EP1029117A1 - Method for separating layers from articles - Google Patents
Method for separating layers from articlesInfo
- Publication number
- EP1029117A1 EP1029117A1 EP98951155A EP98951155A EP1029117A1 EP 1029117 A1 EP1029117 A1 EP 1029117A1 EP 98951155 A EP98951155 A EP 98951155A EP 98951155 A EP98951155 A EP 98951155A EP 1029117 A1 EP1029117 A1 EP 1029117A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- acid
- stripping
- solution
- hydrogen peroxide
- tialn
- 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.)
- Granted
Links
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
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/14—Cleaning or pickling metallic material with solutions or molten salts with alkaline solutions
- C23G1/19—Iron or steel
Definitions
- the present invention relates to a process for stripping bodies, provided with a hard material layer composed of a Ti compound in an alkaline solution
- At least one acid and / or a salt of an acid At least one acid and / or a salt of an acid.
- DD 228 977 describes a process for stripping TiN layers, in particular for stripping TiN layers applied to nickel substrates.
- the parts to be treated are placed in a hydrogen peroxide solution containing 35 mass% peroxide for approx. 3 minutes at a temperature of approx. 70 ° C to 80 ° C, then rinsed in water, dried and then rubbed off.
- This process is unsuitable for stripping TiAlN layers because the TiAlN dissolves poorly in a hydrogen peroxide solution.
- titanium nitride hard material layers on substrates made of stainless steel are decoated in aqueous nitric acid at temperatures above 70 ° C.
- the stripping time for a 1 ⁇ m thick layer is approx. 50 hours at 70 ° C. This extremely long stripping time is very disadvantageous.
- a method for the stripping of hard material layers on different metal substrates is known from US Pat. No. 4,746,369.
- the acidic decoating bath consists of hydrogen peroxide as an oxidizer and a phosphoric acid or nitric acid together.
- Various surface-active substances are also used.
- the solution's very low pH of less than 0.5 is very disadvantageous for use on high-speed steel substrates - HSS (High Speed Steel).
- DE 41 01 843 discloses a method for stripping objects coated with hard material layers, the objects being treated with a solution containing tetra sodium diphosphate and hydrogen peroxide.
- Typical are the hydrogen peroxide concentrations from 8 to 12%, the relatively high tetra sodium diphosphate concentration from 8 to 12%, the high process temperature at boiling temperature and the high pH value from 8 to 12. If the solution is up About half of the initial volume evaporated - which happens relatively quickly at the high temperatures - phosphating of the surface that has already been stripped can occur. Titanium nitride and / or titanium nitride / carbide hard material layers are stripped.
- DE 43 39 502 discloses layer-specific processes for stripping metal substrates, in particular also hard metal substrates, which hard material have layers of either TiN, TiCN or TiAlN, or of layer systems made of TiN / TiAlN.
- An alkaline solution with hydrogen peroxide, at least one base and at least one salt of mono- and dicarboxylic acids is used.
- the solution bath is composed of a large number of components, depending on the layer material.
- High-speed steel is characterized by high carbon concentrations, up to 1.5%, and additions of strongly carbide-forming elements such as chrome, molybdenum, tungsten and vanadium. Up to 12% cobalt is found in some of the more complex grades.
- High-speed steel is so called because it retains its high hardness in high-speed applications (see DT Llewellyn, Steel: Metallurgy and Application, Butterworth-Heihemann Ltd., Oxford 1992, p. 174).
- a salt of a phosphoric acid, diphosphoric acid, triphosphoric acid etc. is understood as phosphate.
- phosphate is the phosphate "calcium phosphate” a salt of phosphoric acid, “disodium dihydrogenphosphate” a salt of diphosphoric acid, further "pentasodium triphosphate” a salt of triphosphoric acid etc.
- a salt of a phosphonic acid in particular an organic phosphonic acid, i.e. a phosphonic acid with organic substituents understood.
- the above-mentioned object is achieved in that at least one substance from the group of the phosphates, phosphonates and phosphonic acids is used for the de-coating of HSS substrates with at least one layer of TiN, TiCN or TiAlN.
- di-sodium dihydrogen pyrophosphate Na-H 2 P 2 0 7 and / or penta-sodium triphosphate (Na s P 3 O 10 ) is preferably used;
- phosphonic acid methylenephosphonic acid
- 1-hydroxyethane 1,1-diphosphonic acid
- phosphonic acids are introduced directly into the solution as such. This applies generally for the use of phosphonates, phosphates and phosphonic acids.
- the process temperature of the solution bath is kept at 20 ° C to 80 ° C, if necessary by heating and / or cooling (the range limits are included);
- the peroxide concentration is chosen between 5 and 50% by weight (the range limits are included);
- the concentration of phosphate and / or phosphonate and / or phosphonic acid is chosen between 0.1 and 10% by weight (the range limits are included);
- the solution preferably consists of distilled water, hydrogen peroxide, the base mentioned, for example NaOH, and the aforementioned phosphates and / or phosphonates and / or phosphonic acids, at least in a predominant proportion.
- TiAlN does not dissolve in hydrogen peroxide solutions even at elevated temperatures. If the pH of the hydrogen peroxide solution is raised by metering in a base, such as NaOH, to the alkaline range with pH> 7, then TiAlN layers are also dissolved in addition to the mentioned TiN and TiCN layers. According to the invention, it was recognized that this is also the case at low process temperatures.
- alkaline hydrogen peroxide is the high level of process reliability with regard to corrosion of HSS material.
- HSS behaves very nobly in the Alaskan media. This means that there is no risk of corrosion for the HSS substrate even if longer stripping times would have to be used.
- the problem of the instability of alkaline hydrogen peroxide solutions in that an autooxidation of the hydrogen peroxide takes place, which is catalyzed by metal ions which are released into the solution during the stripping process, which in turn leads to overheating and boiling over of the stripping bath, according to the invention at least by the metering a phosphate and / or phosphonate and / or at least at least one phosphonic acid dissolved as a stabilizer.
- the decoating is accelerated by this addition, with regard to all the hard material layers mentioned.
- This metering improves the bath stability so that the decoating bath could be operated stably even at an elevated temperature.
- Heating and / or cooling can be provided to maintain the bath temperature; if necessary, the bath temperature is regulated to a desired value, with heating and / or cooling as an actuator.
- the bath service life is relatively short, normally between 1 and 3 batches, which of course is quite sufficient in certain cases.
- This relatively short bath life is due to the limited stability of polyphosphates.
- the stability of polyphosphates in alkaline solutions is only moderate, poor in acidic solutions.
- hydrolysis the polyphosphates are converted into orthophosphates, which are far less effective for stabilizing the peroxide solutions.
- the bath was heated to 60 ° C. and 500 pieces of 12 mm HSS end mill, coated with a TiAlN layer, were introduced into the solution. After 3 hours, the tools were completely stripped and the bath temperature remained stable at 60 ⁇ 2 ° C.
- Example III The temperature of the stripping solution was kept constant by heating / cooling to approximately 60 ° C., and 500 pieces of 12 mm HSS end mills, coated with a TiAlN layer, were introduced into the solution. After three hours, the tools were completely stripped and the bath temperature remained stable at 60 ⁇ 2 ° C. Several of the batches mentioned could be decoated in the same solution. Compared to the use of polyphosphates according to Example I, the belt life could be extended by a factor of 2 to 4.
- Example III Example III
- the advantages of the present invention are the simple solution composition, the simple process control and the short stripping time. With solution temperatures well below the boiling point, stripping can take place within a few hours. There is a high level of security with regard to corrosion on HSS substrates: because the decoating solution is alkaline, there is no corrosion of HSS.
- HSS substrates e.g. mixed with TiN, TiCN and / or TiAlN layers
- high volumes of solution e.g. of over 50 1 or even over 100 1
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- ing And Chemical Polishing (AREA)
- Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
- Detergent Compositions (AREA)
Abstract
Description
Claims
Applications Claiming Priority (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CH258897 | 1997-11-10 | ||
CH258897 | 1997-11-10 | ||
CH140398 | 1998-07-01 | ||
CH140398 | 1998-07-01 | ||
PCT/CH1998/000479 WO1999024642A1 (en) | 1997-11-10 | 1998-11-09 | Method for separating layers from articles |
Publications (2)
Publication Number | Publication Date |
---|---|
EP1029117A1 true EP1029117A1 (en) | 2000-08-23 |
EP1029117B1 EP1029117B1 (en) | 2004-08-25 |
Family
ID=25687544
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP98951155A Expired - Lifetime EP1029117B1 (en) | 1997-11-10 | 1998-11-09 | Method for separating layers from articles |
Country Status (6)
Country | Link |
---|---|
US (1) | US6432219B1 (en) |
EP (1) | EP1029117B1 (en) |
JP (2) | JP4326144B2 (en) |
DE (1) | DE59811875D1 (en) |
ES (1) | ES2226178T3 (en) |
WO (1) | WO1999024642A1 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US9057134B2 (en) | 2008-05-02 | 2015-06-16 | Oerlikon Surface Solutions Ag, Trubbach | Process for the stripping of workpieces and stripping solution |
Families Citing this family (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1999064646A1 (en) * | 1998-06-11 | 1999-12-16 | Unaxis Trading Ag | Method for removing layers of hard material |
JP3909035B2 (en) * | 2003-04-09 | 2007-04-25 | 三井金属鉱業株式会社 | Plating pretreatment liquid and plating pretreatment method |
US7077918B2 (en) | 2004-01-29 | 2006-07-18 | Unaxis Balzers Ltd. | Stripping apparatus and method for removal of coatings on metal surfaces |
CH705281B1 (en) * | 2004-01-29 | 2013-01-31 | Oerlikon Trading Ag | Process for removing a layer system from a workpiece comprises applying a chromium- and aluminum-containing layer directly on the workpiece, and removing the coating on the workpiece using an alkaline solution |
WO2005073433A1 (en) * | 2004-01-29 | 2005-08-11 | Unaxis Balzers Ag | Method for removing a coating and single-chamber device for carrying out said method |
US20070023943A1 (en) * | 2005-07-28 | 2007-02-01 | Forenz Dominick J | Stripping titanium-based wear coatings |
DE102005049249B4 (en) | 2005-10-14 | 2018-03-29 | MTU Aero Engines AG | Process for stripping a gas turbine component |
US9096555B2 (en) | 2009-01-12 | 2015-08-04 | Aerpio Therapeutics, Inc. | Methods for treating vascular leak syndrome |
JP5923033B2 (en) * | 2012-12-25 | 2016-05-24 | 三和油化工業株式会社 | Chromium hard coating stripping solution |
US9879356B2 (en) | 2014-03-18 | 2018-01-30 | Platit Ag | Method for delamination of ceramic hard material layers from steel and cemented carbide substrates |
JP6528092B2 (en) * | 2015-08-31 | 2019-06-12 | 日本表面化学株式会社 | Coating remover and coating removing method |
US10570501B2 (en) | 2017-05-31 | 2020-02-25 | Kennametal Inc. | Multilayer nitride hard coatings |
Family Cites Families (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3854996A (en) | 1972-04-27 | 1974-12-17 | Halliburton Co | Method for removing magnetite scale |
CA1209886A (en) * | 1982-01-11 | 1986-08-19 | Thomas W. Bleeks | Peroxide selective stripping compositions and method |
US4666528A (en) | 1985-11-27 | 1987-05-19 | Halliburton Company | Method of removing iron and copper-containing scale from a metal surface |
WO1992007110A1 (en) | 1990-10-19 | 1992-04-30 | Union Carbide Coatings Service Technology Corporation | Stripping solution and process for stripping compounds of titanium from base metals |
DE4101843C1 (en) * | 1991-01-23 | 1992-04-02 | Eifeler Werkzeuge Gmbh, 4000 Duesseldorf, De | Hard tool coating for economy - by stripping using tetra:sodium di:phosphate soln. and hydrogen peroxide |
DE4110595C1 (en) * | 1991-04-02 | 1992-11-26 | Thyssen Edelstahlwerke Ag, 4000 Duesseldorf, De | Wet-chemical removal of hard coatings from workpiece surfaces - comprises using hydrogen peroxide soln. stabilised by complex former e.g. potassium-sodium tartrate-tetra:hydrate |
JP2597931B2 (en) * | 1991-08-19 | 1997-04-09 | 株式会社不二越 | Removal agent for titanium coating on high speed tool steel |
DE4339502C2 (en) * | 1993-11-24 | 1999-02-25 | Thoene Carl Stefan | Stripping solution for the wet chemical removal of hard material layers and processes for their application |
JPH08188886A (en) * | 1995-01-09 | 1996-07-23 | Sumitomo Metal Mining Co Ltd | Method for stripping surface coating film |
JP3320965B2 (en) * | 1995-03-29 | 2002-09-03 | エムエムシーコベルコツール株式会社 | Hard film peeling method and recoated member obtained by the method |
US6039891A (en) * | 1996-09-24 | 2000-03-21 | Cabot Corporation | Multi-oxidizer precursor for chemical mechanical polishing |
US5847463A (en) * | 1997-08-22 | 1998-12-08 | Micron Technology, Inc. | Local interconnect comprising titanium nitride barrier layer |
-
1998
- 1998-11-09 EP EP98951155A patent/EP1029117B1/en not_active Expired - Lifetime
- 1998-11-09 JP JP2000519631A patent/JP4326144B2/en not_active Expired - Fee Related
- 1998-11-09 DE DE59811875T patent/DE59811875D1/en not_active Expired - Lifetime
- 1998-11-09 WO PCT/CH1998/000479 patent/WO1999024642A1/en active IP Right Grant
- 1998-11-09 US US09/530,460 patent/US6432219B1/en not_active Expired - Lifetime
- 1998-11-09 ES ES98951155T patent/ES2226178T3/en not_active Expired - Lifetime
-
2009
- 2009-04-28 JP JP2009109435A patent/JP5295853B2/en not_active Expired - Fee Related
Non-Patent Citations (1)
Title |
---|
See references of WO9924642A1 * |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US9057134B2 (en) | 2008-05-02 | 2015-06-16 | Oerlikon Surface Solutions Ag, Trubbach | Process for the stripping of workpieces and stripping solution |
Also Published As
Publication number | Publication date |
---|---|
WO1999024642A1 (en) | 1999-05-20 |
EP1029117B1 (en) | 2004-08-25 |
DE59811875D1 (en) | 2004-09-30 |
JP5295853B2 (en) | 2013-09-18 |
JP4326144B2 (en) | 2009-09-02 |
JP2009167534A (en) | 2009-07-30 |
ES2226178T3 (en) | 2005-03-16 |
US6432219B1 (en) | 2002-08-13 |
JP2001522943A (en) | 2001-11-20 |
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