EP0575244A1 - Verfahren zur Behandlung eines Substrats auf Aluminiumbasis für die Eloxierung, das in diesem Verfahren verwendete Bad sowie ein Konzentrat zur Herstellung des Bades - Google Patents

Verfahren zur Behandlung eines Substrats auf Aluminiumbasis für die Eloxierung, das in diesem Verfahren verwendete Bad sowie ein Konzentrat zur Herstellung des Bades Download PDF

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Publication number
EP0575244A1
EP0575244A1 EP93401533A EP93401533A EP0575244A1 EP 0575244 A1 EP0575244 A1 EP 0575244A1 EP 93401533 A EP93401533 A EP 93401533A EP 93401533 A EP93401533 A EP 93401533A EP 0575244 A1 EP0575244 A1 EP 0575244A1
Authority
EP
European Patent Office
Prior art keywords
bath
acid
satin
zirconium
titanium
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
Application number
EP93401533A
Other languages
English (en)
French (fr)
Other versions
EP0575244B1 (de
Inventor
Joseph Schapira
Patrick Droniou
Patrice Pelletier
Stéphane Ganepain
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.)
Compagnie Francaise de Produits Industriels SA
Original Assignee
Compagnie Francaise de Produits Industriels SA
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.)
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Publication date
Application filed by Compagnie Francaise de Produits Industriels SA filed Critical Compagnie Francaise de Produits Industriels SA
Publication of EP0575244A1 publication Critical patent/EP0575244A1/de
Application granted granted Critical
Publication of EP0575244B1 publication Critical patent/EP0575244B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/04—Anodisation of aluminium or alloys based thereon
    • C25D11/16—Pretreatment, e.g. desmutting

Definitions

  • the subject of the invention is a method of treating aluminum-based substrates with a view to their anodization.
  • It also relates to a bath used in this process as well as a concentrate for the preparation of the bath.
  • Substrates i.e. parts and profiles based on aluminum, in other words aluminum or one of its alloys, are used in industry and in particular in architectural applications, in particular for manufacturing doorframes.
  • the above-mentioned parts and profiles can be painted or be subjected to an electrolytic anodizing treatment of aluminum in an acid medium.
  • the parts and profiles are protected by an artificially formed Al2O d'oxide layer; depending on the desired degree of protection which is a function of the use of the parts inside or outside, the alumina layer can be more or less thick; its thickness is generally between 2 and 30 microns.
  • the steps preceding the anodic oxidation include the so-called satin-finishing step producing a pickling which consists in removing the surface layer from the substrates; in practice, the treated parts or profiles are pickled to a thickness of approximately 30 microns, which corresponds to a weight loss of approximately 90 g / m2.
  • the gloss of the substrate which reflects the state of "dullness" obtained and which is measured according to ISO standard 7668, at 60 ° C., is between 35 and 70 after the satin-finishing step and is between 5 and 13 after 1 'oxidation anodic; the lower the figure obtained when measuring the gloss, the higher the dullness of the surface.
  • complexing agents such as gluconate are added to the above baths.
  • Environmental protection means that, on a global level, discharges of both aqueous and solid effluents are increasingly low; we therefore try to recycle used products and regenerate them as well as recover non-regenerable waste.
  • landfill becomes more and more difficult due to the filling of the latter and it therefore appears necessary to minimize, in the context of the surface preparation of aluminum before anodic oxidation , the chemical attacks related to satin-finishing in order to subsequently minimize aluminum hydroxide sludge from neutralization of bath effluents.
  • the invention therefore aims to provide a method and a bath of the kind in question which do not have the drawbacks inherent in the prior art and by which it is possible to impart excellent dullness to the treated substrates.
  • the method according to the invention for treating aluminum-based substrates with a view to their anodization is characterized by the fact that it comprises a surface treatment or satin-finishing step using an acid bath comprising at least one fluorinated derivative of titanium and / or zirconium and / or silicon as well as at least one acid from the group comprising nitric, sulfuric and phosphoric acids.
  • the satin-finishing step using the acid bath is followed by a complementary light satin-finishing step using an alkaline bath, the conditions of this satin-finishing being such that it leads to pickling of up to 40 g / m2 of aluminum.
  • the bath according to the invention for the treatment of aluminum-based substrates with a view to their anodization is characterized in that it comprises at least one fluorinated derivative of titanium and / or zirconium and / or silicon as well as '' at least one acid from the group comprising nitric, sulfuric and phosphoric acids.
  • the concentrate according to the invention which is capable of providing by dilution with water the bath according to the invention can contain the fluorinated derivative of titanium and / or zirconium and / or silicon in a concentration of commercial product of 50 to 99.5% and the acid of the group comprising nitric, sulfuric and phosphoric acids at a concentration of commercial product of 0.5 to 50%.
  • Nitric, sulfuric and phosphoric acids have the advantage of being present on the anodic oxidation lines in acid degreasing (H3PO4), bleaching (HNO3) and anodic oxidation baths. (H2SO4); they can also be regenerated from these baths by already known methods (ion exchange resins for example); they can also be used directly in the acid pickling bath if their pollution rate allows, which is the case in the context of the present invention.
  • a concentrate according to the invention suitable for supplying the bath according to the invention after dilution with water and recycled acid can comprise, in addition to water, a fluorinated derivative of titanium and / or zirconium and / or silicon at a concentration of commercial product of between 50 and 99.5%.
  • Such a concentrate can be diluted in water to a concentration of between 1 per thousand and 10% to constitute the ready-to-use bath.
  • the fluorinated derivative of titanium, zirconium or silicon is chosen from the group comprising the fluometallic acids H2TiF6, H2ZrF6, H2SiF6, as well as their alkali or ammonium salts.
  • the pickling bath according to the invention comprises the fluorinated derivative of titanium and / or zirconium and / or silicon at a concentration of at least 1 g / l, and nitric acid and / or sulfuric and / or phosphoric at a concentration between 0.5 and 100 ml per liter of bath, expressed as concentrated commercial acid.
  • the above concentrations as well as the duration and the temperature of the satin-finishing step are adjusted so as to obtain a pickling rate of at least 5 g / m2 of the substrate.
  • the surfactants in question can be chosen from the group comprising alkylphenols, alcohols and polyalkoxylated amines, alkyl-, alkylaryl- and arylsulfates, sulfonates, phosphates and quaternary ammoniums.
  • the third solvents can for example be glycols.
  • the temperature of the satin-finishing bath is between 15 ° C and 80 ° C and, preferably, between 20 and 60 ° C.
  • the time during which the action of the bath is maintained is between 1 minute and 1 hour.
  • the processing time in industry will preferably not exceed about thirty minutes.
  • a complementary light alkaline pickling carried out according to a process known per se and such that it leads to pickling of at most 40 g / m2 d 'aluminum; one can, for example, use a bath having a temperature between 40 and 70 ° C and containing, on the one hand, between 10 and 180 g / l of aluminum (i.e.
  • Such an additive which is based on gluconate can be that sold by the Applicant Company under the brand PROGAL G 313 TA.
  • the alkaline pickling bath thus formed is used for a period of 2 to 20 minutes on the parts coming out of the acid pickling bath.
  • the temperature of the acid pickling bath is 30 ° C.
  • the treatment time is chosen to have a pickling of approximately 25 g / m2.
  • the treatment time in this bath and when the acid pickling baths are those called b1 to b6, is that necessary to have a pickling rate of approximately 25 g / m2.
  • step 3 the baths b1 and b9 to b14 defined in Table III are used.
  • Baths b1 and b9 to b14 are used at 30 ° C and for the time necessary to cause the treated parts to lose weight in the order of 25 g / m2. These baths are used respectively to carry out the Experiments 1 and 9 to 14, the results of which are collated in Table IV. TABLE IV Exp. No.
  • the time required to obtain a pickling rate of approximately 24 g / m2 was determined for each of the K2TiF6 concentrations and for each of the temperatures selected, the 98% sulfuric acid concentration being 3 ml / l.
  • the processing time is then between six minutes and about thirty minutes, time easily manageable on a production line.
  • the acid pickling bath (step 3) used consists of the bath bl described in example 1. Its working temperature is 30 ° C. and the soaking time is 15 minutes.
  • the mattness of the profiles, measured after step 4 according to ISO standard 7668 (at 60 °) is 22; this mattness is comparable to that obtained in the experiments carried out with baths b1 to b3 of Example 1 and significantly improved compared to that obtained in the experiments carried out with the control baths b7 and b8 of Example 1.
  • the dullness measured according to the same method at the end of step 12, is 5, that is to say markedly improved compared to the dullness measured under the same conditions according to experiment 8 of Example 1 and which is industrially 12-15.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Engineering & Computer Science (AREA)
  • Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
  • ing And Chemical Polishing (AREA)
  • Chemical Treatment Of Metals (AREA)
  • Manufacture And Refinement Of Metals (AREA)
  • Detergent Compositions (AREA)
  • Materials For Photolithography (AREA)
  • Printing Plates And Materials Therefor (AREA)
EP93401533A 1992-06-17 1993-06-15 Verfahren zur Behandlung eines Substrats auf Aluminiumbasis für die Eloxierung, das in diesem Verfahren verwendete Bad sowie ein Konzentrat zur Herstellung des Bades Expired - Lifetime EP0575244B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR9207352 1992-06-17
FR929207352A FR2692599B1 (fr) 1992-06-17 1992-06-17 Procédé de traitement de substrats à base d'aluminium en vue de leur anodisation, bain mis en Óoeuvre dans ce procédé et concentré pour préparer le bain.

Publications (2)

Publication Number Publication Date
EP0575244A1 true EP0575244A1 (de) 1993-12-22
EP0575244B1 EP0575244B1 (de) 1999-05-06

Family

ID=9430843

Family Applications (1)

Application Number Title Priority Date Filing Date
EP93401533A Expired - Lifetime EP0575244B1 (de) 1992-06-17 1993-06-15 Verfahren zur Behandlung eines Substrats auf Aluminiumbasis für die Eloxierung, das in diesem Verfahren verwendete Bad sowie ein Konzentrat zur Herstellung des Bades

Country Status (8)

Country Link
US (1) US5460694A (de)
EP (1) EP0575244B1 (de)
JP (1) JPH06184791A (de)
AT (1) ATE179766T1 (de)
CA (2) CA2098689A1 (de)
DE (1) DE69324729T2 (de)
ES (1) ES2130236T3 (de)
FR (1) FR2692599B1 (de)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10435806B2 (en) 2015-10-12 2019-10-08 Prc-Desoto International, Inc. Methods for electrolytically depositing pretreatment compositions

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KR0183826B1 (ko) * 1996-03-04 1999-05-01 김광호 연마공정 후처리용 세정 용액 및 그를 이용하는 세정 방법
US6043206A (en) 1996-10-19 2000-03-28 Samsung Electronics Co., Ltd. Solutions for cleaning integrated circuit substrates
US5932023A (en) * 1997-02-25 1999-08-03 Ward; Glen Douglas Method of washing a vehicle using a two-part washing composition
US7910218B2 (en) 2003-10-22 2011-03-22 Applied Materials, Inc. Cleaning and refurbishing chamber components having metal coatings
US7618769B2 (en) * 2004-06-07 2009-11-17 Applied Materials, Inc. Textured chamber surface
US7670436B2 (en) 2004-11-03 2010-03-02 Applied Materials, Inc. Support ring assembly
US8617672B2 (en) 2005-07-13 2013-12-31 Applied Materials, Inc. Localized surface annealing of components for substrate processing chambers
US7762114B2 (en) 2005-09-09 2010-07-27 Applied Materials, Inc. Flow-formed chamber component having a textured surface
US9127362B2 (en) 2005-10-31 2015-09-08 Applied Materials, Inc. Process kit and target for substrate processing chamber
US8647484B2 (en) 2005-11-25 2014-02-11 Applied Materials, Inc. Target for sputtering chamber
US7981262B2 (en) 2007-01-29 2011-07-19 Applied Materials, Inc. Process kit for substrate processing chamber
US7942969B2 (en) 2007-05-30 2011-05-17 Applied Materials, Inc. Substrate cleaning chamber and components
US9428410B2 (en) 2007-09-28 2016-08-30 Ppg Industries Ohio, Inc. Methods for treating a ferrous metal substrate
US8097093B2 (en) 2007-09-28 2012-01-17 Ppg Industries Ohio, Inc Methods for treating a ferrous metal substrate
KR101475173B1 (ko) * 2011-06-24 2014-12-19 애플 인크. 양극산화처리된 부품의 미용적 결함 저감
TWI444508B (zh) * 2012-05-07 2014-07-11 Catcher Technology Co Ltd 具止滑皮革質感表面之金屬工件製造方法
DE102012015579A1 (de) * 2012-08-08 2014-02-13 Premium Aerotec Gmbh Oberflächenschutzverfahren für Bauteile aus Aluminium bzw. Aluminiumlegierungen mit einem Nachweis einer unzulässigen Überhitzung
US9273399B2 (en) 2013-03-15 2016-03-01 Ppg Industries Ohio, Inc. Pretreatment compositions and methods for coating a battery electrode
US9101954B2 (en) 2013-09-17 2015-08-11 Applied Materials, Inc. Geometries and patterns for surface texturing to increase deposition retention
EP3498890A1 (de) * 2017-12-12 2019-06-19 Hydro Aluminium Rolled Products GmbH Beizverfahren für profile, gewalzte bänder und bleche aus aluminiumlegierungen

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US4502925A (en) * 1984-06-11 1985-03-05 American Hoechst Corporation Process for aluminum surface preparation

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Cited By (3)

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Publication number Priority date Publication date Assignee Title
US10435806B2 (en) 2015-10-12 2019-10-08 Prc-Desoto International, Inc. Methods for electrolytically depositing pretreatment compositions
US11591707B2 (en) 2015-10-12 2023-02-28 Ppg Industries Ohio, Inc. Methods for electrolytically depositing pretreatment compositions
US12104272B2 (en) 2015-10-12 2024-10-01 Prc-Desoto International, Inc. Treated substrates

Also Published As

Publication number Publication date
DE69324729D1 (de) 1999-06-10
US5460694A (en) 1995-10-24
FR2692599A1 (fr) 1993-12-24
ES2130236T3 (es) 1999-07-01
EP0575244B1 (de) 1999-05-06
JPH06184791A (ja) 1994-07-05
CA2098689A1 (en) 1993-12-18
CA2098690A1 (en) 1993-12-18
DE69324729T2 (de) 1999-12-02
FR2692599B1 (fr) 1994-09-16
ATE179766T1 (de) 1999-05-15

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