WO2006018535A1 - Procede de formation d ' une couche de conversion sur un produit en alliage d ' aluminium avant le procede de brasage sans flux - Google Patents
Procede de formation d ' une couche de conversion sur un produit en alliage d ' aluminium avant le procede de brasage sans flux Download PDFInfo
- Publication number
- WO2006018535A1 WO2006018535A1 PCT/FR2005/001935 FR2005001935W WO2006018535A1 WO 2006018535 A1 WO2006018535 A1 WO 2006018535A1 FR 2005001935 W FR2005001935 W FR 2005001935W WO 2006018535 A1 WO2006018535 A1 WO 2006018535A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- treatment
- solution
- conversion layer
- flux
- temperature
- Prior art date
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
- 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
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/34—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K1/00—Soldering, e.g. brazing, or unsoldering
- B23K1/20—Preliminary treatment of work or areas to be soldered, e.g. in respect of a galvanic coating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K2103/00—Materials to be soldered, welded or cut
- B23K2103/08—Non-ferrous metals or alloys
- B23K2103/10—Aluminium or alloys thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
- B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
- B23K35/36—Selection of non-metallic compositions, e.g. coatings, fluxes; Selection of soldering or welding materials, conjoint with selection of non-metallic compositions, both selections being of interest
- B23K35/3601—Selection of non-metallic compositions, e.g. coatings, fluxes; Selection of soldering or welding materials, conjoint with selection of non-metallic compositions, both selections being of interest with inorganic compounds as principal constituents
- B23K35/3603—Halide salts
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
- B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
- B23K35/36—Selection of non-metallic compositions, e.g. coatings, fluxes; Selection of soldering or welding materials, conjoint with selection of non-metallic compositions, both selections being of interest
- B23K35/3601—Selection of non-metallic compositions, e.g. coatings, fluxes; Selection of soldering or welding materials, conjoint with selection of non-metallic compositions, both selections being of interest with inorganic compounds as principal constituents
- B23K35/3603—Halide salts
- B23K35/3605—Fluorides
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2913—Rod, strand, filament or fiber
- Y10T428/2933—Coated or with bond, impregnation or core
- Y10T428/294—Coated or with bond, impregnation or core including metal or compound thereof [excluding glass, ceramic and asbestos]
- Y10T428/2951—Metal with weld modifying or stabilizing coating [e.g., flux, slag, producer, etc.]
Definitions
- the invention relates to a solder joining method without product flow in
- Aluminum alloy such as sheets, strips or tubes, the absence of flux being permitted by a prior treatment for forming a surface conversion layer of said aluminum alloy products. These products are used in particular in the manufacture of heat exchangers, in particular those used for engine cooling and air conditioning of vehicle interiors.
- brazing process currently the most used for the manufacture of heat exchangers is brazing in a controlled atmosphere with a non-corrosive flow, called Nocolok® brazing. This process gradually replaces the vacuum brazing used previously but which required expensive installations both in initial investment and maintenance.
- the first category concerns soldering processes without flux. Processes using products made of aluminum alloy (s) coated with nickel deposition (see for example WO 02/07928 by Corus Aluminum Walz organization) and the addition of sodium to plating alloy described in WO 01/98019 from Kaiser Alurninum & Chemical Corporation.
- the second category concerns so-called pre-fluxed strips, that is to say strips having a surface layer containing the soldering flux.
- the flux is mechanically inlaid into the strip during rolling.
- the flux is incorporated in a binder and everything is deposited on the aluminum alloy strip.
- US Pat. No. 6,344,237 to Alcoa Inc. the flux is embedded in the metal by high speed spraying.
- Ford Global Technologies patent EP 1067213 describes the treatment of an aluminum alloy strip in an aqueous solution of 2 to 25% by weight of KF at a temperature of between 32 and 100 ° C. for at least 5 seconds. This operation would create on the surface of the metal a conversion layer which contains either substantially K 3 AlF 6 or mainly K 3 AlF 6 and in addition a small proportion of KAlF 4 .
- the subject of the invention is therefore a soldering process without flux of products such as sheets, strips or tubes of heat exchangers, characterized in that, to avoid the use of said flux, said alloy products ( ) of aluminum, are previously subjected to a formation treatment, on all or part of their surface, of a conversion layer using a solution containing K + ions and F " and one or more acid (s) in an amount such that the pH of the solution is less than
- said treatment is preceded by an alkaline pickling.
- the acid is preferably sulfuric acid at a concentration of between 10 and
- the treatment is preferably at a temperature of between 30 and
- the K + and F " ions are advantageously provided in the form of KF or in the form of a KCl + NH 5 F 2 mixture.
- Figures 1a and 1b show, respectively in top view and side view, the V-shaped specimens used in the examples for evaluating the solderability.
- the invention consists in modifying the treatment solution described in patent EP 1067213 to obtain on all or part of the surface of products made of aluminum alloy (s), sheets, strips or tubes, used in the manufacture of heat exchangers , in particular of motor vehicles, a deposit allowing their brazing without additional addition of flux.
- This modification consists in an acidification of the bath, without using the hydrofluoric acid which is mentioned in the application EP 0140267 of Toyota Chuo and which poses too great toxicity problems.
- the invention consists in adding to the KF solution described in the aforementioned patent sulfuric acid at a level of 10 to 40 g / l. It would also be possible to use nitric acid HNO 3 at a concentration of 20 to 50% by volume, but this solution is not preferred because of the possible emission of nitrous vapors. May also be used hydrochloric acid HCl (typically at a concentration of 1 to 50 g / l) 5 one or more organic acids, or any combination thereof inorganic or organic acids which makes it possible to obtain a pH below 3, a zone favorable for the dissolution of aluminum.
- the other treatment conditions recommended in the patent may be retained.
- the minimum temperature value makes it possible to ensure sufficiently strong reaction kinetics.
- Working at room temperature is also possible, with an increase in the duration of the treatment.
- An alternative is to bring the F ' and K + ions through, for example, NH 5 F 2 and KCl solutions, always with acidification of the solution.
- a possible surface preparation, prior to treatment, has the sole purpose of having a clean surface. If the metal resulting from the industrial processing is not noticeably fatty, a simple thermal degreasing is sufficient; for added safety, it is possible to add, for example, an alkaline pickling soda or potash.
- solder alloy layer 4045 of thickness representing 10% of the total thickness.
- Treatment 1 (according to Patent EP 1067213):
- Treatment 3 (according to the invention):
- Treatment 4 replacement of KF with NaF, with acidification: Degreasing the surface with acetone,
- the test piece depicted in FIG. 1 was used to evaluate the ability to solder without flux of the materials having undergone these various treatments.
- the "V" consists of a bare strip of alloy 3003, in the state H24, and of thickness 0.3 mm.
- a degreasing treatment of 15 minutes at 250 ° C. is applied to the metal to be brazed. No other surface preparation is used and in particular no flux is deposited. Brazing is performed in a double-walled glass furnace that displays liquid solder movements and joint formation during processing.
- the thermal cycle consists of a temperature rise up to 600 ° C with a ramp of about 20 ° C / min, a 2 minute hold at 600 ° C, and a descent to a speed of about 30 ° C / min. The whole is carried out under continuous nitrogen sweep, with a flow rate of 8 l / min.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Treatment Of Metals (AREA)
- Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
Abstract
Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP05793591A EP1771601A1 (fr) | 2004-07-28 | 2005-07-26 | Procede de formation d ' une couche de conversion sur un produit en alliage d ' aluminium avant le procede de brasage sans flux |
DE05793591T DE05793591T1 (de) | 2004-07-28 | 2005-07-26 | Verfahren zur herstellung einer konversionsschicht auf einem aluminiumlegierungsprodukt vor dem hartlötverfahren ohne flussmittel |
US11/572,675 US7875129B2 (en) | 2004-07-28 | 2005-07-26 | Method for forming a conversion layer on an aluminum alloy product prior to fluxless brazing |
CA002575175A CA2575175A1 (fr) | 2004-07-28 | 2005-07-26 | Procede de formation d ' une couche de conversion sur un produit en alliage d ' aluminium avant le procede de brasage sans flux |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR0408312A FR2873718B1 (fr) | 2004-07-28 | 2004-07-28 | Procede de formation d'une couche de conversion sur un produit en alliage d'aluminium destine a etre brase |
FR0408312 | 2004-07-28 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2006018535A1 true WO2006018535A1 (fr) | 2006-02-23 |
Family
ID=34948243
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/FR2005/001935 WO2006018535A1 (fr) | 2004-07-28 | 2005-07-26 | Procede de formation d ' une couche de conversion sur un produit en alliage d ' aluminium avant le procede de brasage sans flux |
Country Status (6)
Country | Link |
---|---|
US (1) | US7875129B2 (fr) |
EP (1) | EP1771601A1 (fr) |
CA (1) | CA2575175A1 (fr) |
DE (1) | DE05793591T1 (fr) |
FR (1) | FR2873718B1 (fr) |
WO (1) | WO2006018535A1 (fr) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7875129B2 (en) | 2004-07-28 | 2011-01-25 | Alcan Rhenalu | Method for forming a conversion layer on an aluminum alloy product prior to fluxless brazing |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
HUE053338T2 (hu) | 2012-05-04 | 2021-06-28 | Hydro Aluminium Rolled Prod | Alumínium bevont lemez alkalmazása fluxus nélküli forrasztáshoz |
DE112016005165T5 (de) | 2015-11-10 | 2018-07-19 | Aleris Rolled Products Germany Gmbh | Flussmittelfreies Hartlötverfahren |
WO2017137236A1 (fr) | 2016-02-09 | 2017-08-17 | Aleris Rolled Products Germany Gmbh | Produit de type tôle de brasage multicouche en aluminium et procédé de brasage sans fondant |
WO2020204167A1 (fr) * | 2019-04-04 | 2020-10-08 | 株式会社Uacj | Tôle à brasage en alliage d'aluminium, et son procédé de fabrication |
Citations (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3006790A (en) * | 1958-10-20 | 1961-10-31 | Gen Motors Corp | Flux containing carboxypolymethylene |
US3779839A (en) * | 1970-07-25 | 1973-12-18 | Kobe Steel Ltd | Method of connecting aluminum or aluminum alloy members |
JPS6083771A (ja) * | 1983-10-13 | 1985-05-13 | Toyota Central Res & Dev Lab Inc | アルミニウム系材料のろう付け方法 |
JPS60102271A (ja) * | 1983-11-07 | 1985-06-06 | Toyota Central Res & Dev Lab Inc | アルミニウム系材料のろう付け方法 |
JPS60130463A (ja) * | 1983-12-16 | 1985-07-11 | Toyota Central Res & Dev Lab Inc | アルミニウム系材料のろう付け方法 |
JPS6138777A (ja) * | 1984-07-31 | 1986-02-24 | Toyota Central Res & Dev Lab Inc | アルミニウム系材料のろう付け方法 |
JPS6149770A (ja) * | 1984-08-14 | 1986-03-11 | Toyota Central Res & Dev Lab Inc | アルミニウム系材料のろう付け方法 |
EP0140267B1 (fr) * | 1983-10-13 | 1987-07-29 | Kabushiki Kaisha Toyota Chuo Kenkyusho | Procédé de brasage d'aluminium |
US5102033A (en) * | 1991-04-16 | 1992-04-07 | Kaiser Aluminum & Chemical Corporation | Method for improving the fillet-forming capability of aluminum vacuum brazing sheet products |
US5380374A (en) * | 1993-10-15 | 1995-01-10 | Circle-Prosco, Inc. | Conversion coatings for metal surfaces |
US5441580A (en) * | 1993-10-15 | 1995-08-15 | Circle-Prosco, Inc. | Hydrophilic coatings for aluminum |
JPH08144063A (ja) * | 1994-11-22 | 1996-06-04 | Matsufumi Takatani | アルミニウム系金属材料の表面処理方法 |
US5759244A (en) * | 1996-10-09 | 1998-06-02 | Natural Coating Systems, Llc | Chromate-free conversion coatings for metals |
US6316115B1 (en) * | 1999-10-21 | 2001-11-13 | Hon Hai Precision Ind. Co., Ltd. | Non-chromate chemical treatments used on magnesium alloys |
EP1154041A1 (fr) * | 2000-05-08 | 2001-11-14 | Ford Global Technologies, Inc. | Couche de conversion pour l'aluminium par pulvérisation de solutions de fluoride de potassium |
US6475301B1 (en) * | 1999-07-06 | 2002-11-05 | Visteon Global Technologies, Inc. | Conversion coatings on aluminum from KF solutions |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
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US3819424A (en) * | 1971-06-17 | 1974-06-25 | Oxy Metal Finishing Corp | Method and composition for treating metal surfaces |
JP2835724B2 (ja) * | 1988-04-05 | 1998-12-14 | 三菱アルミニウム株式会社 | アルミニウム又はアルミニウム合金材の熱処理時の酸化皮膜の成長仰制方法並びに熱処理時における酸化皮膜の成長が仰制されたアルミニウム又はアルミニウム合金材及びその製造法 |
JPH07185797A (ja) * | 1993-12-27 | 1995-07-25 | Sky Alum Co Ltd | ろう付け用アルミニウム材の製造方法、およびろう付け方法 |
FR2873718B1 (fr) | 2004-07-28 | 2007-02-02 | Pechiney Rhenalu Sa | Procede de formation d'une couche de conversion sur un produit en alliage d'aluminium destine a etre brase |
US7101469B2 (en) * | 2004-11-10 | 2006-09-05 | Atotech Deutschland Gmbh | Metal pieces and articles having improved corrosion resistance |
-
2004
- 2004-07-28 FR FR0408312A patent/FR2873718B1/fr active Active
-
2005
- 2005-07-26 CA CA002575175A patent/CA2575175A1/fr not_active Abandoned
- 2005-07-26 US US11/572,675 patent/US7875129B2/en active Active
- 2005-07-26 DE DE05793591T patent/DE05793591T1/de active Pending
- 2005-07-26 WO PCT/FR2005/001935 patent/WO2006018535A1/fr active Application Filing
- 2005-07-26 EP EP05793591A patent/EP1771601A1/fr not_active Withdrawn
Patent Citations (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3006790A (en) * | 1958-10-20 | 1961-10-31 | Gen Motors Corp | Flux containing carboxypolymethylene |
US3779839A (en) * | 1970-07-25 | 1973-12-18 | Kobe Steel Ltd | Method of connecting aluminum or aluminum alloy members |
JPS6083771A (ja) * | 1983-10-13 | 1985-05-13 | Toyota Central Res & Dev Lab Inc | アルミニウム系材料のろう付け方法 |
EP0140267B1 (fr) * | 1983-10-13 | 1987-07-29 | Kabushiki Kaisha Toyota Chuo Kenkyusho | Procédé de brasage d'aluminium |
JPS60102271A (ja) * | 1983-11-07 | 1985-06-06 | Toyota Central Res & Dev Lab Inc | アルミニウム系材料のろう付け方法 |
JPS60130463A (ja) * | 1983-12-16 | 1985-07-11 | Toyota Central Res & Dev Lab Inc | アルミニウム系材料のろう付け方法 |
JPS6138777A (ja) * | 1984-07-31 | 1986-02-24 | Toyota Central Res & Dev Lab Inc | アルミニウム系材料のろう付け方法 |
JPS6149770A (ja) * | 1984-08-14 | 1986-03-11 | Toyota Central Res & Dev Lab Inc | アルミニウム系材料のろう付け方法 |
US5102033A (en) * | 1991-04-16 | 1992-04-07 | Kaiser Aluminum & Chemical Corporation | Method for improving the fillet-forming capability of aluminum vacuum brazing sheet products |
US5380374A (en) * | 1993-10-15 | 1995-01-10 | Circle-Prosco, Inc. | Conversion coatings for metal surfaces |
US5441580A (en) * | 1993-10-15 | 1995-08-15 | Circle-Prosco, Inc. | Hydrophilic coatings for aluminum |
JPH08144063A (ja) * | 1994-11-22 | 1996-06-04 | Matsufumi Takatani | アルミニウム系金属材料の表面処理方法 |
US5759244A (en) * | 1996-10-09 | 1998-06-02 | Natural Coating Systems, Llc | Chromate-free conversion coatings for metals |
US6475301B1 (en) * | 1999-07-06 | 2002-11-05 | Visteon Global Technologies, Inc. | Conversion coatings on aluminum from KF solutions |
US6316115B1 (en) * | 1999-10-21 | 2001-11-13 | Hon Hai Precision Ind. Co., Ltd. | Non-chromate chemical treatments used on magnesium alloys |
EP1154041A1 (fr) * | 2000-05-08 | 2001-11-14 | Ford Global Technologies, Inc. | Couche de conversion pour l'aluminium par pulvérisation de solutions de fluoride de potassium |
Non-Patent Citations (7)
Title |
---|
PATENT ABSTRACTS OF JAPAN vol. 009, no. 226 (M - 412) 12 September 1985 (1985-09-12) * |
PATENT ABSTRACTS OF JAPAN vol. 009, no. 252 (M - 420) 9 October 1985 (1985-10-09) * |
PATENT ABSTRACTS OF JAPAN vol. 009, no. 290 (M - 430) 16 November 1985 (1985-11-16) * |
PATENT ABSTRACTS OF JAPAN vol. 010, no. 196 (M - 497) 10 July 1986 (1986-07-10) * |
PATENT ABSTRACTS OF JAPAN vol. 010, no. 207 (M - 500) 19 July 1986 (1986-07-19) * |
PATENT ABSTRACTS OF JAPAN vol. 1996, no. 10 31 October 1996 (1996-10-31) * |
See also references of EP1771601A1 * |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7875129B2 (en) | 2004-07-28 | 2011-01-25 | Alcan Rhenalu | Method for forming a conversion layer on an aluminum alloy product prior to fluxless brazing |
Also Published As
Publication number | Publication date |
---|---|
DE05793591T1 (de) | 2007-09-06 |
CA2575175A1 (fr) | 2006-02-23 |
US7875129B2 (en) | 2011-01-25 |
FR2873718B1 (fr) | 2007-02-02 |
EP1771601A1 (fr) | 2007-04-11 |
FR2873718A1 (fr) | 2006-02-03 |
US20070204935A1 (en) | 2007-09-06 |
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