturierte Beschichtungen für Schneidwerkzeuge und Verfahren zum Herstellen eines Schneidwerkzeugs |
US9427808B2 (en) * | 2013-08-30 | 2016-08-30 | Kennametal Inc. | Refractory coatings for cutting tools |
DE102013019691A1 (de) * | 2013-11-26 | 2015-05-28 | Oerlikon Trading Ag, Trübbach | Hartstoffschicht zur Reduzierung eines Wärmeeintrags in das beschichtete Substrat |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE4239234A1 (de) * | 1992-11-21 | 1994-06-09 | Krupp Widia Gmbh | Werkzeug und Verfahren zur Beschichtung eines Werkzeuggrundkörpers |
WO1998048072A1 (en) * | 1997-04-18 | 1998-10-29 | Sandvik Ab (Publ) | Multilayered coated cutting tool |
Family Cites Families (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4264682A (en) * | 1978-10-27 | 1981-04-28 | Hitachi Metals, Ltd. | Surface hafnium-titanium compound coated hard alloy material and method of producing the same |
DE3152742C2 (de) * | 1981-02-23 | 1985-06-27 | Vsesojuznyj naučno-issledovatel'skij instrumental'nyj institut, Moskva | Werkzeug für die spanabhebende Bearbeitung mit einem mehrschichtigen Überzug |
DE3512986A1 (de) * | 1985-04-11 | 1986-10-16 | Kernforschungszentrum Karlsruhe Gmbh, 7500 Karlsruhe | Viellagige, hochverschleissfeste hartstoffschutzschicht fuer metallische, stark beanspruchte oberflaechen oder substrate |
DE3841731C1 (en) * | 1988-12-10 | 1990-04-12 | Krupp Widia Gmbh, 4300 Essen, De | Process for coating a tool base, and tool produced by this process |
US5516588A (en) * | 1991-03-27 | 1996-05-14 | Widia Gmbh | Composite body, its use and a process for its production |
DE4126851A1 (de) * | 1991-08-14 | 1993-02-18 | Krupp Widia Gmbh | Werkzeug mit verschleissfester schneide aus kubischem bornitrid oder polykristallinem kubischem bornitrid, verfahren zu dessen herstellung sowie dessen verwendung |
DE4140158A1 (de) * | 1991-12-05 | 1993-06-09 | Krupp Widia Gmbh, 4300 Essen, De | Verfahren und vorrichtung zur hartstoffbeschichtung von substratkoerpern |
GB9204791D0 (en) * | 1992-03-05 | 1992-04-22 | Rolls Royce Plc | A coated article |
DE69319531T2 (de) * | 1992-10-12 | 1999-04-15 | Sumitomo Electric Industries | Ultradünnes Filmlaminat |
US5783295A (en) * | 1992-11-09 | 1998-07-21 | Northwestern University | Polycrystalline supperlattice coated substrate and method/apparatus for making same |
EP0760021B1 (de) * | 1994-05-20 | 1998-03-04 | Widia GmbH | Werkzeug, verfahren zur herstellung des werkzeuges und verwendung des werkzeuges |
US5700551A (en) * | 1994-09-16 | 1997-12-23 | Sumitomo Electric Industries, Ltd. | Layered film made of ultrafine particles and a hard composite material for tools possessing the film |
ATE206772T1 (de) * | 1995-08-19 | 2001-10-15 | Widia Gmbh | Verbundkörper und verfahren zu dessen herstellung |
SE517046C2 (sv) * | 1997-11-26 | 2002-04-09 | Sandvik Ab | Plasmaaktiverad CVD-metod för beläggning av skärverktyg med finkornig aluminiumoxid |
-
2000
- 2000-04-06 DE DE10016958A patent/DE10016958A1/de not_active Withdrawn
-
2001
- 2001-03-08 US US10/257,086 patent/US20030108752A1/en not_active Abandoned
- 2001-03-08 EP EP01966772A patent/EP1268878A1/de not_active Withdrawn
- 2001-03-08 WO PCT/DE2001/000903 patent/WO2001077408A1/de not_active Application Discontinuation
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE4239234A1 (de) * | 1992-11-21 | 1994-06-09 | Krupp Widia Gmbh | Werkzeug und Verfahren zur Beschichtung eines Werkzeuggrundkörpers |
DE4417729A1 (de) * | 1992-11-21 | 1995-11-23 | Krupp Widia Gmbh | Werkzeug sowie Verfahren und Vorrichtung zur Herstellung des Werkzeuges und Verwendung des Werkzeuges |
WO1998048072A1 (en) * | 1997-04-18 | 1998-10-29 | Sandvik Ab (Publ) | Multilayered coated cutting tool |
Also Published As
Publication number | Publication date |
---|---|
DE10016958A1 (de) | 2001-10-18 |
US20030108752A1 (en) | 2003-06-12 |
EP1268878A1 (de) | 2003-01-02 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
DE60309992T2 (de) | Ausscheidungsgehärtete Verschleissschutzschicht | |
DE3512986C2 (de) | ||
EP0513662B1 (de) | Verfahren zum Beschichten des Werkstückes und mit einer Hartschicht versehener Grundkörper | |
EP0632850B1 (de) | Verbundkörper und dessen verwendung | |
EP2082079B1 (de) | Schichtsystem mit zumindest einer mischkristallschicht eines mehrfachoxids | |
DE102016108734B4 (de) | Beschichteter Körper und Verfahren zur Herstellung des Körpers | |
EP2753728B1 (de) | Werkzeug mit chromhaltiger funktionsschicht | |
EP2408945B1 (de) | Schneidwerkzeug | |
EP2209929B1 (de) | Beschichtetes werkzeug | |
DE69829581T2 (de) | Verfahren zum Beschichten feinkörnigen Aluminiumoxids auf Schneidwerkzeugen | |
EP1268878A1 (de) | Mit multilagen-schichten beschichteter substratkörper und verfahren zu seiner herstellung | |
EP0668938B1 (de) | Werkzeug und verfahren zur beschichtung eines werkzeuggrundkörpers | |
EP2132358B1 (de) | Mehrlagige cvd-schicht | |
EP0093706B1 (de) | Werkzeug und Verfahren zu dessen Herstellung | |
EP2281072B1 (de) | Werkzeug mit metalloxidbeschichtung | |
EP0845053B1 (de) | Verbundkörper und verfahren zu dessen herstellung | |
DE102009001765A1 (de) | PVD beschichtetes Werkzeug | |
EP1161573A1 (de) | Werkzeug mit einer molybdansulfidschicht und verfahren zu dessen herstellung | |
AT5008U1 (de) | Hartmetallverschleissteil mit mischoxidschicht | |
EP2171121B1 (de) | Werzeug mit mehrlagiger metalloxidbeschichtung und verfahren zum herstellen des beschichteten werkzeugs | |
DE60023628T2 (de) | Verfahren zur herstellung eines pvd ai2o3 beschichteten schneidwerkzeugs | |
WO2016128504A1 (de) | VHM-SCHAFTFRÄSER MIT TiAlN-ZrN-BESCHICHTUNG | |
DE10109523A1 (de) | Hartstoffbeschichtetes Bauteil mit Zwischenschicht zur Verbesserung der Haftfestigkeit der Beschichtung | |
DE102019200681B4 (de) | Schneidwerkzeug mit amorphem Kohlenstoff und Multilagenbeschichtung und Verfahren zu dessen Herstellung | |
CH681083A5 (de) |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AK | Designated states |
Kind code of ref document: A1 Designated state(s): US |
|
AL | Designated countries for regional patents |
Kind code of ref document: A1 Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE TR |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application | ||
DFPE | Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101) | ||
WWE | Wipo information: entry into national phase |
Ref document number: 2001966772 Country of ref document: EP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 10257086 Country of ref document: US |
|
WWP | Wipo information: published in national office |
Ref document number: 2001966772 Country of ref document: EP |
|
WWW | Wipo information: withdrawn in national office |
Ref document number: 2001966772 Country of ref document: EP |