EP1029117B1 - Procede pour l'enlevement de couches sur des corps - Google Patents

Procede pour l'enlevement de couches sur des corps Download PDF

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Publication number
EP1029117B1
EP1029117B1 EP98951155A EP98951155A EP1029117B1 EP 1029117 B1 EP1029117 B1 EP 1029117B1 EP 98951155 A EP98951155 A EP 98951155A EP 98951155 A EP98951155 A EP 98951155A EP 1029117 B1 EP1029117 B1 EP 1029117B1
Authority
EP
European Patent Office
Prior art keywords
process according
acid
solution
layer
hydrogen peroxide
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.)
Expired - Lifetime
Application number
EP98951155A
Other languages
German (de)
English (en)
Other versions
EP1029117A1 (fr
Inventor
Jan Hendrik Wijngaard
Hans Braendle
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Oerlikon Surface Solutions AG Pfaeffikon
Original Assignee
Unaxis Trading AG
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Unaxis Trading AG filed Critical Unaxis Trading AG
Publication of EP1029117A1 publication Critical patent/EP1029117A1/fr
Application granted granted Critical
Publication of EP1029117B1 publication Critical patent/EP1029117B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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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

  • DD 228 977 describes a process for stripping TiN layers, in particular for stripping on nickel substrates applied TiN layers. Thereby, the ones to be treated Parts for approx. 3 minutes at a temperature of approx. 70 ° C up to 80 ° C in a hydrogen peroxide solution with a content of 35 Ma% peroxide introduced, then rinsed in water, dried and then mulled. For stripping TiAlN layers this method is unsuitable because the Badly dissolves TiAlN in a hydrogen peroxide solution.
  • a process for the stripping of hard material layers various metal substrates is known from US 4,746,369.
  • the acidic decoating bath consists of hydrogen peroxide as an oxidizer and a phosphoric acid or nitric acid together.
  • the very low pH of the solution of less than 0.5 is for use on high speed steel substrates - HSS (High Speed Steel) - very disadvantageous.
  • DE 41 01 843 describes a process for the stripping of Hard material coated objects are known, wherein the objects with a solution containing tetra sodium diphosphate and hydrogen peroxide.
  • Typical are the hydrogen peroxide concentrations from 8 to 12% that relatively high tetra sodium diphosphate concentration from 8 to 12%, the high process temperature, at boiling temperature, and the high pH from 8 to 12.
  • the solution is about half of the initial volume evaporated - what at the high temperatures takes place relatively quickly - phosphating can already occur stripped surface occur. Titanium nitride and / or titanium nitride / carbide hard material layers.
  • DE 43 39 502 describes processes specific to layer material for stripping metal substrates, especially of Tungsten carbide substrates, known which hard material layers either from TiN, from TiCN or from TiAlN, or else from Layer systems made of TiN / TiAlN.
  • the solution bath settles, depending on the layer to be removed and while protecting the substrates, layer-specific a variety of components together.
  • High-speed steel is characterized by high carbon concentrations, up to 1.5%, and additions of strong carbide-forming elements such as chrome, molybdenum and tungsten Vanadium. Up to 12% cobalt is in some of the more complex ones Varieties included.
  • High-speed steel is so called because of its high hardness in high speed applications (see D.T. Llewellyn, Steel: Metallurgy and Application, Butterworth-Heihemann Ltd., Oxford 1992, p. 174).
  • a salt of a phosphoric acid, diphosphoric acid, Triphosphoric acid etc. is the phosphate "Calcium phosphate” a salt of phosphoric acid, “disodium dihydrogen phosphate” a salt of diphosphoric acid, further "penta-sodium triphosphate” a salt of triphosphoric acid Etc.
  • Phosphonate is a salt of a phosphonic acid, in particular an organic phosphonic acid, i.e. one Phosphonic acid with organic substituents understood.
  • the above-mentioned task is solved in that for the stripping of HSS substrates from a layer of TiAlN, at least a substance from the group of phosphates, phosphonates and phosphonic acids is used.
  • TiAlN dissolves in hydrogen peroxide solutions not even at elevated temperatures. Will the pH of the hydrogen peroxide solution by metering one Base, as raised by NaOH, to the alkaline range with pH ⁇ 7, then - according to the invention - in addition to those mentioned TiN and TiCN layers also dissolved TiAlN layers. It it was recognized that this is also the case at low process temperatures the case is.
  • alkaline hydrogen peroxide is the high process reliability with regard to corrosion of HSS material.
  • alkaline HSS behaves very noble in the media. So there is also then there is no risk of corrosion for the HSS substrate if longer Stripping times would have to be used.
  • the bath life is relative low, is usually between 1 and 3 batches what Of course, in certain cases it is quite sufficient.
  • This relatively short bath life is due to the limited Stability of polyphosphates.
  • the stability of polyphosphates is only moderate in alkaline solutions, in acidic solutions bad.
  • the polyphosphates are converted into orthophosphates by hydrolysis transferred for the stabilization of the peroxide solutions are far less effective.
  • the bath was heated to 60 ° C and 500 pieces of 12 mm HSS end mills, coated with a TiAlN layer in the solution brought in.
  • the tools were complete after 3 hours decoated and the bath temperature was stable at 60 ⁇ 2 ° C remained.
  • the temperature of the stripping solution was controlled by heating / cooling kept constant at about 60 ° C, and 500 Piece of 12mm HSS end mill, coated with a TiAlN layer, introduced into the solution. After three hours they were Tools completely stripped and the bath temperature was remained stable at 60 ⁇ 2 ° C. Several of the mentioned could Batches can be stripped in the same solution.
  • the advantage of the present invention is that it remains simple Solution composition, the simple process management and the short stripping time. At solution temperatures well below the boiling point can already be within can be stripped within a few hours. Regarding corrosion HSS substrates have a high level of security: Because the stripping solution alkaline, there is no corrosion of HSS instead of.
  • HSS substrates e.g. mixed with TiN, TiCN and / or TiAlN layers
  • a large number HSS substrates e.g. mixed with TiN, TiCN and / or TiAlN layers

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)

Claims (12)

  1. Procédé pour enlever sur des corps une couche de matière dure constituée d'un composé de Ti, dans une solution alcaline contenant
    du peroxyde d'hydrogène
    au moins une base
    au moins un acide et/ou un sel d'un acide,
       caractérisé en ce que pour enlever une couche sur des substrats en acier rapide comportant au moins une couche de TiAlN, l'acide susmentionné et/ou le sel susmentionné contiennent une substance du groupe constitué par les phosphates, les phosphonates, les acides phosphoniques.
  2. Procédé selon la revendication 1, caractérisé en ce que le phosphonate est introduit dans la solution tel quel et/ou grâce à l'introduction d'un acide phosphonique organique.
  3. Procédé selon la revendication 1 ou 2, caractérisé en ce qu'on utilise comme acide phosphonique l'acide AminoTrisMéthylènePhosphonique et/ou de préférence l'acide 1-hydroxyéthane-1,1-diphosphonique.
  4. Procédé selon l'une des revendications 1 à 3, caractérisé en ce qu'on utilise comme phosphate le dihydrogénopyrophosphate disodique et/ou Na2H2P2O7 et/ou le triphosphate pentasodique (Na5P3O10).
  5. Procédé selon la revendication 1 ou 2, caractérisé en ce que la température de solution est maintenue entre 20°C et 80°C inclus.
  6. Procédé selon l'une des revendications 1 à 3, caractérisé en ce qu'on choisit une concentration de peroxyde d'hydrogène située entre 5 et 50% en poids inclus.
  7. Procédé selon l'une des revendications 1 à 4, caractérisé en ce que la concentration de phosphate et/ou de phosphonate et/ou d'acide phosphonique est maintenue entre 0,1 et 10 % en poids inclus.
  8. Procédé selon l'une des revendications 1 à 7, caractérisé en ce qu'on utilise un volume de solution d'au moins 50 1, de préférence d'au moins 100 1.
  9. Procédé pour enlever une couche selon l'une des revendications 1 à 8, caractérisé en ce qu'on enlève en même temps, en plus d'au moins une couche de TiAlN, une couche de TiN et/ou de TiCN.
  10. Procédé selon l'une des revendications 1 à 9, les corps étant constitués par des outils.
  11. Procédé selon la revendication 10, les outils étant des outils d'enlèvement de copeaux ou de façonnage.
  12. Procédé selon la revendication 11, les outils étant des fraises, des plaquettes réversibles ou des outils d'estampage.
EP98951155A 1997-11-10 1998-11-09 Procede pour l'enlevement de couches sur des corps Expired - Lifetime EP1029117B1 (fr)

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 (fr) 1997-11-10 1998-11-09 Procede pour l'enlevement de couches sur des corps

Publications (2)

Publication Number Publication Date
EP1029117A1 EP1029117A1 (fr) 2000-08-23
EP1029117B1 true EP1029117B1 (fr) 2004-08-25

Family

ID=25687544

Family Applications (1)

Application Number Title Priority Date Filing Date
EP98951155A Expired - Lifetime EP1029117B1 (fr) 1997-11-10 1998-11-09 Procede pour l'enlevement de couches sur des corps

Country Status (6)

Country Link
US (1) US6432219B1 (fr)
EP (1) EP1029117B1 (fr)
JP (2) JP4326144B2 (fr)
DE (1) DE59811875D1 (fr)
ES (1) ES2226178T3 (fr)
WO (1) WO1999024642A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9212555B2 (en) 2005-10-14 2015-12-15 Mtu Aero Engines Gmbh Method for removing the coating from a gas turbine component

Families Citing this family (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999064646A1 (fr) * 1998-06-11 1999-12-16 Unaxis Trading Ag Procede pour enlever des couches de substance dure
JP3909035B2 (ja) * 2003-04-09 2007-04-25 三井金属鉱業株式会社 メッキ前処理液およびメッキ前処理方法
CH705281B1 (de) * 2004-01-29 2013-01-31 Oerlikon Trading Ag Entschichtungsverfahren.
WO2005073433A1 (fr) * 2004-01-29 2005-08-11 Unaxis Balzers Ag Procede d'enlevement de couche et dispositif a une chambre destine a la mise en oeuvre du procede d'enlevement de couche
US7077918B2 (en) 2004-01-29 2006-07-18 Unaxis Balzers Ltd. Stripping apparatus and method for removal of coatings on metal surfaces
US20070023943A1 (en) * 2005-07-28 2007-02-01 Forenz Dominick J Stripping titanium-based wear coatings
PL2276875T3 (pl) 2008-05-02 2020-06-01 Oerlikon Surface Solutions Ag, Pfäffikon Sposób usuwania powłok z obrabianych przedmiotów i roztwór do usuwania powłok
US9096555B2 (en) 2009-01-12 2015-08-04 Aerpio Therapeutics, Inc. Methods for treating vascular leak syndrome
JP5923033B2 (ja) * 2012-12-25 2016-05-24 三和油化工業株式会社 クロム系硬質皮膜用剥離液
WO2015139731A1 (fr) * 2014-03-18 2015-09-24 Platit Ag Procédé d'enlèvement de couches en matériau céramique dur de substrats en acier et en métal dur
JP6528092B2 (ja) * 2015-08-31 2019-06-12 日本表面化学株式会社 皮膜除去剤及び皮膜除去方法
US10570501B2 (en) 2017-05-31 2020-02-25 Kennametal Inc. Multilayer nitride hard coatings

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US3854996A (en) 1972-04-27 1974-12-17 Halliburton Co Method for removing magnetite scale
CA1209886A (fr) * 1982-01-11 1986-08-19 Thomas W. Bleeks Compositions au peroxyde de methode de decapage selectif
US4666528A (en) 1985-11-27 1987-05-19 Halliburton Company Method of removing iron and copper-containing scale from a metal surface
WO1992007110A1 (fr) * 1990-10-19 1992-04-30 Union Carbide Coatings Service Technology Corporation Bain de decapage et procede servant a decaper des composes de titane sur des metaux de base
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 (ja) * 1991-08-19 1997-04-09 株式会社不二越 高速度工具鋼のチタンコーティング被膜の除去剤
DE4339502C2 (de) * 1993-11-24 1999-02-25 Thoene Carl Stefan Entschichtungslösung zum naßchemischen Entfernen von Hartstoffschichten und Verfahren zu deren Anwendung
JPH08188886A (ja) * 1995-01-09 1996-07-23 Sumitomo Metal Mining Co Ltd 表面被覆膜の剥離方法
JP3320965B2 (ja) * 1995-03-29 2002-09-03 エムエムシーコベルコツール株式会社 硬質膜の剥離方法および該方法によって得られる再被覆部材
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

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9212555B2 (en) 2005-10-14 2015-12-15 Mtu Aero Engines Gmbh Method for removing the coating from a gas turbine component
DE102005049249B4 (de) 2005-10-14 2018-03-29 MTU Aero Engines AG Verfahren zur Entschichtung eines Gasturbinenbauteils

Also Published As

Publication number Publication date
ES2226178T3 (es) 2005-03-16
EP1029117A1 (fr) 2000-08-23
DE59811875D1 (de) 2004-09-30
JP5295853B2 (ja) 2013-09-18
JP4326144B2 (ja) 2009-09-02
WO1999024642A1 (fr) 1999-05-20
JP2001522943A (ja) 2001-11-20
JP2009167534A (ja) 2009-07-30
US6432219B1 (en) 2002-08-13

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