WO2003106102A1 - 水系アルミニウムろう付け用組成物、及びろう付け方法 - Google Patents
水系アルミニウムろう付け用組成物、及びろう付け方法 Download PDFInfo
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- WO2003106102A1 WO2003106102A1 PCT/JP2003/007604 JP0307604W WO03106102A1 WO 2003106102 A1 WO2003106102 A1 WO 2003106102A1 JP 0307604 W JP0307604 W JP 0307604W WO 03106102 A1 WO03106102 A1 WO 03106102A1
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- brazing
- aluminum
- brazing composition
- zinc
- meth
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Classifications
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F28—HEAT EXCHANGE IN GENERAL
- F28F—DETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
- F28F21/00—Constructions of heat-exchange apparatus characterised by the selection of particular materials
- F28F21/08—Constructions of heat-exchange apparatus characterised by the selection of particular materials of metal
- F28F21/081—Heat exchange elements made from metals or metal alloys
- F28F21/084—Heat exchange elements made from metals or metal alloys from aluminium or aluminium 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
- 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
- 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
- B23K35/288—Al as the principal constituent with Sn or Zn
-
- 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
- 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
- B23K2101/00—Articles made by soldering, welding or cutting
- B23K2101/006—Vehicles
-
- 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
- B23K2103/08—Non-ferrous metals or alloys
- B23K2103/10—Aluminium or alloys thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
- B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
- B23K35/36—Selection of non-metallic compositions, e.g. coatings, fluxes; Selection of soldering or welding materials, conjoint with selection of non-metallic compositions, both selections being of interest
- B23K35/3612—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
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F28—HEAT EXCHANGE IN GENERAL
- F28F—DETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
- F28F1/00—Tubular elements; Assemblies of tubular elements
- F28F1/10—Tubular elements and assemblies thereof with means for increasing heat-transfer area, e.g. with fins, with projections, with recesses
- F28F1/12—Tubular elements and assemblies thereof with means for increasing heat-transfer area, e.g. with fins, with projections, with recesses the means being only outside the tubular element
- F28F1/126—Tubular elements and assemblies thereof with means for increasing heat-transfer area, e.g. with fins, with projections, with recesses the means being only outside the tubular element consisting of zig-zag shaped fins
Definitions
- Aqueous aluminum brazing composition and brazing method Aqueous aluminum brazing composition and brazing method
- the present invention relates to an aluminum brazing composition containing a zinc-based flux that can improve corrosion resistance by forming a zinc diffusion layer when applied and brazed to an aluminum member.
- An aqueous aluminum brazing composition capable of effectively preventing sedimentation of zinc-based flux in a material and maintaining good brazing properties, an aluminum member coated with the brazing composition, and the aluminum member
- the present invention relates to a brazing method and a heat exchanger for mounting on a vehicle manufactured by the brazing method.
- in-vehicle aluminum heat exchangers have been required to be lighter for the purpose of improving fuel efficiency of vehicle engines.
- it is necessary to reduce the thickness of the components such as the tubes of the heat exchanger.
- thinning of the material is likely to cause leakage of fluid (refrigerant) due to perforated corrosion of the aluminum material.
- fluid refrigerant
- the tube forming the passage through which the refrigerant flows is formed into a cross-sectional shape of a flat multi-hole by extrusion of an aluminum material, and is formed on the outer peripheral surface of the flat multi-hole tube.
- the corrosion resistance of the tube is improved by performing Zn spraying to form a Zn diffusion layer with a surface Zn concentration of 0.5% or more.
- the Zn diffusion layer since the Zn diffusion layer has a lower natural potential than the aluminum material constituting the tube, the Zn diffusion layer corrodes (sacrifice corrosion) preferentially over the aluminum material, and thus is made of aluminum.
- the basic principle of improving corrosion resistance is to effectively prevent perforated corrosion of tubes.
- the amount of Zn deposition is controlled in large amounts ignoring cost in order to prevent the above-mentioned defects, a high concentration of Zn will also be present at the brazing portion between the tube and the corgetofin.
- the brazing portion is selectively susceptible to corrosion, and the corrugated fins may fall off.
- an organic binder containing a methacrylate polymer or copolymer as a main component, a non-corrosive flux and a powder such as silicon or zinc are mixed.
- a method of applying this mixture to an aluminum extruded porous flat tube for an automobile heat exchanger by a roll transfer method has been disclosed.
- a paint ie, a brazing composition
- a non-corrosive flux and zinc powder was prototyped and tried to be applied, but within a few hours the paint thickened and became stable. It could not be applied to the tube.
- Zn fluoride which is a more stable metal compound, instead of Zn powder (that is, powder of Zn metal alone) suppresses the formation of Zn ions. It is possible to do.
- the specific component of the Zn fluoride is, for example, an alkali metal salt of fluorozinc acid such as KZn F 3, as described in Japanese Patent Application Laid-Open No. 2002-507748. Also, the choice of fluoride is due to its low corrosive effect on metals and its own flux effect.
- International Patent Publication WO 0 1/3 800 0 A1 contains KZnF 3 which is a Zn fluoride, a homopolymer or a copolymer of methacrylate, and an organic solvent such as xylene.
- An aluminum brazing composition and a brazing method are disclosed.
- a homopolymer of a methacrylate ester having no carboxyl group as a binder. If the number of carbon atoms is small, the glass transition temperature tends to increase, and the brazing composition may fall off the aluminum member or crack the surface.
- the use of highly toxic organic solvents is being restricted from recent environmental issues and safety and health viewpoints, and aromatic solvents such as xylene are particularly problematic.
- the amino alcohol acts as a base and chemically reacts preferentially with the carboxylic acid group of the organic binder dissociated by protons to form a hydroxyl group. It is estimated that the reaction between the Zn ions generated by the decomposition and the organic binder can be suppressed.
- the corrosion resistance is improved by the sacrificial corrosion effect of the zinc diffusion layer, which is the intended purpose.
- the action of the amino alcohol suppresses the reaction between the organic binder and the Zn ion, thereby improving the problem of the composition becoming thicker.
- the present invention provides an aluminum brazing composition in which a zinc-based flux is blended with an organic binder for the purpose of improving corrosion resistance after brazing. Prevention is a technical issue.
- the aluminum brazing composition according to the present invention for solving the above technical problems is as follows.
- a (meth) acrylic acid and a (meth) acrylate-based copolymer emulsion is used as an anti-settling agent. 0.03 to 1.5% by weight in 0.0% by weight, and the logarithmic value of the viscosity at 25 ° C by an EH type viscometer at 10 rpm is the same as the rotational speed at 100 rpm.
- a water-based aluminum brazing composition (the present invention 1) characterized in that the thixotropy value (the value of the quotient) divided by the logarithmic value of the viscosity in (1) is adjusted to 1.01 to 1.20.
- the water-based aluminum brazing composition according to the present invention (2) wherein the zinc-based flux is a K-Zn-F-based Zn braided material.
- a reaction inhibitor that suppresses a reaction between zinc and a carboxyl group in an organic binder or an anti-settling agent.
- the water-based aluminum brazing composition according to the present invention wherein the reaction inhibitor is an amino alcohol having a boiling point of 120 ° C. to 200 ° C. (Invention 5).
- the aluminum member coated with the brazing composition according to the present invention is as follows.
- the brazing composition of any one of the present inventions 1 to 5 is applied to an aluminum member and dried, and the dry residual component in the brazing composition is fixed to the surface of the aluminum member.
- Aluminum member coated with a brazing composition (the present invention 6
- the brazing composition wherein the average thickness of the coating film of the brazing composition is 2 to 15 m and the maximum thickness is 30 m or less.
- An applied aluminum member (the present invention 7).
- an aluminum member coated with the brazing composition according to any one of the present invention 6 to 8 is assembled into a predetermined structure, and heated to a brazing temperature.
- a zinc diffusion layer is formed on the surface of the aluminum member.
- the heat exchanger for vehicle mounting according to the present invention (the present invention 10) is characterized by being manufactured by the aluminum brazing method according to the ninth present invention.
- FIG. 1 is a graph showing the relationship between the amount of adhesion after drying when a brazing composition is applied to an aluminum member and the ⁇ concentration of the aluminum surface after brazing.
- FIG. 2 is a schematic perspective view of a brazing structure in which a tube material and a fin are assembled.
- a first feature of the present invention is that a water-based aluminum brazing composition containing a zinc-based flux for improving corrosion resistance and an organic binder, and a (meth) acrylic acid and a (meth) acrylate ester as anti-settling agents.
- the second feature is that the water-based brazing composition is applied.
- the third feature is that the aluminum member coated with the brazing composition is heated to form a zinc diffusion layer on the surface of the aluminum member, thereby improving corrosion resistance.
- the fourth feature is the aluminum brazing method, which is a heat exchanger for in-vehicle use manufactured by this aluminum brazing method.
- the water-based aluminum brazing composition of the present invention contains a zinc-based flux, an organic binder, and an antisettling agent as essential components.
- the zinc-based flux forms a Zn diffusion layer on the surface of the aluminum member by the action of the Zn component to exert a sacrificial corrosion effect, and reduces and removes an oxide film formed on the aluminum surface. This is to promote the formation of a eutectic alloy of aluminum and brazing material.
- the zinc-based flux is basically a K—Zn—F-based Zn fluoride.
- Zn fluoride has the advantage that it can suppress the generation of Zn ions more than the powder of Zn metal alone, can exert the flux function by the action of fluoride, and has low corrosion to metal. There are advantages.
- the potassium salt portion may be replaced with other alkali metal salts such as Cs and Rb.
- the composition is 2 A 1 F 5 or the like.
- fluoride fluxes such as CsF, RbF, LiF, NaF, and CaF, or zinc fluxes containing these as main components Some may be substituted.
- the above-mentioned organic binder is basically a (meth) acrylic acid ester-based polymer. From the viewpoint of volatilization during brazing and leaving no carbide residue, the methacrylic acid-based polymer is compared with the acrylate-based polymer. Polymers are preferred.
- the methacrylic acid-based polymer is a polymer of methacrylic acid ester or a copolymer of two or more methacrylic acid esters.
- methacrylate examples include methyl methacrylate, methacrylic acid Methyl, propyl methacrylate, 2-methylpropyl methacrylate, n-butyl methacrylate, t-butyl methacrylate, 2-ethylhexyl methacrylate, octyl methacrylate, isodecyl methacrylate, methacrylic acid Lauryl acrylate, tridecyl methacrylate, stearyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, getylaminoethyl methacrylate, t-butylamylaminoethyl methacrylate, glycidyl methacrylate, metatetrahydrol methacrylate Ruffle and the like.
- a monomer copolymerizable therewith such as carboxylic acid such as acrylic acid, methacrylic acid, maleic acid, and itaconic acid. It may be a copolymer containing at least one group-containing monomer. Further, in addition to these monomers, at least one of the following monomers (a) to (c) may be used. A copolymer containing one kind may be used.
- n is an integer of 2 to 4.
- n is an integer of 2 to 12.
- n is an integer of 2 to 12.
- the organic binder is generally isopropyl alcohol (IPA), 3-methoxy-13-methyl-1-butanol, n-propanol, ethylene glycol monoethyl ether, diethylene glycol monoethyl ether, It is manufactured by solution polymerization using a hydrophilic solvent such as triethylene glycol monoethyl ether, ethylene glycol monobutyl ether, and propylene glycol monoethyl ether.
- IPA isopropyl alcohol
- 3-methoxy-13-methyl-1-butanol 3-methoxy-13-methyl-1-butanol
- n-propanol ethylene glycol monoethyl ether
- n-propanol ethylene glycol monoethyl ether
- diethylene glycol monoethyl ether diethylene glycol monoethyl ether
- the organic binder is saponified with amino alcohols, amine, ammonia, and the like, and if necessary, an aqueous solution is obtained by partially removing the solvent and adding water. Then, a zinc-based flux is added to the aqueous solution of the organic binder to produce the organic binder.
- the water-based aluminum brazing composition of the present invention comprises a specific anti-settling agent,
- the TI value was adjusted to 1.01-1.20 by including it in the positive range.
- the TI value of the present invention is obtained by calculating the logarithmic value of the viscosity at 25 rpm at 10 rpm by the EH type viscometer and the logarithmic value of the viscosity at 100 rpm at 25 ° C. Defined as the number divided.
- anti-settling agents for paints containing powders include ultra-fine silica and magnesium aluminum silicate as inorganic materials, and poly (meth) -terminated sodium acrylate and polyvinyl alcohol as organic materials.
- Polyethylene oxide, urethane-modified polyester and the like are known.
- brazing can be performed in a system to which inorganic ultrafine particles such as silica are added, but after brazing, an inorganic substance derived from the anti-settling agent locally adheres, and the corrosion resistance of the portion is significantly reduced. There is a problem. In addition, most of the organic antisettling agents generate carbide during brazing, and there is a problem that the joining strength at the brazed portion is reduced.
- the specific anti-settling agent of the present invention means a (meth) acrylic acid and (meth) acrylic acid ester-based copolymer emulsion.
- (Meth) acrylic acid is a concept that includes acrylic acid and methacrylic acid.
- a (meth) acrylic acid and (meth) acrylic acid ester-based copolymer is a copolymer containing (meth) acrylic acid and (meth) acrylic acid ester as an essential monomer composition.
- the homopolymer of (meth) acrylic acid and the homopolymer of (meth) acrylic acid ester are excluded.
- a copolymer containing (meth) acrylic acid ⁇ (meth) acrylic acid ester and other monomers copolymerizable with these monomers may be used.
- a copolymer of (meth) acrylic acid and (meth) acrylic acid ester is added to the brazing composition in the form of an aqueous emulsion.
- the anti-settling agent of the present invention may be componentally common to the organic binder in some cases, but as shown in Examples below, the weight average molecular weight of the copolymer constituting the anti-settling agent is One order of magnitude or more, and the magnitude of this average molecular weight, is the reason that the overall brazing composition can be given the proper thixotropic viscosity.
- the content of the (meth) acrylic acid (meth) -terminated acrylate-based copolymer emulsion and the TI value of the brazing composition are organically integrated.
- the copolymer emulsion is used in an amount of 0.03 to 1.5% by weight, preferably 0.05 to 1% by weight, based on 100% by weight of the brazing composition. It must be contained at a rate of 50% by weight, more preferably 0.1 to 1.5% by weight.
- the Al Miniumu brazing composition containing zinc-based flux (KZ nF 3), in order to prevent settling of the flux (KZnF 3) is 1.
- TI value 0 It is set to 1-1.20, more preferably 1.05-1.20.
- the TI value is lower than 1.01, it is insufficient to prevent the sedimentation of the zinc-based flux having a high specific gravity, and when the TI value exceeds 1.20, the thixotropic viscosity of the brazing composition becomes high. If it is too much, the fluidity of the paint will be impaired and various problems will easily occur during use.
- the TI value of the brazing composition is defined by the content of the above-mentioned anti-settling agent.
- the amount of the anti-settling agent is less than 0.03% by weight, the target proper TI value cannot be obtained.
- the amount exceeds 1.5% by weight a slight adverse effect of generating carbides appears. Therefore, in order to control the TI value of the brazing composition to an appropriate range of 1.01 to 1.20 and to secure good brazing properties, the content of the anti-settling agent is set to 0.0. Adjust to 3 to 1.5% by weight.
- the water-based aluminum brazing composition of the present invention can be mixed with metal silicon powder as a brazing material other than the flux.
- Si reacts with the aluminum member during brazing to form a eutectic alloy having a lower melting point than aluminum, and the eutectic composition allows the brazing between the aluminum members to be performed smoothly. Therefore, when a brazing composition containing Si powder is applied to an aluminum member, the brazing material is clad on the side of the plurality of aluminum members to be brazed. Since it is possible to braze a plurality of aluminum members without having to do so, the aluminum members can be formed as inexpensive aluminum bare materials, which is extremely advantageous in reducing costs. For example, in the case of an in-vehicle heat exchanger, adopting this method eliminates the need for a clad brazing that was conventionally required for the corrugated fins.
- Si—A1 alloy, copper, germanium, and the like can be mixed with the brazing composition as a brazing material in addition to the metallic gay.
- the organic binder in the water-based aluminum brazing composition has a carboxyl group in its molecule in order to ensure water solubility.
- the reaction inhibitor when a reaction inhibitor is added to the water-based aluminum brazing composition of the present invention, the reaction between the carboxyl group in the organic binder and the zinc-based flux can be suppressed.
- the anti-settling agent since the anti-settling agent also contains a carboxyl group, the reaction between the carboxyl group in the anti-settling agent and the zinc-based flux can be suppressed. This is as shown in the above-mentioned prior art proposed by the present applicant.
- the reaction inhibitor include tertiary amino alcohols such as dimethylaminoethanol and getylaminoethanol, and secondary amino alcohols such as methylaminoethanol, ethylaminoethanol and isopropylaminoethanol.
- the reaction inhibition principle of these amino alcohols is based on the fact that the nitrogen atoms in the amino alcohol molecules have a lawn pair, so that these amino alcohols are converted into carboxyl groups that are dissociated by protons. It is presumed to attack the nucleophile, thereby preventing the ionized zinc (Zn 2 + ) from reacting with the carboxyl group.
- the addition amount of the reaction inhibitor is preferably about 0.2 to 2% by weight based on 100% by weight of the brazing composition. If the content is more than 2% by weight, the amino odor peculiar to amino alcohol increases, which is not preferable for safety and health. If it is less than 0.2% by weight, the effect of suppressing the reaction is reduced.
- amino alcohols used for the reaction inhibitor those having a boiling point of 120 ° C. to 200 ° C. are preferable, as shown in the present invention 5, and more preferably 12 0 to 180 ° C. This is because if the boiling point is lower than 120 ° C, as described above, the odor specific to amino alcohol becomes intense, which is not preferable for safety and health, and conversely, the boiling point is lower than 200 ° C. If it exceeds, the odor is reduced, but in the drying step after the application of the brazing composition, the reaction inhibitor may not be sufficiently volatilized, resulting in poor drying.
- Examples of the amino alcohols having a boiling point of 120 to 200 ° C. include the secondary to tertiary amino alcohols listed above.
- Invention 6 is an aluminum member coated with the above brazing composition.
- the brazing composition is applied to the aluminum member by a known applicator, and the volatile component in the brazing composition is sufficiently removed.
- the non-volatile component in the brazing composition is volatilized and dried and fixed to an aluminum member.
- brazing composition when the brazing composition is applied to an aluminum member, the application form of the brazing composition and the properties of the zinc-based flux in the composition greatly affect the brazing properties. . That is, according to the actual product scale, when brazing the heat exchanger by laminating dozens of aluminum tubes coated with the brazing composition, the brazing properties and corrosion resistance of the aluminum members are as follows: This largely depends on the state of the zinc-based flux powder in the brazing composition or the quality of the coating film applied on the tube.
- the reaction behavior of Zn fluoride in the brazing addition heat process was examined.
- the Zn fluoride reacted with the aluminum tube in contact with it.
- a K—A 1 —F-based compound and Zn are formed, and the average coating thickness of the brazing composition applied to the aluminum material is 2 to 15 m, more preferably, By setting it to 2 to 10, once the molten and solidified flux residue of the crystallized residue is confirmed on the aluminum surface, the attached Zn is sufficiently diffused, and the flux of the heat exchanger is reduced. It was also found that the bonding was good.
- the average thickness of the coating exceeds 15 / ⁇ m, the unmelted flux residue will remain in the form of powder on the surface of the brazed aluminum tube, impeding the contact between the tube and the fin. However, despite the large amount of adhesion, the diffusion amount of Zn into the aluminum tube does not increase so much, and the joining rate of the fin is significantly reduced. In addition, If the average thickness is less than 2 m, the total amount of adhesion is too small, so that the diffusion amount of Zn into the tube is too low and the corrosion resistance is reduced.
- the average thickness of the coating film is preferably 2 to 15 m, and the maximum thickness is preferably 30 m or less. The average thickness is more preferably 3 to 10 m, and the maximum thickness is more preferably 20 m or less.
- the brazing composition has been described from the viewpoint of the thickness of the coating when the brazing composition is applied to an aluminum member.
- the brazing composition using the zinc-based flux has sufficient corrosion resistance after brazing. To achieve this, it is necessary to ensure that the Zn concentration on the aluminum surface is 0.5% or more.
- the brazing composition when the brazing composition is applied to an aluminum member, if the average particle diameter of the zinc-based flux powder in the brazing composition is 30 m or less, the zinc-based flux powder is once melted and solidified. Only the crystallized flux residue is confirmed on the aluminum surface, and the applied Zn diffuses sufficiently, improving the bondability of the fins.However, if the average particle size exceeds 30 ⁇ m, after brazing On the surface of the aluminum tube, a partially unmelted flux residue remains in powder form, and this flux residue layer forms a tube and a film. It was found that the contact with the fin was inhibited and the bonding rate of the fin was significantly reduced.
- the average particle size of the zinc-based flux in the brazing composition is preferably 30 m or less.
- the present invention 9 provides a sacrificial corrosion effect of zinc by assembling an aluminum member coated with the above brazing composition into a predetermined structure, and then heating the aluminum member to a brazing temperature to form a zinc diffusion layer on the surface of the aluminum member.
- This is an aluminum brazing method that improves the corrosion resistance of aluminum materials.
- the brazing method of the present invention 9 can be applied to the production of any aluminum product, but the present invention 10 is a specific example thereof. It is a heat exchanger.
- the term “aluminum” is a concept including an aluminum alloy. ''
- synthesis examples of organic binders, synthesis examples of anti-settling agents, and examples of aqueous aluminum brazing compositions containing these are described in order, and the TI value, settling property and A brazing test example will be described.
- test examples of the viscosity increase and the odor level due to the change in the content of the reaction inhibitor in the brazing composition will be described. Furthermore, the thickness of the coating film on the aluminum member of the brazing composition and the brazing properties, the fin joint ratio, and the maximum corrosion depth due to the change in the average particle size of the Zn-based flux in the composition are determined. Various test examples will be described. Further, “parts” and “%” in the following Synthesis Examples, Examples and Test Examples are all by weight unless otherwise specified.
- a reactor equipped with a stirrer, a cooling pipe, a dropping funnel and a nitrogen inlet pipe was charged with 60%. After charging 0 parts of isopropyl alcohol, the temperature was raised under a nitrogen stream until the temperature in the system reached 80 ° C. Next, a mixed solution of methyl methacrylate (100 parts), isobutyl methacrylate (275 parts), methacrylic acid (25 parts) and benzoyl peroxide (4 parts) was dropped into the system over about 3 hours. The polymerization was completed while maintaining the same temperature to obtain a resin solution having an acid value of about 40 at the time of drying and a nonvolatile content of 40%.
- the organic binder obtained in the above Synthesis Example was mixed with the sedimentation inhibitor composed of the methacrylic acid / methacrylic acid ester copolymer emulsion obtained in the above Synthesis Example, and then the reaction inhibitor And mix thoroughly with stirring. The mixture was further stirred and mixed, and then an appropriate amount of 3-methoxy-3-methyl-butanol was added to prepare a brazing composition having a nonvolatile content of 50%. 1 and 2.
- the content of the anti-settling agent and the type and content of the reaction inhibitor were changed, and the amino alcohols were used as the reaction inhibitor, and KZn was used as the flux.
- F 3 respectively were used (however, example 1 1-1 2 is an example containing no reaction inhibitor).
- Examples 1 to 12 above are examples in which only the flux is used and no brazing material is used, while Example 13 is based on Example 7 and uses the brazing material together with the flux (KZn F 3 ).
- a combination examples, fluxes and KZ n F the compounding ratio of the brazing material 3: S i 2: was adjusted to 1, the other conditions are those treated in the same manner as in example 7.
- Table 2 the organic binder of the above synthesis example and the flux (KZnF
- Comparative Examples 1 and 2 are blank examples that do not contain the above-mentioned anti-settling agent, and Comparative Examples 3 and 4 are 2.0-5.0% of the anti-settling agent to the entire brazing composition.
- Comparative examples 5 to 9 are examples in which a known compound used in powder-containing paint is used as a sedimentation preventive agent instead of a copolymer emulsion of methacrylic acid and nomethacrylic acid ester. .
- the amount of flux or brazing material added in the brazing composition was 90% with respect to 10% of the nonvolatile content of the organic binder. All were prepared as follows.
- T I value 10 g P / 10 g Q... (A)
- Each of the manufactured paints was stored for one week, and the degree of sediment at the bottom of the container was visually observed to evaluate the degree of sedimentation.
- the evaluation criteria are as follows.
- an aluminum alloy tube material 1 containing 0.4% of copper and 0.15% of manganese was added to Examples 1 to 12 and Comparative Examples 1 to 9.
- Each coating was applied over a rollco. After the application, it was dried for 1 minute in a circulation open at 180 ° C. As described above, the amount of the coating was adjusted so that the weight of the adhered component after drying was 8 ⁇ 1 g / m 2 from the viewpoint of ensuring good corrosion resistance.
- brazing structure 3 was heated to 600 ° C. in a nitrogen gas atmosphere to perform brazing, and the carbonization state of the binder and the state of the fillet at the joint were visually observed. Was evaluated. Table 3 shows the test results.
- the evaluation criteria are as follows.
- Example 1 Focusing on the content of the anti-settling agent, in Example 1 where the content is as low as 0.03%, the TI value is 1.01, and Example 1 where the content is as large as 1.5% and At 0, the TI value was 1.05. In Examples 1 and 10, both the sedimentation property and the brazing property were ⁇ . On the other hand, in Comparative Examples 1 and 2 where the content was 0% (blank example), the TI value was 1.0 and the sedimentation property was X in both cases. In Comparative Example 4, the TI value was 1.00, and both the sedimentation and brazing properties were X. In Comparative Example 3 in which the content was slightly excessive at 2%, the TI value was 1.01, but both the sedimentation property and the brazing property were evaluated as poor. Decreased.
- the TI value could not be adjusted within an appropriate range, and the precipitation of zinc-based flux could not be prevented. If the content of the anti-settling agent was too high, carbides were generated, which had an adverse effect on brazing properties.
- methacrylic acid and methacrylic acid ester-based copolymers that constitute anti-settling agents have a common part as an organic binder component.However, if this copolymer is used as an anti-settling agent, It is good to add a small amount at the level of the agent, but as shown in Comparative Examples 3 and 4, it was confirmed that if the organic binder was excessively added, both the sedimentation property and the brazing property were adversely affected.
- the copolymer emulsion of methacrylic acid / methacrylic acid ester was found to be able to secure both good anti-settling properties against zinc-based flux and excellent brazing properties to aluminum materials. It has been shown to exert remarkable effectiveness as an inhibitor.
- the coating materials prepared in Examples 1 to 13 and Comparative Examples 1 to 9 were manufactured at 25 ° C. and 50 rpm. The viscosity value immediately after and the viscosity value after one week were measured, and the rate of increase in viscosity (%) was calculated to evaluate the degree of viscosity increase of the paint.
- the evaluation criteria are as follows.
- the evaluation criteria are as follows.
- the evaluations of the thickening were both ⁇ , indicating that the reaction between the zinc component and the carboxylic acid group such as an organic binder can be satisfactorily suppressed.
- Example 6 and Comparative Example 1 in which the content of these amino alcohols was as low as 0.2 the evaluation of thickening was ⁇ , and the effect of suppressing the above reaction was reduced.
- the evaluation of the viscosity was X.
- each condition of average powder particle size of n F 3 flux are shown in Table 5-6. Further, based on Example 7, the average powder particle diameter of the flux, the average thickness of the coating film of the brazing composition, and the maximum thickness of the coating film were changed.
- the brazing composition of Example 6 and the brazing composition of Example 17 based on Example 2 were similarly prepared as shown in Tables 5 and 6.
- the above-mentioned brazing property test in the coating form test is basically the same as the brazing property test focusing on the above-described anti-settling agent.
- fins 2 were stacked on a tube 1 having a length of 200 thighs, and 20 stages were stacked at a fin pitch of 3 thighs (see Fig. 2).
- the evaluation of the brazeability test was performed by visually observing the carbonization state of the organic binder and the state of the fillet at the joint.
- the evaluation criteria were the same as those in the brazing property test when the anti-settling agent was focused on, and evaluated in three grades of ⁇ , ⁇ , and X.
- the corrugated fin material after the addition of the brazing filler was pressed with a fixture to visually observe the presence or absence of joining, and the joining rate () was determined by the following equation.
- Joining rate (number of unjoined fin peaks / total number of corrugated peaks) X 100 A representative portion was cut out and embedded in resin, and it was examined whether or not the joined portion was buckled.
- the evaluation criteria for the fin joint ratio are as follows.
- the joining ratio was 95% or more.
- the joining ratio was less than 95%.
- a SWAAT corrosion test (ASTMG 85-85) was performed on the core treated in the same process as the above-mentioned brazeability test for 6 weeks, and the maximum tube after the corrosion test was tested. By measuring the pit depth, the pit depth (mm) of the tube was examined to evaluate the superiority of the corrosion resistance of the aluminum member.
- the evaluation criteria for the corrosion resistance are as follows.
- the maximum depth was less than 0.15 mm.
- the maximum depth was 0.15 mm or more.
- the maximum corrosion depth is 0.30 mm (accordingly, the evaluation is X) in Comparative Example 2 because the average coating thickness is too thin, 1 ⁇ ⁇ . As a result, the corrosion resistance decreased. Also, in Example 15, the average coating film thickness was too thick, 20 m, and the fin bonding rate was 88.9%.
- Example 17 since the maximum coating film thickness was too thick at 35 ⁇ m, the fin bonding rate was 93.5 and the maximum corrosion depth was 0.22 mm. And the corrosion resistance were both rated X.
- the average thickness of the coating film of the brazing composition is 2 to 15 urn, the maximum thickness of the coating film is 30 m or less, and the average particle size of the flux in the composition is 30 ⁇ m. m. In Examples satisfying the following conditions, not only the brazing property but also the evaluation of the fin joint rate and the corrosion resistance were good.
- the average thickness of the coating film of the brazing composition in order to improve the fin joint rate and corrosion resistance in addition to the brazing properties, the average thickness of the coating film of the brazing composition, the maximum thickness of the coating film, and the It became clear that it was important to control the average particle size of the flux within the appropriate range described above.
- Aluminum brazing compositions containing zinc-based flux are used to improve corrosion resistance after brazing.
- the zinc-based flux which has a high specific gravity, settles during storage, so that it is necessary to stir during application, and this sedimentation phenomenon occurs within a relatively short time of application to the aluminum member.
- the brazing composition contains an anti-settling agent comprising a (meth) acrylic acid / (meth) acrylic acid ester-based copolymer emulsion to impart appropriate thixotropic viscosity.
- an anti-settling agent comprising a (meth) acrylic acid / (meth) acrylic acid ester-based copolymer emulsion to impart appropriate thixotropic viscosity.
- it prevents the zinc-based flux from settling, and does not require the trouble of re-stirring at the time of application, and can also achieve uniform application to aluminum members smoothly.
- the addition of a very small amount of anti-settling agent Works.
- the anti-settling agent of the present invention may be componentally common with the organic binder in the brazing composition, but as shown in Examples below, the anti-settling agent of the copolymer constituting the anti-settling agent is used.
- the average molecular weight is larger than that of the organic binder, and the size of the average molecular weight is a guarantee for providing proper thixotropic viscosity.
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Abstract
Description
Claims
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
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US10/517,291 US7534309B2 (en) | 2002-06-17 | 2003-06-16 | Aqueous aluminum brazing composition, aluminum material coated with the brazing composition, brazing method using the aluminum material, and automotive heat exchanger manufactured by using the brazing method |
EP03733433.1A EP1533070B1 (en) | 2002-06-17 | 2003-06-16 | Water-base aluminum-brazing composition and process of brazing |
AU2003241670A AU2003241670A1 (en) | 2002-06-17 | 2003-06-16 | Water-base aluminum-brazing composition and process of brazing |
Applications Claiming Priority (2)
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JP2002175318 | 2002-06-17 | ||
JP2002-175318 | 2002-06-17 |
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WO2003106102A1 true WO2003106102A1 (ja) | 2003-12-24 |
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PCT/JP2003/007604 WO2003106102A1 (ja) | 2002-06-17 | 2003-06-16 | 水系アルミニウムろう付け用組成物、及びろう付け方法 |
Country Status (4)
Country | Link |
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US (1) | US7534309B2 (ja) |
EP (1) | EP1533070B1 (ja) |
AU (1) | AU2003241670A1 (ja) |
WO (1) | WO2003106102A1 (ja) |
Families Citing this family (29)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US9283633B2 (en) | 2003-05-06 | 2016-03-15 | Mitsubishi Aluminum Co. Ltd. | Heat exchanger tube precursor and method of producing the same |
JP4413526B2 (ja) * | 2003-05-06 | 2010-02-10 | 三菱アルミニウム株式会社 | 熱交換器用チューブ |
US8640766B2 (en) | 2003-05-06 | 2014-02-04 | Mitsubishi Aluminum Co., Ltd. | Heat exchanger tube |
DE102008009695B4 (de) | 2007-03-02 | 2023-10-12 | Mahle International Gmbh | Halbzeug |
JP5485539B2 (ja) | 2007-12-18 | 2014-05-07 | 昭和電工株式会社 | 熱交換器用部材の製造方法および熱交換器用部材 |
FR2932666B1 (fr) * | 2008-06-23 | 2013-06-07 | Seb Sa | Dispositif de cuisson d'aliments pourvu d'un fond en acier inoxydable ferritique et d'une cuve en acier inoxydable austenitique ou ferritique. |
DE102009035238A1 (de) * | 2009-07-29 | 2011-02-10 | Behr Gmbh & Co. Kg | Solarkollektor und Verfahren zur Herstellung einer lichtabsorbierenden Oberfläche |
PL2467460T3 (pl) * | 2009-08-18 | 2014-05-30 | Lubrizol Corp | Kompozycja smarująca zawierająca środek przeciwzużyciowy |
US8070047B1 (en) * | 2010-12-02 | 2011-12-06 | Rohm And Haas Electronic Materials Llc | Flux composition and method of soldering |
US8070044B1 (en) * | 2010-12-02 | 2011-12-06 | Rohm And Haas Electronic Materials Llc | Polyamine flux composition and method of soldering |
US8070046B1 (en) * | 2010-12-02 | 2011-12-06 | Rohm And Haas Electronic Materials Llc | Amine flux composition and method of soldering |
US8070045B1 (en) * | 2010-12-02 | 2011-12-06 | Rohm And Haas Electronic Materials Llc | Curable amine flux composition and method of soldering |
US8070043B1 (en) * | 2010-12-02 | 2011-12-06 | Rohm And Haas Electronic Materials Llc | Curable flux composition and method of soldering |
CN103502768B (zh) * | 2011-04-25 | 2016-08-17 | 马勒国际有限公司 | 制造具有增强材料系统的换热器的方法 |
US8434666B2 (en) | 2011-09-30 | 2013-05-07 | Rohm And Haas Electronic Materials Llc | Flux composition and method of soldering |
US8430293B2 (en) | 2011-09-30 | 2013-04-30 | Rohm And Haas Electronic Materials Llc | Curable amine, carboxylic acid flux composition and method of soldering |
US8430295B2 (en) | 2011-09-30 | 2013-04-30 | Rohm And Haas Electronic Materials Llc | Curable flux composition and method of soldering |
US8430294B2 (en) | 2011-09-30 | 2013-04-30 | Rohm And Haas Electronic Materials Llc | Amine, carboxylic acid flux composition and method of soldering |
US8434667B2 (en) | 2011-09-30 | 2013-05-07 | Rohm And Haas Electronic Materials Llc | Polyamine, carboxylic acid flux composition and method of soldering |
JP6090736B2 (ja) * | 2012-10-26 | 2017-03-08 | 株式会社Uacj | アルミニウム合金のろう付方法及びフラックス成分被覆アルミニウム合金部材 |
CN106661677B (zh) | 2014-07-30 | 2018-09-21 | 株式会社Uacj | 铝合金钎焊板 |
CN107073618B (zh) | 2014-12-11 | 2019-05-28 | 株式会社Uacj | 钎焊方法 |
CN104551452B (zh) * | 2014-12-26 | 2017-04-12 | 惠州市强达电子工业有限公司 | 一种水基助焊剂及其制备方法 |
JP6460598B2 (ja) * | 2015-06-24 | 2019-01-30 | 株式会社Uacj | フラックス液 |
JP6186455B2 (ja) | 2016-01-14 | 2017-08-23 | 株式会社Uacj | 熱交換器及びその製造方法 |
JP6312968B1 (ja) | 2016-11-29 | 2018-04-18 | 株式会社Uacj | ブレージングシート及びその製造方法 |
JP7053281B2 (ja) | 2017-03-30 | 2022-04-12 | 株式会社Uacj | アルミニウム合金クラッド材及びその製造方法 |
JP6916715B2 (ja) | 2017-11-08 | 2021-08-11 | 株式会社Uacj | ブレージングシート及びその製造方法 |
WO2020054564A1 (ja) | 2018-09-11 | 2020-03-19 | 株式会社Uacj | ブレージングシートの製造方法 |
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US4413084A (en) * | 1980-10-23 | 1983-11-01 | Ford Motor Company | Paint composition comprising hydroxy functional film former and improved stabilized flow control additive |
US5297721A (en) * | 1992-11-19 | 1994-03-29 | Fry's Metals, Inc. | No-clean soldering flux and method using the same |
US5450666A (en) * | 1994-02-28 | 1995-09-19 | S.A. Day Mfg. Co., Inc. | Flux composition for aluminum brazing |
CA2278285C (en) * | 1997-01-21 | 2003-07-08 | Kansai Paint Company, Limited | Aqueous metallic coating composition and method for forming topcoat |
DE19731151C1 (de) * | 1997-07-21 | 1999-01-21 | Degussa | Lotpaste zum Hartlöten und Beschichten von Aluminium und Aluminiumlegierungen |
JP3337416B2 (ja) * | 1998-02-24 | 2002-10-21 | 株式会社デンソー | ろう付け性に優れた自動車熱交換器用アルミニウム押出多孔偏平管およびその製造方法 |
DE69925239T2 (de) * | 1998-10-14 | 2006-01-19 | Jfe Steel Corp. | Beschichtungszusammensetzung und geschmierte metallbleche |
PL355680A1 (en) * | 1999-11-23 | 2004-05-04 | Norsk Hydro Asa | Aluminium product with excellent brazing characteristics |
DE10016257A1 (de) * | 2000-04-03 | 2001-10-04 | Solvay Fluor & Derivate | Alkalimetallfluorzinkat und seine Herstellung |
JP2002285066A (ja) * | 2001-03-27 | 2002-10-03 | Maabii:Kk | ペイントインク組成物および筆記具 |
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2003
- 2003-06-16 US US10/517,291 patent/US7534309B2/en not_active Expired - Fee Related
- 2003-06-16 EP EP03733433.1A patent/EP1533070B1/en not_active Expired - Lifetime
- 2003-06-16 AU AU2003241670A patent/AU2003241670A1/en not_active Abandoned
- 2003-06-16 WO PCT/JP2003/007604 patent/WO2003106102A1/ja active Application Filing
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EP1029630A1 (en) * | 1998-04-14 | 2000-08-23 | Harima Chemicals, Inc. | Water-base binder for aluminum material brazing, brazing composition, and method of brazing with the composition |
JP2003010964A (ja) * | 2001-06-26 | 2003-01-15 | Denso Corp | アルミニウム熱交換器のろう付け方法およびアルミニウム部材ろう付け用溶液 |
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Also Published As
Publication number | Publication date |
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US7534309B2 (en) | 2009-05-19 |
AU2003241670A1 (en) | 2003-12-31 |
AU2003241670A8 (en) | 2003-12-31 |
EP1533070A4 (en) | 2006-03-08 |
US20060102691A1 (en) | 2006-05-18 |
EP1533070B1 (en) | 2013-05-01 |
EP1533070A1 (en) | 2005-05-25 |
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