WO2007003648A1 - Hartstoffbeschichtete körper und verfahren zu deren herstellung - Google Patents
Hartstoffbeschichtete körper und verfahren zu deren herstellung Download PDFInfo
- Publication number
- WO2007003648A1 WO2007003648A1 PCT/EP2006/063881 EP2006063881W WO2007003648A1 WO 2007003648 A1 WO2007003648 A1 WO 2007003648A1 EP 2006063881 W EP2006063881 W EP 2006063881W WO 2007003648 A1 WO2007003648 A1 WO 2007003648A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- hard material
- tii
- layer
- hard
- coated
- Prior art date
Links
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 10
- 238000000576 coating method Methods 0.000 claims abstract description 12
- 239000000460 chlorine Substances 0.000 claims abstract description 9
- 239000011248 coating agent Substances 0.000 claims abstract description 9
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 8
- 239000002243 precursor Substances 0.000 claims abstract description 7
- 229910052984 zinc sulfide Inorganic materials 0.000 claims abstract description 7
- -1 titanium halides Chemical class 0.000 claims abstract description 6
- 229910017464 nitrogen compound Inorganic materials 0.000 claims abstract description 5
- 150000002830 nitrogen compounds Chemical class 0.000 claims abstract description 5
- 239000010936 titanium Substances 0.000 claims abstract description 5
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 4
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 3
- 239000000463 material Substances 0.000 claims description 29
- 238000000034 method Methods 0.000 claims description 24
- 239000000203 mixture Substances 0.000 claims description 11
- 230000005284 excitation Effects 0.000 claims description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 230000008021 deposition Effects 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 abstract description 8
- 238000007254 oxidation reaction Methods 0.000 abstract description 8
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical group [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 abstract description 4
- 239000000919 ceramic Substances 0.000 abstract description 3
- 229910052751 metal Inorganic materials 0.000 abstract description 3
- 239000002184 metal Substances 0.000 abstract description 3
- 229910000831 Steel Inorganic materials 0.000 abstract description 2
- 150000002739 metals Chemical class 0.000 abstract description 2
- 239000010959 steel Substances 0.000 abstract description 2
- 230000000638 stimulation Effects 0.000 abstract 2
- 229910010421 TiNx Inorganic materials 0.000 abstract 1
- 239000004411 aluminium Substances 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 40
- 239000007789 gas Substances 0.000 description 5
- 238000002230 thermal chemical vapour deposition Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 238000005268 plasma chemical vapour deposition Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 238000010896 thin film analysis Methods 0.000 description 2
- 229910018509 Al—N Inorganic materials 0.000 description 1
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 238000009304 pastoral farming Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical class Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 239000002347 wear-protection layer Substances 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
- C23C30/00—Coating with metallic material characterised only by the composition of the metallic material, i.e. not characterised by the coating process
- C23C30/005—Coating with metallic material characterised only by the composition of the metallic material, i.e. not characterised by the coating process on hard metal substrates
-
- 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
- C23C16/22—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 deposition of inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/34—Nitrides
-
- 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
-
- 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
- C23C30/00—Coating with metallic material characterised only by the composition of the metallic material, i.e. not characterised by the coating process
Definitions
- the invention relates to hard material-coated bodies with a single- or multi-layer system that contains at least one Tii -X AI X N hard material layer, and a method for their production.
- the coating according to the invention can be used in particular for tools made of steel, hard metals, cermets and ceramics, such as drills, milling cutters and indexable inserts.
- the bodies coated according to the invention have improved wear resistance and resistance to oxidation.
- Material system Ti-Al-N is already known in accordance with WO 03/085152 A2. It is possible to produce monophase TiAIN layers with the NaCI structure at AIN contents up to 67%. These layers, which are produced by means of PVD, have lattice constants a fCC between 0.412 nm and 0.424 nm (R. Cremer, M. Witthaut, A. von Richthofen, D. Neupetit, Fresenius J. Anal. Chem. 36J. (1998) 642-645). Such cubic TiAIN layers have a relatively high hardness and wear resistance. With AIN contents> 67%, however, a mixture of cubic and hexagonal TiAIN is created and with an AIN content> 75% only the softer and non-wear-resistant hexagonal wurtzite structure.
- PVD or plasma CVD processes are used according to the prior art, which are operated at temperatures below 700 0 C (A. Hörling, L. Hultman, M. Oden , J. Sjölen, L Karlsson, J. Vac. Sei. Technol. A 20 (2002) 5, 1815 - 1823 and D. Heim, R. Hochreiter, Surface and Coatings Technology 98 (1998) 1553 - 1556).
- a disadvantage of these methods is that the coating of complicated component geometries is difficult.
- PVD is a very directional process and plasma CVD requires high plasma homogeneity because the plasma power density has a direct influence on the Ti / Al atomic ratio of the layer. With the PVD processes used almost exclusively in industry, it is not possible to produce single-phase cubic Tii -X AI X N layers with x> 0.75.
- cubic TiAIN layers are a metastable structure, they cannot be produced using conventional CVD processes at high temperatures> 1000 0 C because a mixture of TiN and hexagonal AIN is formed at temperatures above 1000 0 C.
- the invention has for its object to achieve a significantly improved wear resistance and oxidation resistance in hard material coated bodies with a single or multi-layer system that contains at least one Tii -X AI X N hard material layer.
- Tii -X AI X N hard material layer Another feature of this Tii -X AI X N hard material layer is that its chlorine content is in the range between only 0.05 and 0.9 at.%.
- the chlorine content of the Tii -X AI X N hard material layer (s) is advantageously in the range from only 0.1 to 0.5 at.% And the oxygen content in the range from 0.1 to 5 at.%.
- the hardness value of the Tii -X AI X N hard material layer (s) is in the range from 2500 HV to 3800 HV.
- the Tii -X AI X N hard material layer (s) can contain up to 30% by mass of amorphous layer components.
- the layer present on the bodies according to the invention with its high hardness between 2500 HV to 3800 HV and with a significantly improved oxidation resistance compared to the prior art, which is achieved by the high AIN content in the cubic Tii -X AI X N phase , an unprecedented combination of hardness and resistance to oxidation, which results in very good wear resistance, especially at high temperatures.
- the invention includes a method, which is characterized in that the bodies are coated in a reactor at temperatures in the range from 700 ° C. to 900 ° C. by means of CVD without plasma excitation, titanium halides, aluminum halides and reactive nitrogen compounds being used as precursors find that are mixed at elevated temperature.
- NH 3 and / or N 2 H 4 can be used as reactive nitrogen compounds.
- the precursors are advantageously mixed in the reactor immediately before the deposition zone.
- the mixture of the precursors according to the invention is carried out at temperatures in the range of 15O 0 C to 900 ° C.
- the coating is advantageously carried out at pressures in the range from 10 2 Pa to 10 5 Pa.
- a Tii -X AI X N layer is deposited on WC / Co hard metal indexable inserts by means of the thermal CVD process according to the invention.
- a mixture of 100 ml / min of NH 3 and 200 ml / min of N 2 is fed into the reactor via a second gas feed.
- the two gas streams are mixed at a distance of 10 cm in front of the substrate carrier.
- a gray-black layer with a thickness of 6 ⁇ m is obtained for 30 minutes.
- the atomic ratio Ti: Al determined by WDX is 0.107.
- the chlorine and oxygen contents also determined are 0.1 at.% For Cl and 2.0 at.% For O.
- x 0.90.
- a hardness of the layer of 3070 HV [0.05] is measured using a Vickers indenter.
- the Tii -X AI X N layer is resistant to oxidation in air up to 1000 0 C.
- Titanium nitride layer using a known standard CVD process at 95O 0 C. upset.
- a gray-black layer is then deposited using the CVD process according to the invention using the gas mixture described in Example 1, a pressure of 1 kPa and a temperature of 85O 0 C.
- the X-ray thin-film analysis shows that here a heterogeneous
- the hardness of the layer determined using Vickers indenter is 3150 HV [ O 1 OI].
- the two-phase Tii -X AI X N layer is resistant to oxidation in air up to 1050 0 C.
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Vapour Deposition (AREA)
- Cutting Tools, Boring Holders, And Turrets (AREA)
Abstract
Description
Claims
Priority Applications (9)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CA2613091A CA2613091C (en) | 2005-07-04 | 2006-07-04 | Hard-material-coated bodies and method for their production |
MX2008000148A MX2008000148A (es) | 2005-07-04 | 2006-07-04 | Cuerpo revestido macizo y metodo para produccion del mismo. |
JP2008519933A JP4996602B2 (ja) | 2005-07-04 | 2006-07-04 | 硬質膜被覆された物体およびその製造方法 |
PL06777574T PL1902155T3 (pl) | 2005-07-04 | 2006-07-04 | Ciała powlekane materiałem twardym i sposoby ich otrzymywania |
ES06777574.2T ES2567589T3 (es) | 2005-07-04 | 2006-07-04 | Cuerpos recubiertos con materiales duros y procedimiento para su fabricación |
CN2006800244940A CN101218370B (zh) | 2005-07-04 | 2006-07-04 | 硬质材料涂覆体和它们的制备方法 |
US11/922,865 US7767320B2 (en) | 2005-07-04 | 2006-07-04 | Hard-material-coated bodies and method for their production |
EP06777574.2A EP1902155B1 (de) | 2005-07-04 | 2006-07-04 | Hartstoffbeschichtete körper und verfahren zu deren herstellung |
BRPI0613793-8A BRPI0613793B1 (pt) | 2005-07-04 | 2006-07-04 | Corpos revestidos de material duro e método para sua produção |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE102005032860.1 | 2005-07-04 | ||
DE102005032860A DE102005032860B4 (de) | 2005-07-04 | 2005-07-04 | Hartstoffbeschichtete Körper und Verfahren zu deren Herstellung |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2007003648A1 true WO2007003648A1 (de) | 2007-01-11 |
Family
ID=36822291
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP2006/063881 WO2007003648A1 (de) | 2005-07-04 | 2006-07-04 | Hartstoffbeschichtete körper und verfahren zu deren herstellung |
Country Status (13)
Country | Link |
---|---|
US (1) | US7767320B2 (de) |
EP (1) | EP1902155B1 (de) |
JP (1) | JP4996602B2 (de) |
KR (1) | KR20080028980A (de) |
CN (1) | CN101218370B (de) |
BR (1) | BRPI0613793B1 (de) |
CA (1) | CA2613091C (de) |
DE (1) | DE102005032860B4 (de) |
ES (1) | ES2567589T3 (de) |
MX (1) | MX2008000148A (de) |
PL (1) | PL1902155T3 (de) |
RU (1) | RU2405858C2 (de) |
WO (1) | WO2007003648A1 (de) |
Cited By (11)
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DE102008013964A1 (de) | 2008-03-12 | 2009-09-17 | Kennametal Inc. | Hartstoffbeschichteter Körper |
WO2009112116A1 (de) * | 2008-03-12 | 2009-09-17 | Kennametal Inc. | Hartstoffbeschichteter körper |
DE102008013965A1 (de) | 2008-03-12 | 2009-09-17 | Kennametal Inc. | Hartstoffbeschichteter Körper |
US9103036B2 (en) | 2013-03-15 | 2015-08-11 | Kennametal Inc. | Hard coatings comprising cubic phase forming compositions |
US9168664B2 (en) | 2013-08-16 | 2015-10-27 | Kennametal Inc. | Low stress hard coatings and applications thereof |
EP1902155B1 (de) | 2005-07-04 | 2016-02-03 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Hartstoffbeschichtete körper und verfahren zu deren herstellung |
US9896767B2 (en) | 2013-08-16 | 2018-02-20 | Kennametal Inc | Low stress hard coatings and applications thereof |
US20180361447A1 (en) * | 2015-12-07 | 2018-12-20 | Ihi Ionbond Ag | Coated extrusion tool |
EP2825686B1 (de) | 2012-03-14 | 2020-04-29 | BOEHLERIT GmbH & Co.KG. | Beschichteter körper und verfahren zum beschichten eines körpers |
US10968512B2 (en) | 2017-06-22 | 2021-04-06 | Kennametal Inc. | CVD composite refractory coatings and applications thereof |
EP2686462B2 (de) † | 2011-03-18 | 2022-08-10 | Boehlerit GmbH & Co. KG. | Beschichteter körper und verfahren zu dessen herstellung |
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AT505221B1 (de) * | 2007-05-08 | 2009-09-15 | Bihler Edelstahl Gmbh | Werkzeug mit beschichtung |
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DE102012107129A1 (de) * | 2012-08-03 | 2014-02-06 | Walter Ag | TiAIN-beschichtetes Werkzeug |
JP6090063B2 (ja) * | 2012-08-28 | 2017-03-08 | 三菱マテリアル株式会社 | 表面被覆切削工具 |
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Also Published As
Publication number | Publication date |
---|---|
PL1902155T3 (pl) | 2016-07-29 |
RU2405858C2 (ru) | 2010-12-10 |
CN101218370A (zh) | 2008-07-09 |
DE102005032860B4 (de) | 2007-08-09 |
JP4996602B2 (ja) | 2012-08-08 |
DE102005032860A1 (de) | 2007-01-11 |
CN101218370B (zh) | 2010-06-23 |
BRPI0613793A2 (pt) | 2011-02-15 |
US20090123779A1 (en) | 2009-05-14 |
ES2567589T3 (es) | 2016-04-25 |
CA2613091C (en) | 2017-07-04 |
MX2008000148A (es) | 2008-03-26 |
JP2008545063A (ja) | 2008-12-11 |
KR20080028980A (ko) | 2008-04-02 |
CA2613091A1 (en) | 2007-01-11 |
EP1902155A1 (de) | 2008-03-26 |
US7767320B2 (en) | 2010-08-03 |
EP1902155B1 (de) | 2016-02-03 |
BRPI0613793B1 (pt) | 2021-10-13 |
RU2007145953A (ru) | 2009-08-10 |
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