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WO2019110781A1 - Compositions destinées au brasage d'aluminium et d'alliages d'aluminium et leur utilisation - Google Patents

Compositions destinées au brasage d'aluminium et d'alliages d'aluminium et leur utilisation Download PDF

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Publication number
WO2019110781A1
WO2019110781A1 PCT/EP2018/083930 EP2018083930W WO2019110781A1 WO 2019110781 A1 WO2019110781 A1 WO 2019110781A1 EP 2018083930 W EP2018083930 W EP 2018083930W WO 2019110781 A1 WO2019110781 A1 WO 2019110781A1
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WO
WIPO (PCT)
Prior art keywords
flux
flux composition
potassium
equal
weight
Prior art date
Application number
PCT/EP2018/083930
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English (en)
Inventor
Volmer STEFANIE
Hans-Walter Swidersky
Hynek PAWERA
Stephan GENSAC
Original Assignee
Solvay Sa
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Filing date
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Publication of WO2019110781A1 publication Critical patent/WO2019110781A1/fr

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Classifications

    • 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
    • B23K35/24—Selection of soldering or welding materials proper
    • B23K35/28—Selection of soldering or welding materials proper with the principal constituent melting at less than 950 degrees C
    • B23K35/286—Al as the principal constituent
    • 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
    • B23K1/0008—Soldering, e.g. brazing, or unsoldering specially adapted for particular articles or work
    • B23K1/0012—Brazing heat exchangers
    • 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
    • B23K1/012—Soldering with the use of hot gas
    • 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
    • B23K1/19—Soldering, e.g. brazing, or unsoldering taking account of the properties of the materials to be soldered
    • 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
    • B23K1/203—Fluxing, i.e. applying flux onto surfaces
    • 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
    • B23K35/02—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape
    • B23K35/0222—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape for use in soldering, brazing
    • B23K35/0244—Powders, particles or spheres; Preforms made therefrom
    • B23K35/025—Pastes, creams, slurries
    • 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
    • B23K35/24—Selection of soldering or welding materials proper
    • B23K35/28—Selection of soldering or welding materials proper with the principal constituent melting at less than 950 degrees C
    • 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
    • B23K35/24—Selection of soldering or welding materials proper
    • B23K35/30—Selection of soldering or welding materials proper with the principal constituent melting at less than 1550 degrees C
    • 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
    • B23K35/24—Selection of soldering or welding materials proper
    • B23K35/30—Selection of soldering or welding materials proper with the principal constituent melting at less than 1550 degrees C
    • B23K35/302—Cu as the principal constituent
    • 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
    • B23K35/34—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material comprising compounds which yield metals when heated
    • 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
    • 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
    • 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
    • B23K35/3612—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 organic compounds as principal constituents
    • 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
    • B23K35/3612—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 organic compounds as principal constituents
    • B23K35/3613—Polymers, e.g. resins
    • 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
    • B23K35/362—Selection of compositions of fluxes
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C21/00—Alloys based on aluminium
    • 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
    • B23K2101/00—Articles made by soldering, welding or cutting
    • B23K2101/04—Tubular or hollow articles
    • B23K2101/14—Heat exchangers
    • 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
    • B23K2103/02—Iron or ferrous alloys
    • B23K2103/04—Steel or steel alloys
    • 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
    • B23K2103/00—Materials to be soldered, welded or cut
    • B23K2103/08—Non-ferrous metals or alloys
    • B23K2103/12—Copper 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
    • B23K2103/00—Materials to be soldered, welded or cut
    • B23K2103/08—Non-ferrous metals or alloys
    • B23K2103/14—Titanium or alloys thereof

Definitions

  • the present invention concerns compositions comprising a flux, a metal additive, and a specific binder, aluminum or aluminum alloy parts at least partially coated with the flux composition manufactured by the process, and a brazing method.
  • Inorganic fluorides and fluoride complexes are well known to be suitable as a flux for brazing parts of aluminum and aluminum alloys to parts of aluminum and aluminum alloys, and even to parts of copper, steel and titanium.
  • potassium fluoroaluminates optionally comprising cesium and lithium fluoroaluminates. See US-A-4 670,067 and EP-A-2671670.
  • Cesium containing mixtures are especially suitable for fluxing parts of aluminum alloyed with Mg, lithium containing mixtures improve the resistance of brazed parts against corrosion.
  • Other suitable fluxes are zinc fluoride, potassium
  • the fluxes may be applied to the parts to be brazed as a wet composition which comprises the flux, a solvent and a binder and often also other additives. While the flux removes undesired oxide layers on the parts to be brazed, solder metals, solder alloys or solder alloy precursors provide a reliable joint between the parts.
  • One object of the present invention is to provide a composition useful as flux especially for brazing of parts of aluminum or of aluminum alloyed with Mg to parts of aluminum, aluminum alloy, especially Al-Mg alloy, steel, copper and titanium which provides joints protected against corrosion. It is further an object of the present invention to provide parts at least partially coated with the composition, and a brazing method using the composition of the present invention.
  • the flux composition for brazing of aluminum and aluminum alloys comprises a fluoride salt based flux; at least one metal additive selected from the group consisting of solder metal, solder alloy, Si, Ge and Cu; a binder; and a solvent wherein the solvent comprises at least one diester of formula (I) R 1 0-C(0)-(CH 2 ) X -C(0)0R 2 (I)
  • R 1 denotes Cl to C5 alkyl
  • R 2 denotes Cl to C5 alkyl
  • x is an integer 1 to 6, or a mixture of diesters of formula (I).
  • the composition may also contain minor amounts of diesters of dibasic acids with a C7 or C8 chain or diesters unsaturated dibasic acids such as maleic acid and fumaric acid.
  • the term“minor amounts” preferably denotes a total content of these C7, C8 or unsaturated diesters of equal to or lower than 5 % by weight, relative to the total weight of the composition.
  • R 1 and R 2 are the same or different and denote methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl or t-butyl.
  • x is 2, 3 or 4, including mixtures of these selected diesters.
  • Preferred diesters are dimethyl succinate, dimethyl adipate, dimethy glutarate or mixtures of the foregoing.
  • Solvent systems containing such diesters and which can preferably be used according to the present invention include Santosol®
  • the flux composition preferably comprises two or more diesters of formula
  • the flux composition comprises two or more diesters selected from the group consisting of diesters wherein x is 2, 3 or 4.
  • the solvent comprises a mixture of two or more diesters of formula (I) selected from the group consisting of diesters wherein x is 2, 3 or 4, and R 1 and R 2 are the same or different and denote methyl or ethyl.
  • the flux composition may contain minor amounts of water and/or organic liquids other than diesters.
  • the term“minor amounts” preferably denotes a range of from greater than 0 to equal to or less than 20 % by weight, preferably equal to or less than 5 % by weight, relative to the total weight of the solvent in the composition.
  • the diester of formula (I) constitutes equal to or more than 80 %- wt of the total solvent content set to 100 %-wt, still more preferably, equal to or more than 95 %-wt of the total solvent content set to 100 %-wt, and most preferred, the diesters mentioned above are the only solvent.
  • organic liquids are preferably selected from the group consisting of mono-, di- or tribasic aliphatic alcohols, especially those with 1 to 4 carbon atoms, e.g. methanol, ethanol, isopropanol, alkylene glycols, e.g. ethylene glycol, or glycol alkyl ethers, wherein alkyl preferably denotes linear C 1 to C4 alkyl or branched aliphatic C3 to C4 alkyl, including methyl, ethyl, iso-propyl, n-propyl, n-butyl, iso-butyl, sec-butyl, and tert-butyl.
  • alkyl preferably denotes linear C 1 to C4 alkyl or branched aliphatic C3 to C4 alkyl, including methyl, ethyl, iso-propyl, n-propyl, n-butyl, iso-butyl, sec-butyl
  • Non-limiting examples are glycol monoalkyl ethers, e.g. 2-methoxyethanol or diethylene glycol, or glycol dialkyl ethers, for example, dimethyl glycol (dimethoxy ethane). Mixtures comprising two or more of the liquids are also suitable.
  • Suitable fluxes are known in the art of brazing. Alkali metal fluxes of fluoroaluminates, fluorozudies, fluorosilicates and fluorostannates and combinations thereof with zinc fluoride, stannum fluoride are especially suitable.
  • the term“alkali metal” denotes here potassium and lithium.
  • solder metal or“solder ahoy” according to the present invention intends to denote a metal or alloy used to create a permanent bond between metal workpieces, and is often used for brazing processes at
  • the fluoride salt based flux in the composition of the invention is selected from the group consisting of potassium fluoroaluminate, lithium fluoroaluminate, cesium fluoroaluminate, potassium fluorozudie, potassium fluorostannate, potassium fluorosilicate, zinc fluoride, stannum fluoride, and mixtures of two or more thereof.
  • the flux is selected from the group consisting of potassium fluoroaluminate zinc fluoride or a combination of zinc fluoride and potassium fluoride, and potassium
  • the flux is potassium fluorozinese.
  • the flux composition may also contain elemental zinc, preferably in powder form.
  • potassium fluoroaluminate denotes KAlF 4 , K 2 AIF 5 ,
  • the composition comprises a potassium fluoroaluminate selected from the group consisting of KAlF 4 , K 2 AIF 5 , K 2 AIF 5 H 2 O, and mixtures thereof.
  • a potassium fluoroaluminate selected from the group consisting of KAlF 4 , K 2 AIF 5 , K 2 AIF 5 H 2 O, and mixtures thereof.
  • one or more of the other inorganic fluorides and fluoride complexes given above may additionally be comprised.
  • the content of K 3 AIF 6 in the fluoroaluminate mixture is equal to or lower than 5% by weight; preferably, the content of K 3 AlF 6 is equal to or lower than 2% by weight; and especially preferably, the content of K 3 AlF 6 is equal to or lower than 1% by weight, including 0 %.
  • composition is especially useful as flux for brazing of parts of aluminum or aluminum alloy to other parts of aluminum, of aluminum alloys, of steel, of copper or of titanium.
  • the potassium fluoroaluminate is essentially present in the form of KAlF 4 .
  • the potassium fluoroaluminate in the fluoroaluminate mixture is essentially in the form of K 2 AIF 5 , K 2 AIF 5 H 2 O, or mixtures thereof.
  • the potassium fluoroaluminate is present in the form of mixtures comprising KAIF 4 and at least one of K 2 AIF 5 and K 2 AIF 5 H 2 O.
  • the potassium fluoroaluminate is present in the form of mixtures comprising KAlF 4 and K 2 AIF 5 .
  • the flux preferably comprises KAIF 4 and at least one of K 2 AIF 5 and K 2 AIF 5 H 2 O wherein the sum of KAIF 4 and at least one of K 2 AIF 5 and K 2 AIF 5 H 2 O is set to 100 wt-%, the content of KAIF 4 is preferably equal to or greater than 70 wt-%; the content of KAIF 4 is preferably equal to or lower than 90 wt-%.
  • a cesium fluoroaluminate may be present.
  • the content of CsAlF 4 , CS 2 AIF 5 or CS 3 AIF 6 is preferably equal to or lower than 3%, more preferably equal to or lower than 2% by weight of the total fluoroaluminate content set as 100% by weight.
  • the flux comprises or consists of potassium fluorozudie.
  • the particle size is of the flux often in a range of from 0.1 pm to 100 pm. preferably, most of the particles have a particle size in a range of from 0.2 pm to 60 pm. Other solid constituents are preferably in the same particle size range or close to it. Preferred ranges for solder metal, solder alloy and/or solder alloy are given further below.
  • the flux has a particle size distribution of X50 from 1 to and including 7 pm, preferably X50 from 1 to and including 5 pm. It is advantageous if the particle size distribution of the flux has a X90 value of equal to or lower than 25 pm, preferably equal to or lower than 23 pm.
  • the respective X values as reported in the present invention are determined by laser diffraction. They can be measured, for example, in a Sympatec Helos particle size analyzer, e.g. model Helos H2068. The analysis refers to secondary particles.
  • the flux composition contains a binder.
  • binders are selected from the group consisting of organic polymers. Such polymers are physically drying (i.e., they form a solid coating after the liquid is removed), or they are chemically drying (they may form a solid coating e.g. under the influence of chemicals, e.g. oxygen or light which causes a cross linking of the molecules), or both.
  • Suitable polymers include polyolefines, e.g. butyl rubbers, polyurethanes, resins, phthalates, polyacrylates, polymethacrylates, vinyl resins, epoxy resins, and nitrocellulo se .
  • the binder is a polyacrylate ester.
  • composition of the invention may further comprise additives.
  • the composition may comprise additives which improve the brazing.
  • they may contain a solder metal, e.g. in the form of powder or small particles. This may be unnecessary if solder-plated parts are brazed.
  • the composition may additionally or instead comprise elemental Si, Ge or Cu which function as solder metal precursor as described in US-A 5,190,596. It is assumed that the precursors form Al-Si solder, Ge-Al solder or Cu-Al solder during brazing.
  • the composition may comprise Li compounds as additive as disclosed in WO2011/098120 and W02010/060869.
  • Suitable sources of Li ions as additives are, for example, LiF, Li 3 AlF 6 , LiOH, Li oxalate or Li 2 C0 3 . Flux mixtures containing Li ions often display reduced corrosion of their brazing residue.
  • the composition may also comprise alkaline earth metal compounds such as CaF 2 , CaC0 3 , MgF 2 , MgC0 3 , SrF 2 , SrC0 3 , BaF 2 , BaC0 3 , and mixtures of two or more of said second components which also provide reduced corrosion as disclosed in WO 2015/13595.
  • alkaline earth metal compounds such as CaF 2 , CaC0 3 , MgF 2 , MgC0 3 , SrF 2 , SrC0 3 , BaF 2 , BaC0 3 , and mixtures of two or more of said second components which also provide reduced corrosion as disclosed in WO 2015/13595.
  • the composition may comprise compounds, especially salts, of strontium, indium, tin, antimony, bismuth, zirconium, niobium, cerium, yttrium, titanium or lanthanum, e.g. the respective halides, nitrates, carbonates or oxides or any mixture thereof.
  • Such additives can be added during manufacture of the flux mixture or after its manufacture.
  • the respective fluorides such as TiF 4 , ZrF 4 , CeF 3 , CeF 4 , YF 3 or alkaline fluorometallates, e.g. K 2 ZrF 6 or K 2 TiF 6 , are added after manufacture as disclosed in WO 2005/092563 and WO
  • the preferred flux is potassium fluorozudie.
  • the composition may additionally contain elemental zinc, preferably in powder form.
  • the content of zinc is preferably equal to or greater than 0, more preferably, equal to or greater than 2 % by weight, and the content of zinc is preferably equal to or lower than 10 % by weight, more preferably, equal to or lower than 8 % by weight; all percentages relative to the total weight of the composition.
  • composition may also comprise additives which improve handling of the compositions.
  • the composition may comprise at least one additive selected from the group consisting of surfactants, thixotropic agents, defoaming agents, thickeners, biocides, coloring agents, antioxidants, corrosion inhibitors, and suspension stabilizers.
  • antifoaming agent e.g. silicon oil, glycerine, or preferably propylene glycol may be present.
  • a biocide for example, biocides based on 5-chloro-2- methyl-4-isothiazolin-3-one and/or 2-methyl-4-isothiazolin-3-one is suitable.
  • antioxidant e.g., BHT, butyl hydroxytoluene
  • benzotriazol may be used.
  • a suitable suspension stabilizer is for example methyl cellulose.
  • Suitable thixotropic agents are for example gelatin and pectin.
  • Suitable thickeners are, for example, waxes, hardened oil, e.g.
  • Preferred thickeners are ethylene bis-stearamide waxes. Such waxes are available, for example, from Munzing Chemie GmbH under the tradename Ceretan ®, e.g. Ceretan7006, 7008 and 7008. These are micronized waxes with low particle sizes (in the micrometer range).
  • Preferred compositions comprise a thickener, especially a wax thickener, preferably an ethylene bis stearamide wax.
  • Surfactants also known as wetting agent, if present, provide uniform coating, and compensate to some extent for surfaces not cleaned prior to application.
  • the constituents for the flux are given.
  • the percentages refer to the total weight of the composition (including solder metal, solder alloy or solder precursor, flux, solvent and any other ingredients) set as 100 % by weight.
  • the flux is contained in the composition in an amount of equal to or higher than 1 % by weight, more preferably equal to or higher than 5 % by weight.
  • it is contained in an amount of equal to or lower than 60 % by weight, more preferably equal to or lower than 50 % by weight.
  • a preferred range is thus from equal to or higher than 1 % by weight to of equal to or lower than 60 % by weight, more preferably in a range of from equal to or higher than 5 % by weight to of equal to or lower than 50 % by weight. If two or more fluxes are present, then the figures given here relate to the sum of fluxes.
  • Solder metal, solder alloy metal (such as Al-Si alloys) or solder alloy precursor (such as Si, Ge or Cu) are preferably contained in the composition in an amount of equal to or higher than 5 % by weight, more preferably equal to or higher than 5 % by weight.
  • solder metal, solder alloy metal or solder alloy precursor is contained in an amount of equal to or lower than 60 % by weight, more preferably equal to or lower than 50 % by weight.
  • a preferred range is thus from equal to or higher than 5 % by weight to of equal to or lower than 60 % by weight, more preferably in a range of from equal to or higher than 10 % by weight to of equal to or lower than 50 % by weight. If a combination of two or all three of the group consisting of solder metal, solder alloy metal and solder alloy precursor is contained, then the sum of both or all three are preferably in the amounts and the ranges given here.
  • a preferred solder material is AlSil2.
  • the solder metal, solder alloy and/or solder alloy precursor preferably has a particle size distribution of X50 from 16 to and including 25 pm, preferably X50 from 17 to and including 23 pm, and X90 ⁇ 45pm, preferably X90 from 39 to and including 55 pm, more preferably X90 from 40 to and including 51 pm.
  • the composition may also contain Li compounds, alkaline earth metal compounds organic compounds or salts of strontium, indium, tin, antimony, bismuth, zirconium, niobium, cerium, yttrium, titanium or lanthanum, e.g. the respective halides, nitrates, carbonates or oxides or any mixture thereof.
  • Such kind of additive may be present in a range of from equal to or greater than 0, preferably, equal to or greater than 1 % by weight.
  • such kind of additive is present in an amount of equal to or lower than 10 % by weight.
  • the composition is free of such additives (Li compounds, alkaline earth metal compounds organic compounds or salts of strontium etc.).
  • the binder is preferably present in an amount of equal to or higher than 2 % by weight, more preferably, equal to or higher than 5 % by weight.
  • the binder is contained in an amount of equal to or lower than 40 % by weight, more preferably equal to or lower than 25 % by weight.
  • a preferred range is thus from equal to or higher than 2 % by weight to of equal to or lower than 40% by weight, more preferably in a range of from equal to or higher than 5 % by weight to of equal to or lower than 25 % by weight. If two or more binders are present, then the figures given here relate to the sum of binders.
  • the diester is preferably present in an amount of equal to or higher than 5 % by weight, more preferably, equal to or higher than 10 % by weight, still more preferably, equal to or higher than 15 % by weight.
  • the diester is contained in an amount of equal to or lower than 60 % by weight, more preferably equal to or lower than 50 % by weight, still more preferably in an amount of equal to or lower than 40 % by weight.
  • a preferred range is thus from equal to or higher than 5 % by weight to of equal to or lower than 60 % by weight, more preferably in a range of from equal to or higher than 10 % by weight to of equal to or lower than 50 % by weight, still more preferably in a range of from equal to or higher than 15 % by weight to of equal to or lower than 40 % by weight.
  • the diester solvent is composed of two or three or even more dibasic esters, and the figures given here relate to the sum of dibasic ester compounds.
  • composition may, as mentioned above, contain additionally water and/or organic liquids other than the diester or diesters. Preferably, their amount is 0. Preferred percentages of diester solvent in case water and/or other organic liquids are present are given above. Preferably, the upper and lower limits and ranges for the diester content given above apply also for the total solvent content, i.e. the sum of diester and additionally contained water and/or other organic solvent.
  • the composition may further contain other additives, e.g. surfactants, thixotropic agents, defoaming agents, thickeners, biocides, coloring agents, antioxidants, corrosion inhibitors, and/or suspension stabilizers.
  • additives e.g. surfactants, thixotropic agents, defoaming agents, thickeners, biocides, coloring agents, antioxidants, corrosion inhibitors, and/or suspension stabilizers.
  • the amount of additive is in a range of from equal to or greater than 0 to equal to or lower than 10 % by weight, preferably equal to or lower than 5 % by weight. If two or more than 2 additives given here are contained, the figures relate to the sum of them.
  • a further aspect of the present invention concerns aluminum parts or aluminum alloy parts, coated with the composition according to the present invention.
  • These parts preferably are parts used to produce heat exchangers, e.g. tubes and fins, useful for coolers or air conditioning systems of cars or lorries, or for producing“HVAC” apparatus.
  • HVAC means heating, ventilation, air conditioning - the technology of indoor environmental comfort.
  • Another aspect of the present invention concerns assembled parts of aluminum or aluminum alloys brazed using a composition according to the present invention. These parts are, preferably, parts used in transferring heat from one medium to another medium. Preferably, these parts are used in heat exchangers or cooling systems of cars and lorries and in HVAC apparatus.
  • the parts coated with the wet composition are dried (this is of course not necessary in parts coated according to the dry method unless applies fluoroaluminate hydrates and wants to remove crystal water before starting the brazing process). Drying can be performed independently from brazing; the dried coated parts can then be stored until they are brazed. Alternatively, drying can be performed directly in the brazing apparatus or in a separate drying apparatus just before the brazing operation.
  • the weight per area of the flux is preferably equal to or higher than 3 g/m2. More preferably, it is equal to or higher than 5 g/m2. Preferably, it is equal to or lower than 40 g/m2.
  • a process for brazing of parts made from aluminum or aluminum alloys wherein the wet composition comprising is coated on at least one of the parts to be brazed, and the parts are heated to a temperature sufficiently high to braze the parts, is also an aspect of the present invention.
  • the brazing is performed in a manner well known to the expert.
  • the solder metal or solder metal precursor is contained in the composition, and thus, parts to be brazed need not be plated with solder metal.
  • At least one of the parts to be brazed is coated at least partially with the composition; the parts are then assembled and heated to fluidize first the flux mixture and then the solder metal. If the coated parts have not yet been dried as described above, solvent and other constituents with respectively low boiling point or decomposition point vaporize during the process of heating the parts to the brazing temperature.
  • the coated parts to be joined by brazing are assembled (before or after drying if coated according to a wet process) and heated to about 570°C or higher, preferably up to about 600 °C or even higher, e.g. up to
  • a preferred method for brazing of parts of aluminum, aluminum alloy, steel, copper and titanium with parts of aluminum, aluminum alloy comprises steps wherein at least one of the parts to be joined is coated at least partially with a mixture of the invention, a composition of the invention, or both, the parts to be joined are assembled, and heated to a temperature of equal to or higher than 570°C.
  • a flux composition comprising the fluoride salt based flux, solder metal, solder alloy or solder metal precursor as described above, the binder and the solvent wherein the solvent comprises or consists of the diester of formula (I) or a respective mixture of diesters.
  • a solder alloy especially based on Al and Si, is applied.
  • the advantage of the composition is that in one step, flux for oxide removal, solder metal, solder metal alloy or solder alloy precursor are applied in one step to the parts to be brazed and zinc as corrosion protecting agent is preferably included or formed from potassium fluorozudie. Another important advantage is the low flammability of the composition.
  • Example 1 Manufacture of a composition
  • Aluminum-silicon alloy powder 36.15 % by weight
  • composition was in the form of a suspension.
  • Example 2 Al brazing using the composition
  • the composition of example 1 is brushed onto uncladded aluminum 3003 coupons of 2.5 by 2.5 cm.
  • the flux load is approximately 30 gram/m 2 .
  • Two angles are assembled and brazed under typical controlled atmosphere aluminum brazing conditions (in N 2 inert gas).
  • the organic ingredients evaporate while raising the temperature, and at approximately 300 °C, binder, solvent, thixotropic agent and wax are burnt off without any residue.
  • the temperature is further raised to 600 °C to form a brazed joint of the angles. After cooling, the formed joints are inspected and found to be satisfactory.

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
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Abstract

L'invention concerne des compositions destinées au brasage d'aluminium et d'alliages d'aluminium et leur utilisation. Les compositions comprennent un flux à base de sel de fluorure ; un métal de brasure, un alliage de brasure ou un précurseur d'alliage de brasure ; un liant ; et un diester en tant que solvant.
PCT/EP2018/083930 2017-12-08 2018-12-07 Compositions destinées au brasage d'aluminium et d'alliages d'aluminium et leur utilisation WO2019110781A1 (fr)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113146039A (zh) * 2021-04-28 2021-07-23 南昌大学 镁合金钢激光焊接的中间层复合粉末的制备及其焊接方法
DE102020000717A1 (de) 2020-02-04 2021-08-05 Firinit GmbH Pastöse Zusammensetzung zum Aluminiumlöten
WO2023200669A1 (fr) * 2022-04-11 2023-10-19 Honeywell International Inc. Flux micronisé pour distributeur de valve à jet

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US4670067A (en) 1985-04-09 1987-06-02 Kabushiki Kaisha Toyota Chuo Kenkyusho Brazing flux
US5190596A (en) 1991-01-25 1993-03-02 Alcan International Limited Method of brazing metal surfaces
DE19983067T1 (de) * 1998-06-10 2001-05-17 Showa Denko Kk Lötmittelpulver, Flussmittel, Lötmittelpaste, Lötmethode, gelötete Leiterplatte und Lotverbindungsprodukt
US20030102359A1 (en) * 2000-03-30 2003-06-05 Solvay Fluor Und Derivate Gmbh Fluorostannate-containing brazing or soldering fluxes and use thereof in brazing or soldering aluminum or aluminum alloys
WO2005092563A2 (fr) 2004-03-20 2005-10-06 Solvay Fluor Gmbh Substances auxiliaires non corrosives pour soudure a l'aluminium
WO2007131993A1 (fr) 2006-05-15 2007-11-22 Solvay Fluor Gmbh Flux pour brasage d'aluminium
EP2135705A1 (fr) * 2008-06-20 2009-12-23 Solvay Fluor GmbH Fluorozincate de potassium fluidisable
WO2010060869A1 (fr) 2008-11-25 2010-06-03 Solvay Fluor Gmbh Flux anticorrosif
EP1272429B1 (fr) * 2000-04-03 2010-06-16 Solvay Fluor GmbH Fluorozincates de metaux alcalins et leur fabrication
WO2011098120A1 (fr) 2010-02-10 2011-08-18 Solvay Fluor Gmbh Flux formant un résidu de brasage insoluble
US8075706B2 (en) 2007-12-21 2011-12-13 Harima Chemicals, Inc. Paste composition for aluminum brazing
EP2671670A1 (fr) 2012-06-06 2013-12-11 Solvay Sa Dispositif amélioré pour l'élimination de rognures des rouleaux ou rondins de matériau en forme de ruban
WO2015013595A2 (fr) 2013-07-25 2015-01-29 Imvision Software Technologies Ltd. Procédé et appareil permettant la transmission efficace de flux over the top non gérés sur des réseaux de communication cellulaires
US20150364615A1 (en) * 2014-06-12 2015-12-17 E I Du Pont De Nemours And Company Aluminum-tin paste and its use in manufacturing solderable electrical conductors
JP2016002584A (ja) * 2014-06-19 2016-01-12 株式会社タムラ製作所 はんだ付け用フラックス組成物、それを用いた太陽電池モジュールおよび電子基板

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4670067A (en) 1985-04-09 1987-06-02 Kabushiki Kaisha Toyota Chuo Kenkyusho Brazing flux
US5190596A (en) 1991-01-25 1993-03-02 Alcan International Limited Method of brazing metal surfaces
DE19983067T1 (de) * 1998-06-10 2001-05-17 Showa Denko Kk Lötmittelpulver, Flussmittel, Lötmittelpaste, Lötmethode, gelötete Leiterplatte und Lotverbindungsprodukt
US20030102359A1 (en) * 2000-03-30 2003-06-05 Solvay Fluor Und Derivate Gmbh Fluorostannate-containing brazing or soldering fluxes and use thereof in brazing or soldering aluminum or aluminum alloys
EP1272429B1 (fr) * 2000-04-03 2010-06-16 Solvay Fluor GmbH Fluorozincates de metaux alcalins et leur fabrication
WO2005092563A2 (fr) 2004-03-20 2005-10-06 Solvay Fluor Gmbh Substances auxiliaires non corrosives pour soudure a l'aluminium
WO2007131993A1 (fr) 2006-05-15 2007-11-22 Solvay Fluor Gmbh Flux pour brasage d'aluminium
US8075706B2 (en) 2007-12-21 2011-12-13 Harima Chemicals, Inc. Paste composition for aluminum brazing
EP2135705A1 (fr) * 2008-06-20 2009-12-23 Solvay Fluor GmbH Fluorozincate de potassium fluidisable
WO2010060869A1 (fr) 2008-11-25 2010-06-03 Solvay Fluor Gmbh Flux anticorrosif
WO2011098120A1 (fr) 2010-02-10 2011-08-18 Solvay Fluor Gmbh Flux formant un résidu de brasage insoluble
EP2671670A1 (fr) 2012-06-06 2013-12-11 Solvay Sa Dispositif amélioré pour l'élimination de rognures des rouleaux ou rondins de matériau en forme de ruban
WO2015013595A2 (fr) 2013-07-25 2015-01-29 Imvision Software Technologies Ltd. Procédé et appareil permettant la transmission efficace de flux over the top non gérés sur des réseaux de communication cellulaires
US20150364615A1 (en) * 2014-06-12 2015-12-17 E I Du Pont De Nemours And Company Aluminum-tin paste and its use in manufacturing solderable electrical conductors
JP2016002584A (ja) * 2014-06-19 2016-01-12 株式会社タムラ製作所 はんだ付け用フラックス組成物、それを用いた太陽電池モジュールおよび電子基板

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102020000717A1 (de) 2020-02-04 2021-08-05 Firinit GmbH Pastöse Zusammensetzung zum Aluminiumlöten
CN113146039A (zh) * 2021-04-28 2021-07-23 南昌大学 镁合金钢激光焊接的中间层复合粉末的制备及其焊接方法
WO2023200669A1 (fr) * 2022-04-11 2023-10-19 Honeywell International Inc. Flux micronisé pour distributeur de valve à jet

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