WO2003089176A2 - Flux coated brazing sheet - Google Patents

Flux coated brazing sheet Download PDF

Info

Publication number
WO2003089176A2
WO2003089176A2 PCT/US2003/012239 US0312239W WO03089176A2 WO 2003089176 A2 WO2003089176 A2 WO 2003089176A2 US 0312239 W US0312239 W US 0312239W WO 03089176 A2 WO03089176 A2 WO 03089176A2
Authority
WO
WIPO (PCT)
Prior art keywords
brazing
mixture
flux
brazing flux
aluminum
Prior art date
Application number
PCT/US2003/012239
Other languages
French (fr)
Other versions
WO2003089176A3 (en
Inventor
Darwin H. Scott
Raymond J. Kilmer
Joseph R. Dougherty
Robert P. Anthony
Original Assignee
Alcoa Inc.
American Inks And Coatings Corporation
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 Alcoa Inc., American Inks And Coatings Corporation filed Critical Alcoa Inc.
Priority to EP03728450.2A priority Critical patent/EP1497068B8/en
Priority to BRPI0309577-0B1A priority patent/BR0309577B1/en
Priority to CN038118939A priority patent/CN1655903B/en
Priority to KR1020047016761A priority patent/KR101076660B1/en
Priority to JP2003585916A priority patent/JP2005523163A/en
Priority to AU2003234143A priority patent/AU2003234143A1/en
Priority to CA002482867A priority patent/CA2482867C/en
Publication of WO2003089176A2 publication Critical patent/WO2003089176A2/en
Publication of WO2003089176A3 publication Critical patent/WO2003089176A3/en

Links

Classifications

    • BPERFORMING OPERATIONS; TRANSPORTING
    • B23MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23KSOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/22Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
    • B23K35/36Selection 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
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00Layered products comprising a layer of metal
    • B32B15/04Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B23MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23KSOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/02Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape
    • B23K35/0222Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape for use in soldering, brazing
    • B23K35/0233Sheets, foils
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B23MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23KSOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/22Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
    • B23K35/36Selection 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
    • B23K35/3601Selection 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
    • B23K35/3603Halide salts
    • B23K35/3605Fluorides
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B9/00Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B23MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23KSOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/02Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape
    • B23K35/0222Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape for use in soldering, brazing
    • B23K35/0233Sheets, foils
    • B23K35/0238Sheets, foils layered
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B23MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23KSOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/22Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
    • B23K35/24Selection of soldering or welding materials proper
    • B23K35/28Selection of soldering or welding materials proper with the principal constituent melting at less than 950 degrees C
    • B23K35/286Al as the principal constituent
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B23MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23KSOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/22Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
    • B23K35/36Selection 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
    • B23K35/3612Selection 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
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B23MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23KSOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/22Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
    • B23K35/36Selection 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
    • B23K35/3612Selection 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
    • B23K35/3613Polymers, e.g. resins
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B23MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23KSOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/22Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
    • B23K35/36Selection 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
    • B23K35/365Selection of non-metallic compositions of coating materials either alone or conjoint with selection of soldering or welding materials

Definitions

  • the present invention relates to joining together two or more metal objects by brazing. More particularly, the present invention relates to a brazing flux mixture and a method for preparing and using said brazing flux coating mixture to make brazing sheets.
  • Aluminum alloys are used in the construction of heat exchangers, such as evaporators, radiators, heaters and condensers and the like, due to their light weight and excellent heat transfer properties.
  • Heat exchangers are typically manufactured from aluminum alloy parts that are formed from rolled sheet or extruded products. The parts are typically assembled, fixtured, cleaned and joined in a brazing process. In a brazing process, two or more parts, each clad with an aluminum brazing alloy (e.g., an aluminum-silicon alloy), are positioned so that surfaces to be joined on the parts are in close proximity to each other. The parts are heated to a temperature which melts the braze alloy but not the core alloy on underlying parts.
  • an aluminum brazing alloy e.g., an aluminum-silicon alloy
  • the braze alloy from each part melts together to close the gap which separates the parts. Upon cooling, the brazing alloy solidifies and forms a metallurgical bond between the parts.
  • the brazing alloy is typically introduced onto the surfaces of the aluminum stock by cladding thereto in a roll bonding operation.
  • a common brazing practice includes cleaning of the formed parts using a suitable solvent to remove oils and the like from the surfaces to be brazed followed by application of a suitable flux to the pre-brazed parts to be joined.
  • the fluxed parts are heated in a controlled atmosphere, such as dry nitrogen, to retard oxidation. Flux is used to reduce the oxides on the faying surfaces of the parts that are to be joined by brazing.
  • flux is applied after fabrication of the individual parts to be brazed, either after assembly and fixturing of the parts (e.g., as a radiator, condenser, or heater) or prior to assembly for heat exchangers having internal brazed joints (e.g., evaporators) and prior to brazing.
  • the flux may be applied directly as a dry powder or mixed with a carrier such as water or alcohol and applied as slurry over the entire work piece. When applied as slurry, the carrier is subsequently removed by a drying step, leaving the flux as a powder on the surface of the parts to be brazed.
  • Flux is only required in areas where metallurgical bonds or joints are required. Nevertheless, it is common manufacturing practice to apply flux over the entire assembly, often including the fixtures used to contain the parts in the furnace during brazing. This results in overuse and waste of flux, the need to clean the fixtures and increased maintenance of the furnace due to the corrosive nature of the flux. Moreover, the process of applying and removing excess flux is time consuming and expensive. It should be noted that flux is often loosely adhered to the parts as a powder. Hence, care must be taken to avoid removal of the flux during any handling of the fluxed parts prior to brazing.
  • An alternative to fluxing an entire assembly of parts is to apply flux to the metal sheets prior to working or forming the sheets into parts. Applying flux to a metal sheet prior to forming the sheet into a desired part is advantageous in that the flux can be applied only on the braze alloy cladding where joints are to be formed between parts. The unclad areas of the metal, which are not to be joined, can remain free of flux.
  • flux coated brazing sheet has not found broad commercial applications due to the rigorous demands on the flux coating. The flux on prefluxed sheet must survive stamping and forming operations, not degrade when exposed to the forming lubricants and not interfere with the brazing operation.
  • brazing flux mixture which can be applied over an entire aluminum alloy brazing sheet or can be applied on the brazing sheet only where metallurgical bonds or joints are required, that is sufficiently durable to withstand processing operations such as stamping, forming, and handling prior to brazing and also provides good metallurgical bonds upon brazing.
  • brazing flux mixture which can be applied over an entire aluminum alloy brazing sheet, or can be applied on the brazing alloy only where metallurgical bonds or joints are required, that is sufficiently durable to withstand processing operations and also provides good metallurgical bonds upon brazing.
  • the invention provides a brazing flux mixture for coating an unformed brazing sheet prior to sheet formation into a shaped product.
  • the mixture is comprised of brazing flux, a polyvinyl butyral resin binder, and an organic solvent.
  • the invention further provides a method of making a brazing flux mixture comprising combining a brazing flux with a polyvinyl butyral binder to form a first mixture; shearing said first mixture to form a second mixture having uniformly dispersed brazing flux in said binder, and combining said second mixture with a organic solvent to form a brazing flux mixture.
  • the invention also provides a method of making a flux-coated aluminum brazing sheet comprising:
  • Fig. 1 is a graph of the weight percent of polyvinyl butyral binder on a coated alloy versus heating. Detailed Description of Preferred Embodiments
  • the present invention provides a brazing flux mixture which can be applied over an entire aluminum alloy brazing sheet or can be applied on a brazing sheet only where metal joints or bonds are needed.
  • the brazing flux mixture is sufficiently durable to survive manufacturing operations such as forming and stamping of parts from the aluminum alloy brazing sheet, and provides acceptable metallurgical brazing bonds.
  • the brazing flux mixture is comprised of brazing flux, a polyvinyl butyral resin binder and an organic solvent.
  • the brazing flux can be any flux material suitable for joining two or more aluminum alloy objects together by brazing.
  • the preferred brazing flux is comprised of potassium fluoroaluminate Such preferred fluxes are available commercially from Solvay Fluor und Derivate GmbH under the trademark NOCOLOK ® flux.
  • Suitable brazing fluxes may also include elements such as chlorides, cesium (Cs 0. o 2 1 - 2 AlF - 5 ) to provide increased tolerance to magnesium in the base metal, zinc (KZnF 3 ) to provide for corrosion resistance, or silicon (K ⁇ - 3 AlF 4 - 6 plus silicon powder) to promote brazing joint formation.
  • the polyvinyl butyral resin binder of this invention is a reaction product of polyvinyl alcohol and butyraldehyde.
  • Preferred polyvinyl butyral resin binders are binders having about 10 to 21 wt.% vinyl alcohol content, about 1 to 2 wt.% vinyl acetal content, and having a viscosity at 10% TNV in 95% ethyl alcohol in the range of 15 to 2500 centipoise at 25°C (77°F).
  • Preferred binders are available commercially, such as PIOLOFORM ® BN18 resins from Wacker Polymer Systems GmbH & Company KG, Sekisui S-Lec BM5Z available from Synthetic Specialties Company, Middleton, New Jersey, and Butvar B-75 Resins from Solutia.
  • the organic solvent used for this invention can be any organic solvent which facilitates uniform mixing of the brazing flux and polyvinyl butyral resin binder.
  • Esters such as ethyl acetate, n-butyl acetate, n-propyl acetate and ketones, such as acetone and cyclohexanone can be used as solvents.
  • Blends of alcohols and aromatic hydrocarbons such as toluene are suitable solvents despite the fact that aromatic hydrocarbons are not individually active solvents for polyvinyl butyral resins.
  • the preferred solvents for this invention are alcohols, such as ethyl alcohol, isopropyl alcohol, n-butanol, n-propyl alcohol and diacetone alcohol.
  • Glycol ethers and glycol ether acetates such as dipropylene glycol monomethyl ether and propylene glycol methyl ether acetate are also preferred as solvents for this invention.
  • the most preferred solvents are mixtures of either propylene glycol methyl ether acetate, isopropyl alcohol and ethyl acetate, or dipropylene monomethyl glycol ether, isopropyl alcohol and ethyl acetate.
  • the brazing flux mixture is prepared by combining a brazing flux with a polyvinyl butyral binder and then mixing the combined flux and binder with an organic solvent.
  • the preferred method for combining flux and binder is to subject the flux and binder to shearing. Any shearing method known to the skilled artisan may be applied such as high-speed mixers, media mills or 2-roll mills.
  • the preferred shearing method is to combine the brazing flux and polyvinyl butyral binder in a 2-roll mill.
  • a two-roll mill comprises two cylindrical rolls that rotate at different speeds and in opposite directions in relation to each other. Shearing occurs as the flux and binder blend is passed between the rolls.
  • an organic solvent such as an alcohol, an acetate, a glycol ether, or mixtures thereof, as previously described herein, may be added to the flux-binder combination prior to or during shearing.
  • the most preferred solvent for shearing is isopropyl alcohol.
  • the amount of binder suitable for this invention is an amount sufficient to maintain adherence of the flux to a surface of an object to be brazed, during handling, forming and stamping operations, yet does not interfere with the formation of brazing joints.
  • the flux-binder combination subjected to shearing contains from about 5 to 30 wt.% binder, from about 70 to 95 wt.% flux, and optionally up to about 10 wt.% organic solvent to equal a total of 100 wt.%.
  • the most preferred flux-binder combination subjected to shearing contains from about 5 to 15 wt.% binder, and from about 85 to 95 wt.% flux, and optionally up to about 10 wt.% organic solvent to equal a total of 100 wt.%.
  • the shearing operation uniformly distributes the flux in the binder and helps provide uniform flux particle size within the mixture.
  • the inventors believe that the flux particle sizes of this invention provide for a flux coating which can be uniformly applied to an object to be brazed and facilitate adhesion of the dry flux onto the metal object.
  • the flux particle size will vary depending on the amount of shearing applied to the mixture, mixture viscosity and the composition of the mixture the inventors believe that the preferred particle size is about 1 micron or smaller.
  • the flux-binder combination is then dissolved in a polar organic solvent or a mixture of polar organic solvents to form a mixture suitable for coating an aluminum alloy brazing sheet or part to be brazed.
  • the amount of solvent in the invention mixture is an amount sufficient to evenly distribute the flux and binder onto a metal substrate.
  • the preferred amount of solvent is from about 10 to 70 wt.% solvent and from 30 to 90 wt.% flux-binder combination.
  • the most preferred amount of solvent in the mixture is from about 30 to 60 wt.% solvent and from 40 to 70 wt.% flux-binder combination.
  • the most preferred brazing mixtures of this invention are comprised of about 62 wt.% potassium fluoroaluminate flux, about 6.9 wt.% polyvinyl butyral resin binder, about 27.5 wt.% propylene glycol methyl ether acetate of dipropylene monomethyl ether, about 2.3 wt.% isopropyl alcohol, and about 1.3 wt.% ethyl acetate.
  • the solvent based mixture provides for good surface wetting on the aluminum brazing sheet, yet depending on the aluminum product to be coated, it may still be desirable to clean the brazing sheet prior to application of a coating of the invention brazing flux mixture.
  • cleaning may improve adhesion of the invention mixture.
  • cleaning solutions include organic solvents and aqueous cleaners.
  • the invention brazing flux mixture can be applied to an aluminum alloy brazing sheet by conventional rolling coating processes, by immersion processes, by spray processes, by manual coating such as by brushing or the like.
  • the sheet may be fully coated or partially coated in a pattern on one or both sides.
  • the sheet may be heated to drive off the solvent component of the invention mixture and to facilitate drying.
  • the amount of dry flux remaining on the surface of the sheet is in the range of about 2 to 40 grams of flux per square meter of brazing sheet (g/m ).
  • the flux loading is from about 3 g/m to about 10 g/m .
  • a suitable color pigment can be added to the coating formulation to produce a colored coating.
  • Suitable pigments include Pigment Blue 15 Phthalo Blue, Thalocyanine Blue 15:4, Pigment Red 52 B in Red, Bon Red 52, Pigment Green 7 Phthalo Green, and Thalocyanine Green 7.
  • any aluminum alloy brazing sheet may be used with the flux coating of this invention.
  • the aluminum brazing sheet preferably comprises a 3XXX, 5XXX, or 6XXX aluminum core alloy clad on at least one side with a 4XXX series brazing alloy.
  • the inventors also believe the flux coating of this invention can be used on unclad aluminum alloy sheet and extrusions.
  • a coating, C31 was prepared by combining 10 wt.% of polyvinyl butyral with 90 wt.% of NOCOLOK ® potassium fluoroaluminate flux and subjecting the mixture to a high shear dispersion process using a two-roll mill. Next, 68.9 wt.% of the highly dispersed mixture of polyvinyl butyral and NOCOLOK ® flux was combined and mixed with 31.1 wt.% of dipropylene glycol mono methyl ether. [0031] The coating was uniformly applied to both sides of aluminum brazing sheet samples by making drawdowns with a #6, #7, #8 or a #9 Meyer rod.
  • the aluminum brazing sheet was of the type commercially used in the production of automotive heat exchangers (e.g., evaporators) and had a 3XXX aluminum core alloy containing about 1% manganese, 0.3% copper and 0.15% titanium.
  • the 4XXX aluminum braze alloy clad on each side of the core comprised about 10% of the total sheet thickness and contained about 10% silicon.
  • the aluminum sheet was about 0.017 inches thick and had been fully annealed to an -O temper.
  • the coating was dried by placing the sheet into a 500°F furnace for a period of 15 seconds to evaporate the solvent.
  • dry coating weights on each side of the aluminum brazing sheet samples varied from about 5 to 11 grams/meter and the dry coating thicknesses varied from about 0.0002 to 0.0006 inch.
  • mini evaporator plates patterned after actual production evaporator plates were stamped from the coated sheet on a five-stage progressive die using a commercially available lubricant, Draw Lube 485 from Circle-Prosco Inc., Bloomington, Indiana. The stamped plates were rubbed with a finger, visually examined for coating loss and rated as follows.
  • Mini evaporators were prepared for the brazing tests by alternately stacking plates stamped from the coated sheet and non-coated 3003 alloy fins in suitable fixture to hold the parts in place. The fixtured parts were then placed in a furnace and brazed by heating to about 600°C in a suitable nitrogen gas atmosphere.
  • the brazeability evaluation criteria were as follows. Acceptable: The braze joint is a well-formed fillet and there is very little or no black carbon residue on the surface.
  • the braze joint is small and incomplete or there is a significant amount of black residue on the surface.
  • Example 2 Weight loss tests were conducted to assess the compatibility of the coating and two commercial forming lubricants. Weighed 2.5 inch x 5 inch samples of sheet coated by using a # 9 Meyer rod were immersed in beakers containing two commercial forming lubricants, Circle-Prosco Inc. Draw Lube 485 and Calvary Industries Inc. CAL Lube 180-M+, at room temperature. After five days, the samples were removed from the lubricants, thermally degreased by heating to about 450°F, and reweighed. The very small differences in initial and final weights shown below indicated that the coating was compatible with the two forming lubricants.
  • Example 3 Thermal gravimetric analyses were conducted on dried samples of the coating. Coating samples were continuously weighed while being heated at 10°C/min from room temperature to about 600°C in both air and nitrogen. Test results shown in Figure 1 indicated that volatilization of the polyvinyl butyral binder was about complete by the time the coating sample reached 500°C.
  • Example 4 Binders other than polyvinyl butyral were investigated. Samples containing both RS and SS types of nitrocellulose including viscosity grades 10 to 15 centipoise and 60 to 80 seconds were tested. In an attempt to improve coating adhesion and scratch resistance, modifiers that were copolymers of butyl acrylate and vinyl isobutyl ether, butyl benzyl phthalate and dioctyl adipate were added to the nitrocellulose in the range of 1 to 100 wt.%. The experimental binders were combined with NOCOLOK ® potassium fluoroaluminate flux in varying proportions to produce the 31 coatings described in Table 3.
  • the flux-binder mixtures were subjected to processing on several different types of dispersion equipment, including a Cowles high-speed mixer, a steel shot media mill and a 2-roll shearing mill. Subsequently the flux-binder mixtures were combined with various solvents including isopropyl acetate, ethyl acetate, butyl acetate, methoxypropanol acetate, dipropylene monomethyl glycol ether, isopropyl alcohol and ethyl alcohol. Polyvinyl pyrolidone was added to some of the coating formulations as a suspending agent to reduce flux drop out. Polyethylene was added to some coating formulations to improve coating lubricity.
  • the coatings were uniformly applied to aluminum brazing sheet samples by making draw downs with different Meyer rods varying from a #3 up to a #22.
  • the aluminum brazing sheet was of the type commercially used in the production of automotive heat exchangers (e.g., evaporators) and had a 3XXX aluminum core alloy containing about 1% manganese, 0.3% copper and 0.15% titanium.
  • the 4XXX aluminum braze alloy clad on each side of the core comprised about 10% of the total sheet thickness and contained about 10% silicon.
  • the aluminum sheet was about 0.017 inches thick and had been fully annealed to an - O temper.
  • the coatings were dried by placing the sheets into a 500°F furnace for a period of 15 seconds to evaporate the solvent. Depending upon which Meyer rod was used to make the draw down, dry coating weights on the aluminum brazing sheet samples varied from about 5 to 35 grams/meter 2 and the dry coating thicknesses varied from about 0.0002 to 0.0012 inches.
  • the scratch resistance of the coating was subjectively evaluated by scratching the coated sheet with a fingernail. The sheet was rated as being either acceptable or not acceptable.
  • Brazeability of the sheet was evaluated by brazing standard "T joints" specimens or by brazing mini evaporators produced by alternately stacking plates stamped from the coated sheet and non-coated 3003 alloy fins.
  • the test specimens were placed in a furnace and brazed by heating to about 600°C in a suitable nitrogen gas atmosphere.
  • the brazeability evaluation criteria were as follows. Acceptable: The braze joint is a well-formed fillet and there is very little or no black carbon residue on the surface.
  • the braze joint is small and incomplete or there is a significant amount of black residue on the surface.
  • Table 3 clearly shows that only a brazing flux coating mixture, comprising brazing flux, a polyvinyl butyral binder and an organic solvent provide a flux-binder coating on a metal object which is both sufficiently durable to maintain adherence on a metal object during stamping and forming and also provides a suitable brazing joint.
  • Coatings were formulated to evaluate the effects of polyvinyl butyral viscosity and flux/binder ratio on coating performance.
  • Ten coatings, described in Table 4, were prepared by combining samples of commercially available polyvinyl butyral of different viscosities with NOCOLOK ® potassium fluoroaluminate flux in varying proportions and subjecting the mixtures to a high shear dispersion process using a 2-roll mill. Subsequently, the highly dispersed mixtures of polyvinyl butyral and NOCOLOK ® flux were combined and mixed with varying amounts of dipropylene glycol mono methyl ether.
  • the coatings were uniformly applied to both sides of aluminum brazing sheet samples by making draw downs with a #6, #7, #9 or a #12 Meyer rod.
  • the aluminum brazing sheet was of the type commercially used in the production of automotive heat exchangers (e.g., evaporators) and had a 3XXX aluminum core alloy containing about 1% manganese, 0.3% copper and 0.15% titanium.
  • the 4XXX aluminum braze alloy clad on each side of the core comprised about 10% of the total sheet thickness and contained about 10% silicon.
  • the aluminum sheet was about 0.017 inches thick and had been fully annealed to an -O temper.
  • the coatings were dried by placing the sheet into a 500°F furnace for a period of 15 seconds to evaporate the solvent.
  • flux coating weights on each side of the aluminum brazing sheet samples varied from about 3.7 to 10.7 grams/meter 2 .
  • Mini evaporators were prepared for the brazing tests by alternately stacking plates stamped from the coated sheet and non-coated 3003 alloy fins in suitable fixture to hold the parts in place. The fixtured parts were then placed in a furnace and brazed by heating to about 600°C in a suitable nitrogen gas atmosphere.
  • the brazeability evaluation criteria were as follows.
  • the braze joint is a well-formed fillet and there is very little or no black carbon residue on the surface.
  • the braze joint is small and incomplete or there is a significant amount of black residue on the surface.

Abstract

A brazing flux mixture comprised of brazing flux, a polyvinyl butyral resin binder, and an organic solvent which can be applied over an entire aluminum alloy brazing sheet, or can be applied on the brazing sheet only where metallurgical bonds or joints are required, that is sufficiently durable to withstand processing operations and also provides good metallurgical bonds upon brazing.

Description

FLUX COATED BRAZING SHEET
Field of the Invention
[0001] The present invention relates to joining together two or more metal objects by brazing. More particularly, the present invention relates to a brazing flux mixture and a method for preparing and using said brazing flux coating mixture to make brazing sheets.
Background of the Invention
[0002] Aluminum alloys are used in the construction of heat exchangers, such as evaporators, radiators, heaters and condensers and the like, due to their light weight and excellent heat transfer properties. Heat exchangers are typically manufactured from aluminum alloy parts that are formed from rolled sheet or extruded products. The parts are typically assembled, fixtured, cleaned and joined in a brazing process. In a brazing process, two or more parts, each clad with an aluminum brazing alloy (e.g., an aluminum-silicon alloy), are positioned so that surfaces to be joined on the parts are in close proximity to each other. The parts are heated to a temperature which melts the braze alloy but not the core alloy on underlying parts. The braze alloy from each part melts together to close the gap which separates the parts. Upon cooling, the brazing alloy solidifies and forms a metallurgical bond between the parts. The brazing alloy is typically introduced onto the surfaces of the aluminum stock by cladding thereto in a roll bonding operation.
[0003] A common brazing practice includes cleaning of the formed parts using a suitable solvent to remove oils and the like from the surfaces to be brazed followed by application of a suitable flux to the pre-brazed parts to be joined. The fluxed parts are heated in a controlled atmosphere, such as dry nitrogen, to retard oxidation. Flux is used to reduce the oxides on the faying surfaces of the parts that are to be joined by brazing.
[0004] In most commercial brazing operations, flux is applied after fabrication of the individual parts to be brazed, either after assembly and fixturing of the parts (e.g., as a radiator, condenser, or heater) or prior to assembly for heat exchangers having internal brazed joints (e.g., evaporators) and prior to brazing. The flux may be applied directly as a dry powder or mixed with a carrier such as water or alcohol and applied as slurry over the entire work piece. When applied as slurry, the carrier is subsequently removed by a drying step, leaving the flux as a powder on the surface of the parts to be brazed.
[0005] Flux is only required in areas where metallurgical bonds or joints are required. Nevertheless, it is common manufacturing practice to apply flux over the entire assembly, often including the fixtures used to contain the parts in the furnace during brazing. This results in overuse and waste of flux, the need to clean the fixtures and increased maintenance of the furnace due to the corrosive nature of the flux. Moreover, the process of applying and removing excess flux is time consuming and expensive. It should be noted that flux is often loosely adhered to the parts as a powder. Hence, care must be taken to avoid removal of the flux during any handling of the fluxed parts prior to brazing.
[0006] An alternative to fluxing an entire assembly of parts is to apply flux to the metal sheets prior to working or forming the sheets into parts. Applying flux to a metal sheet prior to forming the sheet into a desired part is advantageous in that the flux can be applied only on the braze alloy cladding where joints are to be formed between parts. The unclad areas of the metal, which are not to be joined, can remain free of flux. However, flux coated brazing sheet has not found broad commercial applications due to the rigorous demands on the flux coating. The flux on prefluxed sheet must survive stamping and forming operations, not degrade when exposed to the forming lubricants and not interfere with the brazing operation.
[0007] Thus, a need exists for a brazing flux mixture which can be applied over an entire aluminum alloy brazing sheet or can be applied on the brazing sheet only where metallurgical bonds or joints are required, that is sufficiently durable to withstand processing operations such as stamping, forming, and handling prior to brazing and also provides good metallurgical bonds upon brazing.
[0008] It is therefore an object of this invention to provide a brazing flux mixture which can be applied over an entire aluminum alloy brazing sheet, or can be applied on the brazing alloy only where metallurgical bonds or joints are required, that is sufficiently durable to withstand processing operations and also provides good metallurgical bonds upon brazing.
[0009] Additional objectives and advantages of our invention will become apparent to persons skilled in the art from the following detailed description of some particularly preferred embodiments.
Summary of the Invention
[0010] The invention provides a brazing flux mixture for coating an unformed brazing sheet prior to sheet formation into a shaped product. The mixture is comprised of brazing flux, a polyvinyl butyral resin binder, and an organic solvent.
[0011] The invention further provides a method of making a brazing flux mixture comprising combining a brazing flux with a polyvinyl butyral binder to form a first mixture; shearing said first mixture to form a second mixture having uniformly dispersed brazing flux in said binder, and combining said second mixture with a organic solvent to form a brazing flux mixture.
The invention also provides a method of making a flux-coated aluminum brazing sheet comprising:
(a) combining a brazing flux with polyvinyl butyral binder and optionally an organic solvent to form a first mixture;
(b) shearing said first mixture to form a second mixture having uniformly dispersed brazing flux particles in said second mixture;
(c) combining said second mixture with an organic solvent to form a brazing flux mixture;
(d) coating at least a portion of the surface of an aluminum brazing sheet with said brazing flux mixture; and
(e) drying said brazing flux mixture on said aluminum brazing sheet surface.
Brief Description of the Drawing [0012] Fig. 1 is a graph of the weight percent of polyvinyl butyral binder on a coated alloy versus heating. Detailed Description of Preferred Embodiments
[0013] The present invention provides a brazing flux mixture which can be applied over an entire aluminum alloy brazing sheet or can be applied on a brazing sheet only where metal joints or bonds are needed. The brazing flux mixture is sufficiently durable to survive manufacturing operations such as forming and stamping of parts from the aluminum alloy brazing sheet, and provides acceptable metallurgical brazing bonds.
[0014] The brazing flux mixture is comprised of brazing flux, a polyvinyl butyral resin binder and an organic solvent.
[0015] The brazing flux can be any flux material suitable for joining two or more aluminum alloy objects together by brazing. The preferred brazing flux is comprised of potassium fluoroaluminate
Figure imgf000006_0001
Such preferred fluxes are available commercially from Solvay Fluor und Derivate GmbH under the trademark NOCOLOK® flux. Suitable brazing fluxes may also include elements such as chlorides, cesium (Cs0.o2 1-2AlF -5) to provide increased tolerance to magnesium in the base metal, zinc (KZnF3) to provide for corrosion resistance, or silicon (Kι-3AlF4-6 plus silicon powder) to promote brazing joint formation.
[0016] The polyvinyl butyral resin binder of this invention is a reaction product of polyvinyl alcohol and butyraldehyde. Preferred polyvinyl butyral resin binders are binders having about 10 to 21 wt.% vinyl alcohol content, about 1 to 2 wt.% vinyl acetal content, and having a viscosity at 10% TNV in 95% ethyl alcohol in the range of 15 to 2500 centipoise at 25°C (77°F). Preferred binders are available commercially, such as PIOLOFORM® BN18 resins from Wacker Polymer Systems GmbH & Company KG, Sekisui S-Lec BM5Z available from Synthetic Specialties Company, Middleton, New Jersey, and Butvar B-75 Resins from Solutia.
[0017] The organic solvent used for this invention can be any organic solvent which facilitates uniform mixing of the brazing flux and polyvinyl butyral resin binder. Esters, such as ethyl acetate, n-butyl acetate, n-propyl acetate and ketones, such as acetone and cyclohexanone can be used as solvents. Blends of alcohols and aromatic hydrocarbons such as toluene are suitable solvents despite the fact that aromatic hydrocarbons are not individually active solvents for polyvinyl butyral resins. The preferred solvents for this invention are alcohols, such as ethyl alcohol, isopropyl alcohol, n-butanol, n-propyl alcohol and diacetone alcohol. Glycol ethers and glycol ether acetates such as dipropylene glycol monomethyl ether and propylene glycol methyl ether acetate are also preferred as solvents for this invention. The most preferred solvents are mixtures of either propylene glycol methyl ether acetate, isopropyl alcohol and ethyl acetate, or dipropylene monomethyl glycol ether, isopropyl alcohol and ethyl acetate.
[0018] The brazing flux mixture is prepared by combining a brazing flux with a polyvinyl butyral binder and then mixing the combined flux and binder with an organic solvent. The preferred method for combining flux and binder is to subject the flux and binder to shearing. Any shearing method known to the skilled artisan may be applied such as high-speed mixers, media mills or 2-roll mills. The preferred shearing method is to combine the brazing flux and polyvinyl butyral binder in a 2-roll mill. A two-roll mill comprises two cylindrical rolls that rotate at different speeds and in opposite directions in relation to each other. Shearing occurs as the flux and binder blend is passed between the rolls.
[0019] To facilitate the shearing operation, an organic solvent such as an alcohol, an acetate, a glycol ether, or mixtures thereof, as previously described herein, may be added to the flux-binder combination prior to or during shearing. The most preferred solvent for shearing is isopropyl alcohol.
[0020] The amount of binder suitable for this invention is an amount sufficient to maintain adherence of the flux to a surface of an object to be brazed, during handling, forming and stamping operations, yet does not interfere with the formation of brazing joints. The flux-binder combination subjected to shearing contains from about 5 to 30 wt.% binder, from about 70 to 95 wt.% flux, and optionally up to about 10 wt.% organic solvent to equal a total of 100 wt.%. The most preferred flux-binder combination subjected to shearing contains from about 5 to 15 wt.% binder, and from about 85 to 95 wt.% flux, and optionally up to about 10 wt.% organic solvent to equal a total of 100 wt.%. [0021] The shearing operation uniformly distributes the flux in the binder and helps provide uniform flux particle size within the mixture. The inventors believe that the flux particle sizes of this invention provide for a flux coating which can be uniformly applied to an object to be brazed and facilitate adhesion of the dry flux onto the metal object. Although the flux particle size will vary depending on the amount of shearing applied to the mixture, mixture viscosity and the composition of the mixture the inventors believe that the preferred particle size is about 1 micron or smaller.
[0022] The flux-binder combination is then dissolved in a polar organic solvent or a mixture of polar organic solvents to form a mixture suitable for coating an aluminum alloy brazing sheet or part to be brazed.
[0023] The amount of solvent in the invention mixture is an amount sufficient to evenly distribute the flux and binder onto a metal substrate. The preferred amount of solvent is from about 10 to 70 wt.% solvent and from 30 to 90 wt.% flux-binder combination. The most preferred amount of solvent in the mixture is from about 30 to 60 wt.% solvent and from 40 to 70 wt.% flux-binder combination.
[0024] The most preferred brazing mixtures of this invention are comprised of about 62 wt.% potassium fluoroaluminate flux, about 6.9 wt.% polyvinyl butyral resin binder, about 27.5 wt.% propylene glycol methyl ether acetate of dipropylene monomethyl ether, about 2.3 wt.% isopropyl alcohol, and about 1.3 wt.% ethyl acetate.
[0025] The solvent based mixture provides for good surface wetting on the aluminum brazing sheet, yet depending on the aluminum product to be coated, it may still be desirable to clean the brazing sheet prior to application of a coating of the invention brazing flux mixture. For sheet that is produced in an H IX temper and has residual-rolling lubricants present on the surface, cleaning may improve adhesion of the invention mixture. For products produced in -O or -H2X tempers, where the rolling lubricants may be burned off during a final anneal, cleaning of the brazing sheet prior to application of the invention brazing flux mixture would have less effect on mixture adhesion. Suitable cleaning solutions include organic solvents and aqueous cleaners. [0026] The invention brazing flux mixture can be applied to an aluminum alloy brazing sheet by conventional rolling coating processes, by immersion processes, by spray processes, by manual coating such as by brushing or the like. Depending on the brazing requirements, the sheet may be fully coated or partially coated in a pattern on one or both sides. After coating, the sheet may be heated to drive off the solvent component of the invention mixture and to facilitate drying. Depending upon brazing requirements, the amount of dry flux remaining on the surface of the sheet is in the range of about 2 to 40 grams of flux per square meter of brazing sheet (g/m ). Preferably from about 3-20 g/m2 of brazing sheet and most preferably the flux loading is from about 3 g/m to about 10 g/m .
[0027] To aid in materials identification, a suitable color pigment can be added to the coating formulation to produce a colored coating. Suitable pigments include Pigment Blue 15 Phthalo Blue, Thalocyanine Blue 15:4, Pigment Red 52 B in Red, Bon Red 52, Pigment Green 7 Phthalo Green, and Thalocyanine Green 7.
[0028] Any aluminum alloy brazing sheet may be used with the flux coating of this invention. The aluminum brazing sheet preferably comprises a 3XXX, 5XXX, or 6XXX aluminum core alloy clad on at least one side with a 4XXX series brazing alloy. The inventors also believe the flux coating of this invention can be used on unclad aluminum alloy sheet and extrusions.
[0029] The invention will now be further described with reference to a number of specific examples which are to be regarded solely as illustrative and not as restricting the scope of the present invention.
Example 1
[0030] A coating, C31, was prepared by combining 10 wt.% of polyvinyl butyral with 90 wt.% of NOCOLOK® potassium fluoroaluminate flux and subjecting the mixture to a high shear dispersion process using a two-roll mill. Next, 68.9 wt.% of the highly dispersed mixture of polyvinyl butyral and NOCOLOK® flux was combined and mixed with 31.1 wt.% of dipropylene glycol mono methyl ether. [0031] The coating was uniformly applied to both sides of aluminum brazing sheet samples by making drawdowns with a #6, #7, #8 or a #9 Meyer rod. The aluminum brazing sheet was of the type commercially used in the production of automotive heat exchangers (e.g., evaporators) and had a 3XXX aluminum core alloy containing about 1% manganese, 0.3% copper and 0.15% titanium. The 4XXX aluminum braze alloy clad on each side of the core comprised about 10% of the total sheet thickness and contained about 10% silicon. The aluminum sheet was about 0.017 inches thick and had been fully annealed to an -O temper. The coating was dried by placing the sheet into a 500°F furnace for a period of 15 seconds to evaporate the solvent. Depending upon which Meyer rod was used to make the draw down, dry coating weights on each side of the aluminum brazing sheet samples varied from about 5 to 11 grams/meter and the dry coating thicknesses varied from about 0.0002 to 0.0006 inch.
[0032] To evaluate the scratch resistance, pencil hardness measurements were made on the coated sheet. Pencil hardness increases in the order of 3B, 2B, B, HB, F.
[0033] To assess coating adhesion and in preparation for the brazing tests, mini evaporator plates patterned after actual production evaporator plates were stamped from the coated sheet on a five-stage progressive die using a commercially available lubricant, Draw Lube 485 from Circle-Prosco Inc., Bloomington, Indiana. The stamped plates were rubbed with a finger, visually examined for coating loss and rated as follows.
Acceptable: Coating able to withstand forming operation, only minor coating loss in highly formed areas of the formed plate.
Unacceptable: Coating not able to withstand forming operation, significant coating loss from the formed plate.
[0034] Mini evaporators were prepared for the brazing tests by alternately stacking plates stamped from the coated sheet and non-coated 3003 alloy fins in suitable fixture to hold the parts in place. The fixtured parts were then placed in a furnace and brazed by heating to about 600°C in a suitable nitrogen gas atmosphere. The brazeability evaluation criteria were as follows. Acceptable: The braze joint is a well-formed fillet and there is very little or no black carbon residue on the surface.
Unacceptable: The braze joint is small and incomplete or there is a significant amount of black residue on the surface.
[0035] Scratch resistance Coating adhesion and brazeability test results for the coating are summarized in Table 1 below.
Table 1
Figure imgf000011_0001
Example 2 [0036] Weight loss tests were conducted to assess the compatibility of the coating and two commercial forming lubricants. Weighed 2.5 inch x 5 inch samples of sheet coated by using a # 9 Meyer rod were immersed in beakers containing two commercial forming lubricants, Circle-Prosco Inc. Draw Lube 485 and Calvary Industries Inc. CAL Lube 180-M+, at room temperature. After five days, the samples were removed from the lubricants, thermally degreased by heating to about 450°F, and reweighed. The very small differences in initial and final weights shown below indicated that the coating was compatible with the two forming lubricants.
Table 2
Figure imgf000011_0002
Example 3 [0037] Thermal gravimetric analyses were conducted on dried samples of the coating. Coating samples were continuously weighed while being heated at 10°C/min from room temperature to about 600°C in both air and nitrogen. Test results shown in Figure 1 indicated that volatilization of the polyvinyl butyral binder was about complete by the time the coating sample reached 500°C.
Example 4 [0038] Binders other than polyvinyl butyral were investigated. Samples containing both RS and SS types of nitrocellulose including viscosity grades 10 to 15 centipoise and 60 to 80 seconds were tested. In an attempt to improve coating adhesion and scratch resistance, modifiers that were copolymers of butyl acrylate and vinyl isobutyl ether, butyl benzyl phthalate and dioctyl adipate were added to the nitrocellulose in the range of 1 to 100 wt.%. The experimental binders were combined with NOCOLOK® potassium fluoroaluminate flux in varying proportions to produce the 31 coatings described in Table 3. To facilitate mixing and to reduce flux particle size, the flux-binder mixtures were subjected to processing on several different types of dispersion equipment, including a Cowles high-speed mixer, a steel shot media mill and a 2-roll shearing mill. Subsequently the flux-binder mixtures were combined with various solvents including isopropyl acetate, ethyl acetate, butyl acetate, methoxypropanol acetate, dipropylene monomethyl glycol ether, isopropyl alcohol and ethyl alcohol. Polyvinyl pyrolidone was added to some of the coating formulations as a suspending agent to reduce flux drop out. Polyethylene was added to some coating formulations to improve coating lubricity. The coatings were uniformly applied to aluminum brazing sheet samples by making draw downs with different Meyer rods varying from a #3 up to a #22. The aluminum brazing sheet was of the type commercially used in the production of automotive heat exchangers (e.g., evaporators) and had a 3XXX aluminum core alloy containing about 1% manganese, 0.3% copper and 0.15% titanium. The 4XXX aluminum braze alloy clad on each side of the core comprised about 10% of the total sheet thickness and contained about 10% silicon. The aluminum sheet was about 0.017 inches thick and had been fully annealed to an - O temper. The coatings were dried by placing the sheets into a 500°F furnace for a period of 15 seconds to evaporate the solvent. Depending upon which Meyer rod was used to make the draw down, dry coating weights on the aluminum brazing sheet samples varied from about 5 to 35 grams/meter2 and the dry coating thicknesses varied from about 0.0002 to 0.0012 inches.
[0039] The scratch resistance of the coating was subjectively evaluated by scratching the coated sheet with a fingernail. The sheet was rated as being either acceptable or not acceptable.
[0040] To assess coating adhesion, either small cup specimens or mini evaporator plates, patterned after actual production evaporator plates, were stamped from the coated sheet using a commercially available lubricant, Draw Lube 485 from Circle-Prosco Inc. The stamped plates were rubbed with a finger, visually examined for coating loss and rated as follows.
Acceptable: Coating able to withstand forming operation, only minor coating loss in highly formed areas of the formed plate.
Unacceptable: Coating not able to withstand forming operation, significant coating loss from the formed plate.
[0041] Brazeability of the sheet was evaluated by brazing standard "T joints" specimens or by brazing mini evaporators produced by alternately stacking plates stamped from the coated sheet and non-coated 3003 alloy fins. The test specimens were placed in a furnace and brazed by heating to about 600°C in a suitable nitrogen gas atmosphere. The brazeability evaluation criteria were as follows. Acceptable: The braze joint is a well-formed fillet and there is very little or no black carbon residue on the surface.
Unacceptable: The braze joint is small and incomplete or there is a significant amount of black residue on the surface.
[0042] Scratch resistance, coating adhesion and brazeability test results for the coating are summarized in Table 3. Table 3
Figure imgf000014_0001
Figure imgf000014_0002
Figure imgf000015_0001
Figure imgf000015_0002
Figure imgf000016_0001
Figure imgf000016_0002
Figure imgf000017_0001
Figure imgf000017_0002
Figure imgf000018_0001
Figure imgf000018_0002
Figure imgf000019_0001
Figure imgf000019_0002
Figure imgf000020_0001
Figure imgf000020_0002
[0043] Table 3 clearly shows that only a brazing flux coating mixture, comprising brazing flux, a polyvinyl butyral binder and an organic solvent provide a flux-binder coating on a metal object which is both sufficiently durable to maintain adherence on a metal object during stamping and forming and also provides a suitable brazing joint.
Example 5
[0044] Coatings were formulated to evaluate the effects of polyvinyl butyral viscosity and flux/binder ratio on coating performance. Ten coatings, described in Table 4, were prepared by combining samples of commercially available polyvinyl butyral of different viscosities with NOCOLOK® potassium fluoroaluminate flux in varying proportions and subjecting the mixtures to a high shear dispersion process using a 2-roll mill. Subsequently, the highly dispersed mixtures of polyvinyl butyral and NOCOLOK® flux were combined and mixed with varying amounts of dipropylene glycol mono methyl ether.
[0045] The coatings were uniformly applied to both sides of aluminum brazing sheet samples by making draw downs with a #6, #7, #9 or a #12 Meyer rod. The aluminum brazing sheet was of the type commercially used in the production of automotive heat exchangers (e.g., evaporators) and had a 3XXX aluminum core alloy containing about 1% manganese, 0.3% copper and 0.15% titanium. The 4XXX aluminum braze alloy clad on each side of the core comprised about 10% of the total sheet thickness and contained about 10% silicon. The aluminum sheet was about 0.017 inches thick and had been fully annealed to an -O temper. The coatings were dried by placing the sheet into a 500°F furnace for a period of 15 seconds to evaporate the solvent. Depending upon which Meyer rod was used to make the draw down, flux coating weights on each side of the aluminum brazing sheet samples varied from about 3.7 to 10.7 grams/meter2.
[0046] To evaluate the scratch resistance of the coatings, pencil hardness measurements were made on dry coated sheet samples and on samples that were wetted with water. Pencil hardness increases in the order of 3B, 2B, B, HB, F. [0047] To assess coating adhesion and in preparation for the brazing tests, mini evaporator plates patterned after actual production evaporator plates were stamped from the coated sheet on a five stage progressive die using a commercially available lubricant, Draw Lube 485 from Circle-Prosco Inc. The stamped plates were rubbed with a finger, visually examined for coating loss and rated as follows. Acceptable: Coating able to withstand forming operation, only minor coating loss in highly formed areas of the formed plate.
Unacceptable: Coating not able to withstand forming operation, significant coating loss from the formed plate.
[0048] Mini evaporators were prepared for the brazing tests by alternately stacking plates stamped from the coated sheet and non-coated 3003 alloy fins in suitable fixture to hold the parts in place. The fixtured parts were then placed in a furnace and brazed by heating to about 600°C in a suitable nitrogen gas atmosphere. The brazeability evaluation criteria were as follows.
Acceptable: The braze joint is a well-formed fillet and there is very little or no black carbon residue on the surface.
Unacceptable: The braze joint is small and incomplete or there is a significant amount of black residue on the surface.
[0049] Scratch resistance Coating adhesion and brazeability test results for the coating are summarized in Table 4 below.
Table 4
Figure imgf000023_0001
Figure imgf000024_0001
Figure imgf000024_0002
Figure imgf000025_0001
Figure imgf000025_0002
[0050] While this invention has been described with respect to particular embodiments thereof, it is apparent that numerous other forms and modifications of the invention will be obvious to the skilled artisan. The appended claims and this invention should be construed to cover all such obvious forms and modifications which are within the true spirit and scope of the present invention. Having described the presently preferred embodiments, it is to be understood that the invention may be otherwise embodied within the scope of the appended claims.
[0051] Having thus described the invention, what is claimed is:

Claims

1. A method of making a flux-coated aluminum brazing sheet comprising:
(a) combining a brazing flux with polyvinyl butyral binder and optionally an organic solvent to form a first mixture;
(b) shearing said first mixture to form a second mixture having uniformly dispersed brazing flux particles in said second mixture;
(c) combining said second mixture with an organic solvent to form a brazing flux mixture;
(d) coating at least a portion of the surface of an aluminum brazing sheet with said brazing flux mixture; and
(e) drying said brazing flux mixture on said aluminum brazing sheet surface.
2. The method of claim 1 wherein said solvent is selected from the group consisting of alcohols, glycol ethers, ketones, esters and mixtures thereof.
3. The method of claim 1 wherein said organic solvent is selected from the group consisting of ethyl acetate, n-butyl acetate, n-propyl acetate, acetone, cyclohexanone, ethyl alcohol, isopropyl alcohol, n-butanol, n-propyl alcohol, diacetone alcohol, dipropylene glycol monomethyl ether, propylene glycol methyl ether acetate and mixtures thereof.
4. The method of claim 1 wherein said organic solvent is a selected from the group consisting of toluene mixed with at least one alcohol selected from the group consisting of ethyl alcohol, isopropyl alcohol, n-butanol, n-propyl alcohol, and diacetone alcohol.
5. The method of claim 1 wherein said solvent is a mixture of either propylene glycol methyl ether acetate, isopropyl alcohol and ethyl acetate; or dipropylene monomethyl glycol ether, isopropyl alcohol and ethyl acetate.
6. The method of claim 1 wherein said brazing flux is a potassium fluoroaluminate, a cesium potassium fluoroaluminate, a zinc potassium fluoroaluminate, or a silicon and potassium fluoroaluminate mixture.
7. The method of claim 1 wherein said aluminum brazing sheet comprises a 3XXX, 5XXX, or 6XXX aluminum core alloy clad on at least one side with a 4XXX series brazing alloy.
8. The method of claim 1 wherein said aluminum brazing sheet comprises a 3XXX aluminum core alloy comprising about 1 wt.% manganese, about 0.3 wt.% copper, and about 0.15 wt.% titanium, and the balance aluminum, said core alloy clad with a 4XXX aluminum braze alloy comprising about 10 wt.% silicon, and the balance aluminum, and wherein said 4XXX alloy is clad to at least one side of said 3XXX series alloy, and said 4XXX series alloy comprises at least 5% of said total brazing sheet thickness, and said 3XXX series alloy comprises not more than 95% of said total brazing sheet thickness.
9. A method of making a brazing flux mixture comprising:
(a) combining a brazing flux with a polyvinyl butyral binder to form a first mixture;
(b) shearing said first mixture to form a second mixture having uniformly dispersed brazing flux in said binder; and
(c) combining said second mixture with an organic solvent to form a brazing flux mixture.
10. The method of claim 9 wherein said brazing flux is potassium fluoroaluminate, a cesium potassium fluoroaluminate, a zinc potassium fluoroaluminate, or a silicon and potassium fluoroaluminate mixture.
11. The method of claim 9 wherein said solvent is selected from the group consisting of alcohols, glycol ethers, ketones, esters and mixtures thereof.
12. The method of claim 9 wherein said organic solvent is selected from the group consisting of ethyl acetate, n-butyl acetate, n-propyl acetate, acetone, cyclohexanone, ethyl alcohol, isopropyl alcohol, n-butanol, n-propyl alcohol, diacetone alcohol, dipropylene glycol monomethyl ether, propylene glycol methyl ether acetate and mixtures thereof.
13. The method of claim 9 wherein said organic solvent is a selected from the group consisting of toluene mixed with at least one alcohol selected from the group consisting of ethyl alcohol, isopropyl alcohol, n-butanol, n-propyl alcohol, and diacetone alcohol.
14. The method of claim 9 wherein said solvent is a mixture of either propylene glycol methyl ether acetate, isopropyl alcohol and ethyl acetate; or dipropylene monomethyl glycol ether, isopropyl alcohol and ethyl acetate.
15. An unformed aluminum alloy brazing sheet product, having at least a portion of said sheet surface coated with a brazing flux compound comprising brazing flux and polyvinyl butyral.
16. The aluminum alloy brazing sheet product of claim 15 wherein said portion of said sheet surface coated with a brazing flux compound is coated with from about 2 to about 40 grams of brazing flux compound per square meter of said coated portion of said brazing sheet product.
17. The aluminum alloy brazing sheet product of claim 15 wherein said portion of said sheet surface coated with a brazing flux compound is coated with from about 3 to about 20 grams of brazing flux compound per square meter of said coated portion of said brazing sheet product.
18. The aluminum alloy brazing sheet product of claim 15 wherein said portion of said sheet surface coated with a brazing flux compound is coated with from about 3 to about 10 grams of brazing flux compound per square meter of said coated portion of said brazing sheet product.
19. A method of making a shaped metal alloy product comprising:
(a) combining a brazing flux with polyvinyl butyral binder and optionally an organic solvent to form a first mixture;
(b) shearing said first mixture to form a second mixture having uniformly dispersed brazing flux particles in said second mixture;
(c) combining said second mixture with an organic solvent to form a brazing flux mixture;
(d) coating at least a portion of the surface of at least two aluminum alloy brazing sheets with said brazing flux mixture;
(e) drying said brazing flux mixture on said aluminum alloy brazing sheet surfaces;
(f) forming said flux coated aluminum alloy brazing sheets into flux coated parts having predetermined shapes; and
(g) brazing said parts together to form a shaped metal alloy product.
20. A brazing flux mixture for coating brazing sheet prior to sheet formation into a shaped product, said mixture comprising:
(a) brazing flux;
(b) a polyvinyl butyral resin binder; and
(c) an organic solvent selected from the group consisting of ethyl acetate, n-butyl acetate, n-propyl acetate, acetone, cyclohexanone, ethyl alcohol, isopropyl alcohol, n-butanol, n-propyl alcohol, diacetone alcohol, dipropylene glycol monomethyl ether, propylene glycol methyl ether acetate and mixtures thereof.
21. The brazing flux mixture of claim 20 comprising:
(a) about 35-65 wt.% potassium fluoroaluminate flux;
(b) about 2-11 wt.% polyvinyl butyral resin binder; and
(c) the balance to 100 wt.% of organic solvent.
22. The brazing flux mixture of claim 21 comprising:
(a) about 47-62 wt.% potassium fluoroaluminate flux;
(b) about 5-7 wt.% polyvinyl butyral resin binder; and
(c) the balance to 100 wt.% of organic solvent.
23. The brazing flux mixture of claim 21 comprising from about 40-70 wt.% solvent and from about 30-60 wt.% flux and polyvinyl butyral resin binder.
24. The brazing flux mixture of claim 21 wherein the range of ratios of flux to binder is from about 95 wt.% flux to about 5wt.% binder to about 85 wt.% flux to about 15 wt% binder.
25. The brazing flux mixture of claim 21 further comprising a pigment.
PCT/US2003/012239 2002-04-22 2003-04-21 Flux coated brazing sheet WO2003089176A2 (en)

Priority Applications (7)

Application Number Priority Date Filing Date Title
EP03728450.2A EP1497068B8 (en) 2002-04-22 2003-04-21 Flux coated brazing sheet
BRPI0309577-0B1A BR0309577B1 (en) 2002-04-22 2003-04-21 Method for producing a brazing flux mixture, brazing sheet non-conforming product and brazing flux mixture to coat the brazing sheet
CN038118939A CN1655903B (en) 2002-04-22 2003-04-21 Brazing flux mixture , flux coated brazing sheet, method for manufacturing brazing flux mixture
KR1020047016761A KR101076660B1 (en) 2002-04-22 2003-04-21 Flux coated brazing sheet
JP2003585916A JP2005523163A (en) 2002-04-22 2003-04-21 Brazing sheet coated with flux
AU2003234143A AU2003234143A1 (en) 2002-04-22 2003-04-21 Flux coated brazing sheet
CA002482867A CA2482867C (en) 2002-04-22 2003-04-21 Flux coated brazing sheet

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US37439802P 2002-04-22 2002-04-22
US60/374,398 2002-04-22

Publications (2)

Publication Number Publication Date
WO2003089176A2 true WO2003089176A2 (en) 2003-10-30
WO2003089176A3 WO2003089176A3 (en) 2004-06-17

Family

ID=29251185

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2003/012239 WO2003089176A2 (en) 2002-04-22 2003-04-21 Flux coated brazing sheet

Country Status (10)

Country Link
US (1) US7337941B2 (en)
EP (1) EP1497068B8 (en)
JP (1) JP2005523163A (en)
KR (1) KR101076660B1 (en)
CN (1) CN1655903B (en)
AU (1) AU2003234143A1 (en)
BR (1) BR0309577B1 (en)
CA (1) CA2482867C (en)
RU (1) RU2334604C2 (en)
WO (1) WO2003089176A2 (en)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
USRE42329E1 (en) 2002-07-24 2011-05-10 Lucas-Milhaupt, Inc. Flux cored preforms for brazing
EP2608919A1 (en) 2010-08-23 2013-07-03 Norsk Hydro ASA Brazing pre-flux coating
US9314862B2 (en) 2013-05-30 2016-04-19 Lucas-Milhaupt, Inc. Process for flux coating braze preforms and discrete parts
US9731383B2 (en) 2014-07-09 2017-08-15 Bellman-Melcor Development, Llc Filler metal with flux for brazing and soldering and method of using same
US10071445B2 (en) 2006-05-25 2018-09-11 Bellman-Melcor Development, Llc Filler metal with flux for brazing and soldering and method of making and using same
WO2019081690A1 (en) * 2017-10-27 2019-05-02 Solvay Sa Improved brazing process and flux coated parts
US10744601B2 (en) 2015-08-07 2020-08-18 Bellman-Melcor Development, Llc Bonded brazing ring system and method for adhering a brazing ring to a tube
JP2021020225A (en) * 2019-07-24 2021-02-18 三菱マテリアル株式会社 Brazing flux composition and powder brazing filler metal composition, aluminum alloy member, heat exchanger, aluminum alloy member and method for manufacturing heat exchanger

Families Citing this family (28)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006150436A (en) 2004-12-01 2006-06-15 Denso Corp Method for forming flux layer on sheet member made of aluminum, flux composition and sheet member made of aluminum with flux layer formed
KR100625090B1 (en) * 2005-03-02 2006-09-20 모딘코리아 유한회사 Adhesive sheet for brazing magnesium alloy and method for brazing magnesium and aluminum alloy
EP1945397B1 (en) * 2005-11-10 2016-03-02 Lucas-Milhaupt, Inc. Brazing material with continuous length layer of elastomer containing a flux
EP2038085B1 (en) * 2006-05-25 2019-09-11 Bellman-melcor Development, Llc Wire with flux for brazing and soldering and method of making the same
AU2007304895A1 (en) * 2006-10-05 2008-04-10 Waratek Pty Limited Advanced contention detection
CN101600535B (en) * 2006-12-11 2015-05-20 卢卡斯米尔霍特公司 Low and non-silver filler metals and alloys and corresponding joinder systems and methods
CA2688325A1 (en) * 2007-05-25 2008-12-04 Lucas Milhaupt, Inc. Brazing material
US7828089B2 (en) * 2007-12-14 2010-11-09 Baker Hughes Incorporated Erosion resistant fluid passageways and flow tubes for earth-boring tools, methods of forming the same and earth-boring tools including the same
US8252225B2 (en) 2009-03-04 2012-08-28 Baker Hughes Incorporated Methods of forming erosion-resistant composites, methods of using the same, and earth-boring tools utilizing the same in internal passageways
WO2011053506A1 (en) 2009-10-26 2011-05-05 Lucas-Milhaupt, Inc. Low silver, low nickel brazing material
US8247083B2 (en) * 2010-05-18 2012-08-21 Kobe Steel, Ltd. Aluminium alloy brazing sheet
JP5715779B2 (en) * 2010-07-21 2015-05-13 ハリマ化成株式会社 Method for producing aluminum brazing composition and inner fin tube brazing method
JP6137663B2 (en) * 2012-10-26 2017-05-31 株式会社Uacj Flux composition used for flux brazing of aluminum member or aluminum alloy member
JP6090736B2 (en) * 2012-10-26 2017-03-08 株式会社Uacj Aluminum alloy brazing method and flux component-coated aluminum alloy member
JP6649889B2 (en) 2014-07-30 2020-02-19 株式会社Uacj Aluminum alloy brazing sheet
WO2016093017A1 (en) 2014-12-11 2016-06-16 株式会社Uacj Brazing method
JP6186455B2 (en) 2016-01-14 2017-08-23 株式会社Uacj Heat exchanger and manufacturing method thereof
RU2731572C2 (en) 2016-04-12 2020-09-04 Гренгес Аб Sheet for high-temperature soldering
CN106378549B (en) * 2016-11-08 2019-04-19 金锚电力控股有限公司 A kind of cleaning-free scaling powder for copper aluminium soldering
JP6312968B1 (en) 2016-11-29 2018-04-18 株式会社Uacj Brazing sheet and method for producing the same
JP7053281B2 (en) 2017-03-30 2022-04-12 株式会社Uacj Aluminum alloy clad material and its manufacturing method
JP6446087B2 (en) * 2017-04-21 2018-12-26 株式会社Uacj Flux composition
EP3704279A4 (en) 2017-10-31 2021-03-10 Howmet Aerospace Inc. Improved aluminum alloys, and methods for producing the same
JP6916715B2 (en) 2017-11-08 2021-08-11 株式会社Uacj Brazing sheet and its manufacturing method
US11131511B2 (en) 2018-05-29 2021-09-28 Cooler Master Co., Ltd. Heat dissipation plate and method for manufacturing the same
US11571769B2 (en) 2018-09-11 2023-02-07 Uacj Corporation Method of manufacturing a brazing sheet
US11913725B2 (en) 2018-12-21 2024-02-27 Cooler Master Co., Ltd. Heat dissipation device having irregular shape
CN111230359A (en) * 2020-03-09 2020-06-05 浙江新锐焊接科技股份有限公司 Bonding system for brazing flux and application thereof

Family Cites Families (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3951328A (en) * 1972-08-02 1976-04-20 Alcan Research And Development Limited Joining of metal surfaces
JPS5482342A (en) * 1977-12-14 1979-06-30 Sato Kiyoshi Flux for mat finished soldering
US4228214A (en) * 1978-03-01 1980-10-14 Gte Products Corporation Flexible bilayered sheet, one layer of which contains abrasive particles in a volatilizable organic binder and the other layer of which contains alloy particles in a volatilizable binder, method for producing same and coating produced by heating same
US4513062A (en) * 1978-06-17 1985-04-23 Ngk Insulators, Ltd. Ceramic body having a metallized layer
JPS6098691A (en) * 1983-11-04 1985-06-01 Mitsubishi Rayon Co Ltd Manufacture of laminated type piezoelectric actuator
US4981526A (en) * 1988-11-29 1991-01-01 Mitsubishi Aluminum Co., Ltd. Composition for brazing aluminum or aluminum alloy and an aluminum or aluminum alloy product
US5156326A (en) * 1990-12-12 1992-10-20 Park Metallurgical Corporation Brazing flux and method of using the same
US5476725A (en) * 1991-03-18 1995-12-19 Aluminum Company Of America Clad metallurgical products and methods of manufacture
JPH04333390A (en) * 1991-05-07 1992-11-20 Nippon Genma:Kk Aluminum brazing paste
US5330090A (en) 1991-12-27 1994-07-19 Showa Aluminum Corporation Brazing agent and a brazing sheet both comprising an aluminum alloy containing a flux
US5547517A (en) * 1991-12-27 1996-08-20 Showa Aluminum Corporation Brazing agent and a brazing sheet both comprising an aluminum alloy containing a flux
JPH0691367A (en) * 1992-09-14 1994-04-05 Showa Alum Corp Heating and welding method for aluminum materials
JPH06339790A (en) * 1993-05-31 1994-12-13 Showa Alum Corp Production of flux-containing al alloy brazing filler metal and flux-containing al brazing sheet
US5356725A (en) * 1993-09-09 1994-10-18 Kaiser Aluminum & Chemical Corporation Corrosion-resistant aluminum alloy brazing composite
JP2714358B2 (en) * 1994-10-11 1998-02-16 昭和アルミニウム株式会社 Flux-containing Al alloy brazing material and method for producing the same
JP3815576B2 (en) * 1995-07-25 2006-08-30 三菱アルミニウム株式会社 Brazing flux composition, Al material, and heat exchanger manufacturing method
JPH1110389A (en) * 1997-06-20 1999-01-19 Denso Corp Binder for coating aluminum brazing flux
JPH11123588A (en) * 1997-10-27 1999-05-11 Denso Corp Binder for brazing aluminum
US6203628B1 (en) * 1998-08-20 2001-03-20 Toyo Aluminium Kabushiki Kaisha Flux compositions for brazing aluminum, their films and brazing method
JP2000317683A (en) * 1999-05-14 2000-11-21 Furukawa Electric Co Ltd:The Production of surface coated aluminum alloy material
DE19925301A1 (en) 1999-06-02 2000-12-07 Solvay Fluor & Derivate Components coated with aluminum-silicon alloy
US6497770B2 (en) 2000-02-17 2002-12-24 Toyo Aluminium Kabushiki Kaisha Flux-containing compositions for brazing aluminum, films and brazing method thereby

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
None
See also references of EP1497068A4

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
USRE42329E1 (en) 2002-07-24 2011-05-10 Lucas-Milhaupt, Inc. Flux cored preforms for brazing
US10071445B2 (en) 2006-05-25 2018-09-11 Bellman-Melcor Development, Llc Filler metal with flux for brazing and soldering and method of making and using same
EP2608919A1 (en) 2010-08-23 2013-07-03 Norsk Hydro ASA Brazing pre-flux coating
JP2013536085A (en) * 2010-08-23 2013-09-19 ノルスク・ヒドロ・アーエスアー Pre-flux coating for brazing
US9314862B2 (en) 2013-05-30 2016-04-19 Lucas-Milhaupt, Inc. Process for flux coating braze preforms and discrete parts
US9731383B2 (en) 2014-07-09 2017-08-15 Bellman-Melcor Development, Llc Filler metal with flux for brazing and soldering and method of using same
US10744601B2 (en) 2015-08-07 2020-08-18 Bellman-Melcor Development, Llc Bonded brazing ring system and method for adhering a brazing ring to a tube
WO2019081690A1 (en) * 2017-10-27 2019-05-02 Solvay Sa Improved brazing process and flux coated parts
JP2021020225A (en) * 2019-07-24 2021-02-18 三菱マテリアル株式会社 Brazing flux composition and powder brazing filler metal composition, aluminum alloy member, heat exchanger, aluminum alloy member and method for manufacturing heat exchanger
JP7196032B2 (en) 2019-07-24 2022-12-26 Maアルミニウム株式会社 Brazing flux composition and brazing powder composition, aluminum alloy member and heat exchanger, and method for producing aluminum alloy member and heat exchanger

Also Published As

Publication number Publication date
EP1497068A2 (en) 2005-01-19
WO2003089176A3 (en) 2004-06-17
KR101076660B1 (en) 2011-10-26
JP2005523163A (en) 2005-08-04
US20040009358A1 (en) 2004-01-15
CN1655903A (en) 2005-08-17
EP1497068A4 (en) 2006-02-15
RU2004133907A (en) 2005-06-10
CA2482867A1 (en) 2003-10-30
EP1497068B8 (en) 2013-12-25
CN1655903B (en) 2011-03-30
EP1497068B1 (en) 2013-11-20
CA2482867C (en) 2009-06-23
BR0309577A (en) 2005-03-01
US7337941B2 (en) 2008-03-04
AU2003234143A1 (en) 2003-11-03
RU2334604C2 (en) 2008-09-27
BR0309577B1 (en) 2013-12-31
KR20050011751A (en) 2005-01-29

Similar Documents

Publication Publication Date Title
US7337941B2 (en) Flux coated brazing sheet
EP1127653B1 (en) Flux-containing compositions for brazing aluminum, films and brazing method thereby
EP0980738B1 (en) Flux compositions for brazing aluminium, their films and brazing methods
AU751115B2 (en) Composite sheet material for brazing
JP2009106947A (en) Aluminum alloy tube
CA2636345C (en) Method of manufacturing a brazed assembly
JP3534450B2 (en) Heat exchanger manufacturing method
JPH0663734A (en) Method for brazing al and al alloy member
US20070187462A1 (en) Method of manufacturing a brazed assembly
US7041385B2 (en) Composite sheet material for brazing
JP2001191176A (en) Brazing method for aluminum, flux composition and same flux composition-coated aluminum alloy
JP3705939B2 (en) Paste composition for aluminum brazing, coating film thereof, and brazing method
JP2009058140A (en) Member for aluminum heat exchanger having superior corrosion resistance, and manufacturing method of aluminum heat exchanger having superior corrosion resistance
JPH08112667A (en) Aluminum heat exchanger core and its brazing method
JPH0623536A (en) Method for brazing aluminum or aluminum alloy
JPS6037293A (en) Brazing method of aluminum and alloy thereof
JPH01202396A (en) Flux for brazing aluminum and its coating method
JPH07256481A (en) Composition for brazing, al material provided with composition for brazing and heat exchanger

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A2

Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EC EE ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NI NO NZ OM PH PL PT RO RU SC SD SE SG SK SL TJ TM TN TR TT TZ UA UG UZ VC VN YU ZA ZM ZW

AL Designated countries for regional patents

Kind code of ref document: A2

Designated state(s): GH GM KE LS MW MZ SD SL SZ TZ UG ZM ZW AM AZ BY KG KZ MD RU TJ TM AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LU MC NL PT RO SE SI SK TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG

121 Ep: the epo has been informed by wipo that ep was designated in this application
DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
WWE Wipo information: entry into national phase

Ref document number: 2482867

Country of ref document: CA

WWE Wipo information: entry into national phase

Ref document number: 1020047016761

Country of ref document: KR

Ref document number: 2003234143

Country of ref document: AU

WWE Wipo information: entry into national phase

Ref document number: 2003728450

Country of ref document: EP

Ref document number: 2003585916

Country of ref document: JP

ENP Entry into the national phase

Ref document number: 2004133907

Country of ref document: RU

Kind code of ref document: A

WWE Wipo information: entry into national phase

Ref document number: 20038118939

Country of ref document: CN

WWP Wipo information: published in national office

Ref document number: 2003728450

Country of ref document: EP

WWP Wipo information: published in national office

Ref document number: 1020047016761

Country of ref document: KR