WO2007080160A1 - Composition de fondant pour brasage comprenant un lubrifiant - Google Patents

Composition de fondant pour brasage comprenant un lubrifiant Download PDF

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Publication number
WO2007080160A1
WO2007080160A1 PCT/EP2007/050158 EP2007050158W WO2007080160A1 WO 2007080160 A1 WO2007080160 A1 WO 2007080160A1 EP 2007050158 W EP2007050158 W EP 2007050158W WO 2007080160 A1 WO2007080160 A1 WO 2007080160A1
Authority
WO
WIPO (PCT)
Prior art keywords
flux
composition
brazing
aluminium
resin
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/EP2007/050158
Other languages
English (en)
Inventor
Peter Shaw
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Akzo Nobel Coatings International BV
Original Assignee
Akzo Nobel Coatings International BV
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
Priority claimed from EP06100227A external-priority patent/EP1808264A1/fr
Application filed by Akzo Nobel Coatings International BV filed Critical Akzo Nobel Coatings International BV
Priority to EP07703709A priority Critical patent/EP1986812A1/fr
Publication of WO2007080160A1 publication Critical patent/WO2007080160A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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
    • B23K35/24Selection of soldering or welding materials proper
    • B23K35/28Selection of soldering or welding materials proper with the principal constituent melting at less than 950°C
    • 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 or fluxes; Selection of soldering or welding materials, conjoint with selection of non-metallic compositions, both selections being of interest

Definitions

  • compositions comprising a flux, which compositions are sometimes referred to as 'flux compositions'.
  • the invention further relates to the application of such compositions to aluminium comprising substrates, and the use of such compositions in the brazing of aluminium comprising substrates.
  • Aluminium comprising substrates for example aluminium or aluminium alloy comprising sheets, are used to make shaped, or formed, products.
  • parts of (shaped) aluminium comprising substrates are interconnected.
  • One end of a substrate may be interconnected with the other end, or one substrate may be assembled with one or more other substrates.
  • This is commonly done by brazing.
  • a brazing filler metal or brazing alloy, or a composition producing a brazing alloy upon heating is applied to at least one portion of the substrate to be brazed.
  • the melting point of the brazing material is lower than the melting point of the aluminium comprising substrate(s).
  • a flux composition comprises a flux, or fluxing agent, for example an oxyfluoroaluminium, a hydroxyfluoroaluminium, a potassium fluoroaluminate, a fluoroborate, or a fluorozudie.
  • the flux promotes the brazing connection between the aluminium comprising parts.
  • the flux may facilitate the melting of the brazing material, e.g. by removing oxides from the surfaces to be joined, or by preventing the formation of oxides on the surface.
  • flux compositions comprising a synthetic resin which mainly comprises a methacrylate homopolymer, a methacrylate copolymer or a olefin-acrylate copolymer.
  • the flux compositions are applied to a sheet like aluminium or aluminium containing substrates, these substrates are shaped, and after the shaping the brazing takes place.
  • a lubricant e.g. a lubricating oil. This lubricant has to be removed before or after the brazing process.
  • EP 1233345-A2 describes a process in which a surface of an aluminium member is coated with a resin; the aluminium member is subsequently deformed, and then joined with another resin-coated aluminium member. The resin is fused to join the aluminium members.
  • a resin having lubricating properties is used so that the deformation step of the aluminium substrate can be performed without using an additional lubricant.
  • lubricating resins are mentioned (polyester resin, nylon resin, and vinylidene fluoride resin) and normally the bond formed between the aluminium members using a process as described in EP 1233345-A2 will be less strong than the bond formed in a metal brazing process.
  • the present invention relates to flux compositions that can be applied to sheet material for brazing, that can be shaped into various forms without the need to use an additional lubricant.
  • the composition according to the present invention comprises a resin, a wax, and a flux and/or flux-producing compound.
  • a wax is a naturally occurring or synthetic material that is solid at 20 0 C.
  • the melting point a wax normally is at least 40 0 C, and at the melting temperature the material does not decompose.
  • Waxes that are suitable for use in a composition according to the present invention may have a consistency at 20 0 C ranging from soft and plastic to brittle and hard.
  • An advantage of a composition according to the present invention is that the flux composition of the present invention is self lubricating, in other words, the frictional properties are improved.
  • an aluminium comprising substrate which is coated with a flux composition according to the present invention can be deformed without using an additional lubricant.
  • the composition also works as an anti-blocking agent during the deformation.
  • the wax in the composition reduces or eliminates the problem of sticking of the flux composition to the deformation equipment.
  • the use of a flux composition according to the present invention reduces the wear on the deformation equipment.
  • a substrate coated with a flux composition according to the present invention does not need to be cleaned and dried after deforming.
  • Another advantage is the improved scratch and abrasion resistance of the substrate because the composition forms a protective layer, especially during deforming.
  • An applied layer of the composition of the present invention has, optionally after drying, an improved resistance to damage compared to conventional flux compositions.
  • composition according to the present invention is very suitable to be used in a controlled application process. It is relatively easy to obtain a uniform application of the composition of the invention.
  • a uniformly applied flux composition is advantageous as it results in an improved flux distribution.
  • An improved flux distribution is advantageous as it results in an improved joint quality, a reduced rejection rate, and reduced waste when the substrate is brazed.
  • the flux or flux-producing compound in a composition according to the present invention may be chloride comprising, and preferably comprises fluoride.
  • the flux or flux-producing compound is solid at room temperature, more preferably it is added to the composition as a powder.
  • the composition may comprise a mixture of one or more flux compounds and/or one or more flux-producing compounds.
  • potassium fluoride comprising flux compounds
  • potassium fluoride aluminium fluoride (AIF 3 ), caesium fluoride (CsF), rubidium fluoride (RbF), lithium fluoride (LiF), sodium fluoride (NaF), and calcium fluoride (CaF2).
  • Potassium fluoroaluminates such as potassium tetrafluoroaluminate (KAIF 4 ), potassium pentafluoroaluminate (K 2 AIF 5 , K 2 AIF 5 -H 2 O), and potassium hexafluoroaluminate (K 3 AIF 6 ).
  • Oxyfluoroaluminum such as AI 2 F 4 O and AIFO.
  • Hydroxyfluoroaluminium such as AIF 2 (OH), AIF 2 (OH)-H 2 O, and AIF(OH) 2 .
  • Fluoroborates such as potassium tetrafluoroborate (KBF 4 ) and sodium tetrafluoroborate (NaBF 4 ). Examples of such fluxes have been described in GB 899171 -A, GB 1007039-A, and US 4235649.
  • Fluorozineses such as potassium trifluorozinese (KZnF 3 ), potassium tetrafluorozonule (K 2 ZnF 4 ), caesium trifluorozinese (CsZnF 3 ), and caesium tetrafluorozinese (Cs 2 ZnF 4 ). Examples of such fluxes have been described in DE 19913111 -A and WO 9948641 -A.
  • Alkali metal fluorosilicates such as caesium hexafluorosilicate (Cs 2 SiF 6 ), potassium hexafluorosilicate (K 2 SiF 6 ), lithium hexafluorosilicate (Si 2 SiF 6 ), rubidium hexafluorosilicate (Rb 2 SiF 6 ), sodium hexafluorosilicate (Na 2 SiF 6 ), and ammonium hexafluorosilicate ((NH 4 J 2 SiF 6 ).
  • Examples of such fluxes have been described in US 5785770, DE 19636897-A, US 5985233, US 6019856-A, US 5980650, and WO 9810887-A.
  • Alkali bimetal fluorosilicates such as potassium caesium hexafluorosilicate (KCsSiF 6 ), lithium caesium hexafluorosilicate (LiCsSiF 6 ), rubidium caesium hexafluorosilicate (RbCsSiF 6 ), rubidium potassium hexafluorosilicate (RbKSiF 6 ) and ammonium caesium hexafluorosilicate (NH 4 CsSiF 6 ).
  • KsSiF 6 potassium caesium hexafluorosilicate
  • LiCsSiF 6 lithium caesium hexafluorosilicate
  • RbCsSiF 6 rubidium caesium hexafluorosilicate
  • RbKSiF 6 rubidium potassium hexafluorosilicate
  • NH 4 CsSiF 6 ammonium caesium hexaflu
  • Alkali metal bifluorosilicates also referred to as alkali metal hydrofluorosilicates
  • alkali metal hydrofluorosilicates such as caesium hydrofluorosilicate (CsHSiF 6 ), potassium hydrofluorosilicate (KHSiF 6 ), lithium hydrofluorosilicate (LiHSiF 6 ), and ammonium hydrofluorosilicate (NH 4 HSiF 6 ).
  • Caesiumfluoroaluminate complexes such as caesium fluoride (CsF), caesium hexafluoroaluminate (CSsAIF 6 ), caesium tetrafluoroaluminate (CsAIF 4 , CsAIF 4 -H 2 O), and caesium pentafluoroaluminate (CsAIF 5 , CsAIF 5 -H 2 O).
  • Examples of such fluxes have been described in US 4670067, US 5171377, US 5806752, US 5771962, and US 4655385. So-called super-fluid fluxes can be used as well.
  • the composition may comprise fluxes based upon K 2 SiF 6 or KZnF ⁇ . This type of reactive fluxes can produce potassium fluoroaluminate, which acts as a flux material.
  • the composition of the present invention comprises at least one flux or flux- producing compound. It may comprise mixtures of the above-mentioned examples of flux and flux-producing compounds.
  • potassium fluoroaluminate(s) or compound(s) producing potassium fluoroaluminates, or mixtures thereof are used.
  • examples of commercially available potassium fluoroaluminate comprising flux materials can be mentioned: Nocolok ® and Nocolok Sil ® (ex Solvay Chemicals).
  • the composition according to the present invention comprises a resin.
  • this resin is a synthetic resin.
  • the (synthetic) resin comprises as its main constituent, an acrylic acid ester, preperably a methacrylic acid ester.
  • the resin mainly comprises a methacrylate homopolymer or a methacrylate copolymer. It is also possible to use mixtures of such resins.
  • the resin used in the present invention evaporates and/or decomposes during the brazing process, and can thus attain an excellent outward appearance of a brazed portion after brazing, without causing brazing insufficiency such as residual carbon.
  • the resin is a synthetic resin comprising 90-100 wt% of an acrylic acid ester, for example the resin comprises 90-100 wt% polymethyl methacrylate.
  • the resin has a composition which volatilizes in the range of 175- 400 0 C, and preferably below 35O 0 C.
  • the wax in a composition according to the present invention is a wax that evaporates or decomposes during the brazing process, preferably preferably during heat-up in a brazing process, which takes place at a temperature above 450 0 C, and more typically takes place in the range of 500 to 64O 0 C, more typically in the range of 560 to 62O 0 C, when aluminium substrate is involved.
  • the composition according to the present invention comprises at least one wax.
  • a single wax may be used, but it is also possible to use two or more waxes, for example a blend of two or more waxes.
  • the wax may be modified or unmodified. Naturally occurring waxes, such as vegetable waxes or animal waxes, may be used. Additionally, or alternatively, synthetic waxes may be used.
  • the wax is a hydrocarbon wax, i.e. a wax consisting of carbon and hydrogen atoms and no or substantially no other atoms; the hydrocarbon wax preferably consists of more than 90%, even more preferably of more than 95% of carbon and hydrogen atoms.
  • the wax is a polyolefin wax, i.e. a saturated hydrocarbon wax.
  • mixtures of hydrocarbon waxes (a) hydrocarbon wax(es) and (a) polyolefin wax(es) or mixtures of polyolefin waxes are used. and mixtures of hydrocarbon wax(es) and/or polyolefin wax(es) are preferred.
  • the brazing composition according to the present invention may further comprise a brazing material formed by a brazing metal or brazing alloy, or a composition producing a brazing alloy upon heating.
  • the brazing material forms an eutectic alloy or near-eutectic with aluminium upon brazing.
  • the brazing composition may comprise Si, for example Si-particles in powder form, Zn, Cu, or Ge.
  • Other examples are alloys of metals (e.g. Si, Zn, Cu, Sn, Ge) with aluminium or with zinc.
  • Zinc alloys being another frequently used filler metal for brazing.
  • alloys of Si with aluminium can be mentioned AA4047 and AA 4045 (ex Solvay Chemicals).
  • the brazing alloy is an Al-Si alloy having additions of Cu and/or Zn to substantially lower the melting point of the alloy, thereby allowing a brazing operation to be carried out at lower temperatures such as 52O 0 C, 54O 0 C or 56O 0 C.
  • the brazing alloy is an Al-Si-Zn hypereutectic alloy, preferably composed of a powder or mixture of powders, each powder or mixture of powders consisting essentially of one or more of Al, Si or Zn, and wherein in the Al-Si-Zn hypereutectic alloy has a composition such that Si is in a range of 14 to 45 wt.% and the Zn is in a range of 5 to 30 wt.%.
  • a low-melting brazing alloy is used for brazing at a temperature in the range of 520 to 580oC.
  • the brazing alloy comprises 0.001 to 3.0 wt.% of rare-earth element, 20 to 50 wt.% of Zn, 10 wt.% or less of Si, optionally 0.005 to 3.0 wt.% of Ti, and the balance Al and impurities.
  • Ti as optionally present has an effect for preventing a solidification cracking of the brazed connection. All rare-earth elements or a mixture thereof may be employed. Among these elements, misch metal, La, Ce or Sm, which can be obtained at lower cost, are preferably used.
  • the composition may comprise one or more solvents.
  • the composition comprises an organic solvent.
  • a solvent having hydrophilic properties is used.
  • a solvent or mixture of solvents is used that has good polymer solvation and/or application properties.
  • preferred solvents are 2-propanol, 1-propanol, ethylene glycol mono-ethyl ether, di-ethylene glycol mono-ethyl ether, tri-ethylene glycol mono-ethyl ether, ethylene glycol mono- butyl ether, propylene glycol mono-ethyl ether, propylene glycol mono ethyl ether, propylene glycol mono ethyl ether, propylene glycol ester, butan-1-ol, 1 -methyoxy-2- propanol, 4-hydroxy-4-methyl-pentan-2-one, and 1-methoxy-2-propylacetate, or mixtures thereof.
  • Additives may be added to the composition according to the present invention.
  • an anti-oxidant for example, an anti-corrosive agent, an anti-foaming agent, a thickener, a plasticizer, a tackifier, a coupling agent, and the like may be added.
  • mineral oils, paraffin oils, silicone fluids and/or polysiloxane compounds may be added, as these may influence the lubricating / slip properties of the composition.
  • the weight ratio of the flux and/or flux-producing compound(s) to the resin(s) normally is in the range of 1 :2 to 6:1 , preferably in the range of 1 :2 to 3:1 , and highly preferably in the range of 3:2 to 5:2, the weight ratio being calculated on the weight of these components in the uncured coating composition.
  • the ratio of the weight of the wax(es) to the combined weight of the flux and/or flux-producing compound(s) and of the resin(s) normally is in the range of 1 :99 to 30:70, preferably in the range of 1 :99 to 15:85, and highly preferably in the range of 2:98 to 10:90, the weight ratio being calculated on the weight of these components in the uncured coating composition.
  • the ratio of the weight of the dispersion agent(s) to the combined weight of the flux and/or flux-producing compound(s) and of the resin(s) and of the wax(es) normally is in the range of 0.2:99.8 to 10:90, preferably in the range of 0.3:99.7 to 4:96, and highly preferably in the range of 0.4:99.6 to 3:97.
  • a composition is prepared that evaporates and/or decomposes during the brazing process in which process the brazing temperature is within the range of 500 to 700 0 C. In a further embodiment the brazing temperature is within the range of 580 to 640 0 C. In a further embodiment the brazing is performed in an inert atmosphere, e.g. an inert nitrogen atmosphere. Brazing may be performed in batch type furnaces or, more commonly, in continuous tunnel furnaces.
  • the composition according to the present invention can be applied to an aluminium comprising substrate.
  • the composition may be applied by means of a roller coating, a spray method, immersion method, roll-transfer printing, or the like.
  • the solvent preferably is removed partially or completely from the composition after it has been applied to the substrate.
  • the coating may be allowed to dry naturally or may be forced to dry.
  • the applied composition is heated; more preferably, the applied composition is heated until the composition is dry, i.e. until the composition comprises less than 5 weight% of solvent, calculated on the total weight of the dried composition.
  • the substrate may be cleaned or surface treated before the composition is applied.
  • the surface is degreased before the composition is applied.
  • the surface of the substrate is etched using, e.g. an acid or any other etching medium, before the composition is applied.
  • the present invention further relates to a method in which a composition according to the present invention is used in the brazing of aluminium comprising substrates.
  • a composition according to the present invention is applied to (parts of) aluminium comprising substrate(s); optionally one or more substrates are shaped; and brazing is performed.
  • Coating compositions were prepared comprising aluminium potassium fluoride, a methyl methacrylate copolymer, optionally a synthetic hydrocarbon wax, fumed silica, and a mixture of 4-hydroxy-4-methyl-pentan-2-one and 1-methoxy- 2-propyl acetate to adjust the viscosity.
  • compositions were applied to a pre-treated aluminium alloy brazing sheet using a 3 Roll Coater (Reverse Application configuration)at 4 to 8 g/m 2 , sufficient to obtain a dry film thickness of 5 to 10 ⁇ m.
  • the sheets were dryed in a convection oven at a temperature in the range of 200 to 230 0 C.
  • Methyl Methacrylate Copolymer 14 14 Synthetic Wax 2 0

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Paints Or Removers (AREA)

Abstract

L’invention concerne une composition comprenant un fondant ou un composé produisant un fondant, une résine et une cire. L’invention concerne également l’utilisation d’une telle composition pour le brasage d’un substrat comprenant de l’aluminium. Lors de l’utilisation d’une composition selon la présente invention, il n’est pas nécessaire d'utiliser un lubrifiant supplémentaire durant le déformage.
PCT/EP2007/050158 2006-01-11 2007-01-09 Composition de fondant pour brasage comprenant un lubrifiant Ceased WO2007080160A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP07703709A EP1986812A1 (fr) 2006-01-11 2007-01-09 Composition de fondant pour brasage comprenant un lubrifiant

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US75788806P 2006-01-11 2006-01-11
EP06100227.5 2006-01-11
EP06100227A EP1808264A1 (fr) 2006-01-11 2006-01-11 Composition de flux de soudure comportant un lubrifiant
US60/757,888 2006-01-11

Publications (1)

Publication Number Publication Date
WO2007080160A1 true WO2007080160A1 (fr) 2007-07-19

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Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2007/050158 Ceased WO2007080160A1 (fr) 2006-01-11 2007-01-09 Composition de fondant pour brasage comprenant un lubrifiant

Country Status (2)

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EP (1) EP1986812A1 (fr)
WO (1) WO2007080160A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107614191A (zh) * 2015-06-24 2018-01-19 株式会社Uacj 焊剂液
WO2019081690A1 (fr) * 2017-10-27 2019-05-02 Solvay Sa Procédé de brasage amélioré et pièces revêtues de flux
WO2021033624A1 (fr) * 2019-08-20 2021-02-25 ハリマ化成株式会社 Matériau de brasage, élément de brasage et échangeur de chaleur

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3977916A (en) * 1974-12-20 1976-08-31 Chevron Research Company Wax-flux composition containing alkylaryl sulfonic acid for soldering
WO1994029072A1 (fr) * 1993-06-15 1994-12-22 Lexor Technologies Limited Procede de brasage
JPH09314380A (ja) * 1996-05-30 1997-12-09 Sumitomo Light Metal Ind Ltd アルミニウム材料ろう付け用組成物及びろう付け用アルミニウム材料、並びにアルミニウム材料のろう付け方法
US20030203137A1 (en) * 1998-02-24 2003-10-30 Shoei Teshima Aluminum-extruded multi-cavity flat tube having excellent brazing characteristics for use in automotive heat exchanger and manufacturing method therefor

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3977916A (en) * 1974-12-20 1976-08-31 Chevron Research Company Wax-flux composition containing alkylaryl sulfonic acid for soldering
WO1994029072A1 (fr) * 1993-06-15 1994-12-22 Lexor Technologies Limited Procede de brasage
JPH09314380A (ja) * 1996-05-30 1997-12-09 Sumitomo Light Metal Ind Ltd アルミニウム材料ろう付け用組成物及びろう付け用アルミニウム材料、並びにアルミニウム材料のろう付け方法
US20030203137A1 (en) * 1998-02-24 2003-10-30 Shoei Teshima Aluminum-extruded multi-cavity flat tube having excellent brazing characteristics for use in automotive heat exchanger and manufacturing method therefor

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
PATENT ABSTRACTS OF JAPAN vol. 1998, no. 04 31 March 1998 (1998-03-31) *

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107614191A (zh) * 2015-06-24 2018-01-19 株式会社Uacj 焊剂液
EP3299115A4 (fr) * 2015-06-24 2018-12-12 UACJ Corporation Fluide de flux
WO2019081690A1 (fr) * 2017-10-27 2019-05-02 Solvay Sa Procédé de brasage amélioré et pièces revêtues de flux
WO2021033624A1 (fr) * 2019-08-20 2021-02-25 ハリマ化成株式会社 Matériau de brasage, élément de brasage et échangeur de chaleur
JPWO2021033624A1 (fr) * 2019-08-20 2021-02-25
CN114269504A (zh) * 2019-08-20 2022-04-01 哈利玛化成株式会社 硬焊材料、硬焊构件和热交换器
EP4019184A4 (fr) * 2019-08-20 2023-03-15 Harima Chemicals, Incorporated Matériau de brasage, élément de brasage et échangeur de chaleur
US11826859B2 (en) 2019-08-20 2023-11-28 Harima Chemicals, Incorporated Brazing material, brazing member, and heat exchanger
CN114269504B (zh) * 2019-08-20 2024-04-26 哈利玛化成株式会社 硬焊材料、硬焊构件和热交换器
JP7571030B2 (ja) 2019-08-20 2024-10-22 ハリマ化成株式会社 ろう付け材、ろう付け部材および熱交換器

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