WO2012035829A1 - ろう接用ニッケル基塩酸耐食合金 - Google Patents

ろう接用ニッケル基塩酸耐食合金 Download PDF

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Publication number
WO2012035829A1
WO2012035829A1 PCT/JP2011/062094 JP2011062094W WO2012035829A1 WO 2012035829 A1 WO2012035829 A1 WO 2012035829A1 JP 2011062094 W JP2011062094 W JP 2011062094W WO 2012035829 A1 WO2012035829 A1 WO 2012035829A1
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hydrochloric acid
brazing
mass
strength
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PCT/JP2011/062094
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English (en)
French (fr)
Inventor
勝則 乙部
信一 西村
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福田金属箔粉工業株式会社
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Application filed by 福田金属箔粉工業株式会社 filed Critical 福田金属箔粉工業株式会社
Priority to JP2012533889A priority Critical patent/JP5783641B2/ja
Priority to US13/822,597 priority patent/US20130224069A1/en
Priority to EP11824841.8A priority patent/EP2617516A4/en
Priority to KR1020137006458A priority patent/KR101862061B1/ko
Priority to CN2011800429609A priority patent/CN103079752A/zh
Publication of WO2012035829A1 publication Critical patent/WO2012035829A1/ja

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    • 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
    • B23K35/30Selection of soldering or welding materials proper with the principal constituent melting at less than 1550 degrees 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
    • B23K35/24Selection of soldering or welding materials proper
    • B23K35/30Selection of soldering or welding materials proper with the principal constituent melting at less than 1550 degrees C
    • B23K35/3033Ni as the principal constituent
    • B23K35/304Ni as the principal constituent with Cr as the next major 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
    • B23K35/02Rods, 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
    • B23K35/0227Rods, wires
    • 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
    • B23K35/02Rods, 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
    • B23K35/0244Powders, particles or spheres; Preforms made therefrom
    • B23K35/025Pastes, creams, slurries
    • 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
    • B23K35/30Selection of soldering or welding materials proper with the principal constituent melting at less than 1550 degrees C
    • B23K35/3033Ni as the principal constituent
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C1/00Making non-ferrous alloys
    • C22C1/02Making non-ferrous alloys by melting
    • C22C1/023Alloys based on nickel
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C1/00Making non-ferrous alloys
    • C22C1/04Making non-ferrous alloys by powder metallurgy
    • C22C1/0433Nickel- or cobalt-based alloys
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C19/00Alloys based on nickel or cobalt
    • C22C19/03Alloys based on nickel or cobalt based on nickel
    • C22C19/05Alloys based on nickel or cobalt based on nickel with chromium
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C19/00Alloys based on nickel or cobalt
    • C22C19/03Alloys based on nickel or cobalt based on nickel
    • C22C19/05Alloys based on nickel or cobalt based on nickel with chromium
    • C22C19/051Alloys based on nickel or cobalt based on nickel with chromium and Mo or W
    • C22C19/055Alloys based on nickel or cobalt based on nickel with chromium and Mo or W with the maximum Cr content being at least 20% but less than 30%
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C19/00Alloys based on nickel or cobalt
    • C22C19/03Alloys based on nickel or cobalt based on nickel
    • C22C19/05Alloys based on nickel or cobalt based on nickel with chromium
    • C22C19/051Alloys based on nickel or cobalt based on nickel with chromium and Mo or W
    • C22C19/056Alloys based on nickel or cobalt based on nickel with chromium and Mo or W with the maximum Cr content being at least 10% but less than 20%
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C30/00Alloys containing less than 50% by weight of each constituent
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C30/00Alloys containing less than 50% by weight of each constituent
    • C22C30/02Alloys containing less than 50% by weight of each constituent containing copper
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00Making metallic powder or suspensions thereof
    • B22F9/02Making metallic powder or suspensions thereof using physical processes
    • B22F9/06Making metallic powder or suspensions thereof using physical processes starting from liquid material
    • B22F9/08Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying
    • B22F9/082Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying atomising using a fluid
    • 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
    • B23K2101/00Articles made by soldering, welding or cutting
    • B23K2101/04Tubular or hollow articles
    • B23K2101/14Heat exchangers
    • 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
    • B23K35/38Selection of media, e.g. special atmospheres for surrounding the working area
    • 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
    • B23K35/38Selection of media, e.g. special atmospheres for surrounding the working area
    • B23K35/383Selection of media, e.g. special atmospheres for surrounding the working area mainly containing noble gases or nitrogen
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F28HEAT EXCHANGE IN GENERAL
    • F28FDETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
    • F28F19/00Preventing the formation of deposits or corrosion, e.g. by using filters or scrapers
    • F28F19/02Preventing the formation of deposits or corrosion, e.g. by using filters or scrapers by using coatings, e.g. vitreous or enamel coatings
    • F28F19/06Preventing the formation of deposits or corrosion, e.g. by using filters or scrapers by using coatings, e.g. vitreous or enamel coatings of metal
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F28HEAT EXCHANGE IN GENERAL
    • F28FDETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
    • F28F21/00Constructions of heat-exchange apparatus characterised by the selection of particular materials
    • F28F21/08Constructions of heat-exchange apparatus characterised by the selection of particular materials of metal
    • F28F21/081Heat exchange elements made from metals or metal alloys
    • F28F21/087Heat exchange elements made from metals or metal alloys from nickel or nickel alloys
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F28HEAT EXCHANGE IN GENERAL
    • F28FDETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
    • F28F21/00Constructions of heat-exchange apparatus characterised by the selection of particular materials
    • F28F21/08Constructions of heat-exchange apparatus characterised by the selection of particular materials of metal
    • F28F21/089Coatings, claddings or bonding layers made from metals or metal alloys

Definitions

  • the present invention relates to a brazing material for joining various stainless steel members used in various heat exchangers such as general-purpose heat exchangers, EGR (Exhaust Gas Recirculation) coolers, and waste heat recovery devices.
  • the present invention relates to a hydrochloric acid corrosion-resistant alloy for brazing used for joining members requiring hydrochloric acid corrosion resistance.
  • BNi-2, BNi-5, and BNi-7 described in JIS Z 3265: 1998 ⁇ Nickel brazing '' are the most commonly used for joining various stainless steel members. Poor brazing such as wetting, flow and spreading. Moreover, since it contains B, when it brazes, B will approach into the grain boundary of a stainless steel base material, and the intensity
  • the Ni—Cr—Si—P brazing material shown in Patent Document 1 below, the Ni—Cr—B—Si—P based brazing material shown in Patent Document 2, and the Ni—Cr— Cu-Si-P brazing filler metal has an appropriate melting point and bonding strength, and is excellent in brazing properties, but it is not suitable for applications where corrosion resistance to hydrochloric acid is low and hydrochloric acid corrosion resistance is required. is there.
  • Japanese Patent Laid-Open No. 2002-144080 Japanese Unexamined Patent Publication No. 2007-75867 Japanese Unexamined Patent Publication No. 2009-202198
  • Ni brazing materials used in industry require heat resistance / oxidation resistance, corrosion resistance, suitable melting point, brazing property, bonding strength, etc., and there is no brazing material that has all of them.
  • Ni brazing filler metal is used properly.
  • Ni brazing filler metal is widely used in various heat exchangers at present as a brazing filler metal having bonding strength, heat resistance and corrosion resistance.
  • One of the heat exchangers is an EGR cooler for an exhaust gas recirculation system, and the applicable range of the EGR cooler has been expanded from the viewpoint of reducing the environmental load in recent years.
  • the hydrochloric acid corrosion-resistant alloy for brazing of the present invention satisfying all of the above target values (1) to (4) has a composition of mass%, Mo is 6.0 to 18.0%, Cr is 10.0 to 25.0%, and Si is 0.5. It is characterized in that it contains ⁇ 5.0%, P is 4.5 ⁇ 8.0%, the balance is 40.0 ⁇ 73.0% Ni and inevitable impurities, and the total of Si and P is 6.5 ⁇ 10.5%.
  • the inevitable impurities are impurities that are inevitably mixed in the manufacturing process of each raw material even though they are not intentionally added. Examples of such impurities include Mg, S, O, N , V, Zr, Sn, etc., and their total amount is usually 0.3% by mass or less, and does not affect the function of the present invention.
  • the present invention is characterized in that the hydrochloric acid corrosion-resistant alloy for brazing having the above-mentioned characteristics contains 12.0% by mass or less of Cu.
  • the present invention provides a brazing-resistant hydrochloric acid corrosion-resistant alloy having the above-described characteristics.
  • Co is 20.0 mass% or less
  • Fe is 15.0 mass% or less
  • W is 8.0 mass% or less
  • Mn is an additive element that does not affect the characteristics.
  • the total of C, B, Al, Ti, and Nb is 0.5 mass% or less, and the total of these is 20.0 mass% or less.
  • Mo has the effect of improving the corrosion resistance of hydrochloric acid by dissolving in a Ni solid solution serving as a substrate (matrix), but if the content is less than 6.0% by mass (hereinafter referred to as%), a sufficient effect cannot be obtained. On the other hand, if it exceeds 18.0%, a large amount of P and an intermetallic compound are formed and the strength is lowered, and the target bending strength (500 N / mm 2 or more) cannot be obtained. For this reason, the Mo content is set in the range of 6.0 to 18.0%.
  • Cr dissolves in Ni solid solution, improves heat resistance / oxidation resistance and strength, and contributes to the adjustment of melting point. However, if it is less than 10.0%, the target material strength cannot be obtained, and the solidus temperature , The temperature range of the solidus and liquidus widens and melts and separates during brazing. On the other hand, if it exceeds 25.0%, the corrosion resistance to hydrochloric acid is remarkably lowered, so the Cr content is set in the range of 10.0 to 25.0%.
  • Si has the effect of lowering the melting point of the alloy due to the eutectic reaction with Ni.
  • the content is less than 0.5%, sufficient effects cannot be obtained, and the target liquidus temperature (1130 ° C or lower) cannot be achieved. Exceed.
  • it exceeds 5.0% it becomes hypereutectic, the material strength is greatly reduced, and the target bending strength cannot be obtained.
  • the Si content is set in the range of 0.5 to 5.0%.
  • P like Si, lowers the melting point of the alloy by eutectic reaction with Ni and further improves the brazing property. However, if it is less than 4.5%, a sufficient effect is obtained in terms of melting point and brazing property. Absent. Moreover, when it exceeds 8.0%, it will become a hypereutectic, strength will fall significantly, and the target bending strength will not be obtained. Therefore, the content of P is set in the range of 4.5 to 8.0%.
  • the melting point and material strength can be controlled in particular by limiting the amount of Si + P. That is, when Si + P is less than 6.5%, the melting point becomes high and exceeds the target liquidus temperature. Moreover, when Si + P exceeds 10.5%, it becomes hypereutectic and the strength is greatly reduced, and the target bending strength cannot be obtained. For this reason, Si + P is set in the range of 6.5 to 10.5%.
  • Cu is dissolved in Ni solid solution to improve corrosion resistance, but if it exceeds 12.0%, the material strength decreases and the target bending strength cannot be obtained, so Cu was made 12.0% or less.
  • Co is 20.0% or less
  • Fe is 15.0% or less
  • W is 8.0% or less
  • Mn is 5.0% or less
  • C, B, Al Ti and Nb can be contained in total of 0.5% or less, but in order not to impair hydrochloric acid corrosion resistance, melting point, material strength, brazing, Co, Fe, W, Mn, C, B, Al, Ti
  • the upper limit of the total amount of Nb was set to 20.0%.
  • the Ni brazing material of the present invention has the following characteristics, it can be applied to a wide range of uses as a Ni brazing material having hydrochloric acid corrosion resistance.
  • the liquidus temperature is 1130 ° C or lower, brazing using a general-purpose industrial atmospheric furnace is possible.
  • the bending strength is 500 N / mm 2 or more, and it has moderate strength as a Ni brazing material.
  • the area of wetting and spreading after brazing to SUS304 is 110 mm 2 or more, and the brazing material at the time of brazing is well wetted, flows and spreads on the surface of the base material, so the workability in brazing is excellent.
  • the alloy of the present invention is prepared by adjusting and blending Ni as a base and additive components Mo, Cr, Si, and P, and adding Cu, Fe, Co, Mn, etc. to a predetermined mass% as necessary. After the molten metal is completely melted in the crucible of the melting furnace, the molten alloy can be made into a powder by an atomizing method or a melt pulverization method, or cast into a predetermined mold to obtain a rod shape or a plate shape. .
  • the alloy powder produced by the atomizing method is adjusted to a particle size suitable for the intended construction method, but as a method of installing the brazing material of the present invention on a stainless steel base material, a binder and powder are sprinkled and applied to the base material surface ( A method of spraying), a method of applying in the form of a paste in which a binder and powder are mixed, a method of processing and installing into a sheet or foil, a method of spraying and installing powder, and the like can be selected.
  • Example alloys and comparative example alloys of the present invention prepared and mixed as described above were melted, and the melting point (liquidus temperature), bending strength, wetting and spreading properties, and corrosion resistance against hydrochloric acid were evaluated by the following methods. did.
  • melt point (liquidus temperature) measurement 100g of ingot with the composition of each alloy was melted by heating to about 1500 ° C in an argon stream using an electric furnace, and then naturally cooled in the furnace The melting point temperature was measured by a thermal analysis method in which the temperature of the alloy was continuously measured. That is, a thermal analysis curve was drawn on a recorder connected to a thermocouple inserted in the center of the melt, and the liquidus temperature was read from the cooling curve.
  • Table 1 shows examples of the present invention, and Tables 2 and 3 show comparative examples.
  • Comparative Example (e) Si is below the lower limit of the claim and the sum of Si + P is below the lower limit, and in Comparative Example (i), P is above the upper limit of the claim and the sum of Si + P is In all cases, the liquidus temperature does not satisfy the target value, and Comparative Example (i) has low bending strength.
  • Comparative Examples (f) and (j) each additive element is within the scope of the claims, but is outside the scope of claims of Si + P, and the liquidus temperature does not satisfy the target value.
  • Comparative Example (j) does not meet the target for bending strength.
  • Comparative Example (g) Si exceeds the upper limit of the claims, and the bending strength does not satisfy the target value.
  • Comparative Example (h) P is lower than the lower limit of the claims and Ni is higher than the upper limit, the liquidus temperature is high, and the wettability does not satisfy the target value.
  • Comparative Example (k) Cu exceeds the upper limit of the claims and the bending strength is low.
  • Comparative Examples (l) to (o) other additive elements exceed the upper limit of the claims, and in Comparative Example (l), the range of Ni falls below the lower limit. The liquidus temperature, the bending strength, One of the wettability does not satisfy the target value.
  • Comparative Example (A), (B), (C) of the comparative example alloys shown in Table 3 are typical Ni brazing materials defined in JIS Z 3265, and the comparative alloys (D) to (K) Alloys described in Patent Document 1, Patent Document 2, and Patent Document 3, respectively.
  • Comparative Example (A) the weight loss and wetting and spreading states do not satisfy the target values
  • Comparative Example (B) the liquidus temperature, corrosion weight loss, and wetting and spreading properties do not satisfy the target values.
  • Comparative Example (C) has a low bending strength.
  • Comparative Examples (G) and (H) have low bending strength, and all the alloys of Comparative Examples (D) to (K) do not satisfy the target value for corrosion weight loss.
  • the alloys of Examples 1 to 31 of the present invention satisfy the target values for the liquidus temperature, the bending strength, the wet spreadability, and the corrosion weight loss.
  • a nickel brazing material it has an appropriate melting point, material strength, brazing property, and excellent hydrochloric acid corrosion resistance.
  • the alloy of the present invention will be good for austenitic stainless steel, ferritic stainless steel, martensitic stainless steel other than SUS304, and Ni-based heat-resistant alloys and corrosion-resistant alloys such as Inconel and Hastelloy. Shows connectivity.
  • the brazing atmosphere exhibits good brazing even in a reducing hydrogen atmosphere, an inert argon atmosphere, or a nitrogen atmosphere.
  • the example alloys In addition to hydrochloric acid, the example alloys have good corrosion resistance against various acids such as sulfuric acid and nitric acid, and ammonia water. Especially in the example alloys to which Cu is added, the corrosion resistance to sulfuric acid is remarkably improved.
  • the Ni brazing material of the present invention is excellent in melting point, strength, corrosion resistance, and brazing of various stainless steels and Ni alloy members. It can be widely used as a joining material for manufacturing brazing equipment parts such as environment- and energy-related heat exchangers and hot water supply parts.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Powder Metallurgy (AREA)
  • Fuel Cell (AREA)
  • Electric Connection Of Electric Components To Printed Circuits (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)
  • Laminated Bodies (AREA)

Abstract

 各種ステンレス鋼をろう接する際に、実用的な温度(1150℃以下)でのろう接が可能であり、基材に対するろう接性や接合強度が良好で、塩酸に対する耐食性を備えたろう接用塩酸耐食合金を提供する。本発明のろう接用塩酸耐食合金は、質量%でMoを6.0~18.0%、Crを10.0~25.0% 、Siを0.5~5.0%、Pを4.5~8.0%含有し、残部が40.0~73.0%のNiおよび不可避不純物からなり、SiとPの合計は6.5~10.5%である。この際、Cuを12.0%以下含有してもよく、Coを20.0%以下、Feを15.0%以下、Wを8.0%以下、Mnを5.0%以下、C、B、Al、Ti、Nbを合計で0.5%以下含有してもよい。

Description

ろう接用ニッケル基塩酸耐食合金
 本発明は、汎用の熱交換器やEGR(排気ガス再循環、Exhaust Gas Recirculation)クーラー、廃熱回収装置などの各種熱交換器に用いられる各種ステンレス鋼などの部材を接合するろう材に関するものであり、特に塩酸耐食性が要求される部材の接合に用いられるろう接用塩酸耐食合金に関するものである。
 従来、各種ステンレス鋼部材の接合で最もよく使用されているものに、JIS Z 3265:1998「ニッケルろう」に記載されるBNi-2、BNi-5、BNi-7があるが、BNi-2は濡れ、流れおよび拡がりなどのろう接性が悪い。また、Bを含有しているため、ろう接するとステンレス鋼基材の粒界内にBが進入して、基材の強度や耐食性が低下する。BNi-5はろう接性が悪いほか、他のNiろう材と比較して融点が高いため、熱影響によりステンレス基材に変形や劣化などの影響を及ぼす可能性がある。BNi-7は材料強度が低いため、ろう接した場合の接合強度が低いという問題がある。
 また、下記の特許文献1に示されるNi-Cr-Si-P系ろう材、特許文献2に示されるNi-Cr-B-Si-P系ろう材、特許文献3に示されるNi-Cr-Cu-Si-P系ろう材は、適度な融点と接合強度を有し、ろう接性に優れているが、塩酸に対する耐食性が低く、塩酸耐食性が要求される部材への適用には不適当である。
特開2002-144080号公報 特開2007-75867号公報 特開2009-202198号公報
 現在、産業用に使用されている各種Niろう材には、耐熱・耐酸化性、耐食性、適度な融点、ろう接性、接合強度などが要求され、その全てを兼ね備えたろう材が存在しないことから、使用環境に応じてNiろう材は使い分けられている。
 一般に、Niろう材は接合強度と耐熱性および耐食性を備えたろう材として、現在、各種の熱交換器に広く用いられている。そして、その熱交換器のひとつに、排気ガス再循環システム用のEGRクーラーが挙げられ、近年の環境負荷低減の観点から、EGRクーラーの適応範囲が拡大している。
 このEGRクーラーには接合強度と耐酸化性と耐硫化腐食性が要求されるため、現在、BNi-2、BNi-5や特許文献1に示されるNi-Cr-Si-P系ろう材、特許文献2に示されるNi-Cr-B-Si-P系ろう材、特許文献3に示されるNi-Cr-Cu-Si-P系ろう材などが使用されている。しかしながら、その使用環境は、近年厳しさを増しており、特に不純物の多い燃料を使用した場合には、耐酸化性、耐硫化腐食性以外に塩酸腐食が生じるため、塩酸耐食性に優れたNiろう材の開発が課題となっている。
 本発明では、塩酸耐食性に優れたNiろう材の開発を行うための合金組成の検討にあたっては、下記の目標値を設定し、これを全て満足することを条件とした。
(目標値)
 (1) 液相線温度〔融点〕が1130℃以下であること
 (2) 抗折力〔材料強度〕が500N/mm2以上であること
 (3) ろう接性〔SUS304に対する濡れ拡がり試験〕において、ろう付後の濡れ拡がった面積が110mm2以上であること
 (4) 塩酸耐食性〔10%塩酸に対する腐食減量〕が3.0mg/m2・s以下であること
 上記の目標値(1)~(4)を全て満足する本発明のろう接用塩酸耐食合金は、その組成が質量%で、Moを6.0~18.0%、Crを10.0~25.0% 、Siを0.5~5.0%、Pを4.5~8.0%含み、残部が40.0~73.0%のNiおよび不可避不純物からなり、SiとPの合計が6.5~10.5%であることを特徴とする。
 ここで、不可避不純物とは、意図的に添加していないのに、各原料の製造工程等で不可避的に混入する不純物のことであり、このような不純物としては、Mg, S, O, N, V, Zr, Snなどが挙げられ、これらの総量は通常0.3質量%以下であり、本発明の作用に影響を及ぼす程ではない。
 また、本発明は、上記の特徴を有するろう接用塩酸耐食合金において、Cuを12.0質量%以下含有することを特徴とするものでもある。
 さらに、本発明は、上記の特徴を有するろう接用塩酸耐食合金において、特性に影響を及ぼさない添加元素としてCoを20.0質量%以下、Feを15.0質量%以下、Wを8.0質量%以下、Mnを5.0質量%以下、C、B、Al、Ti、Nbの合計が0.5質量%以下で、これらの合計が20.0質量%以下であることを特徴とするものでもある。
 次に、本発明に係わる塩酸耐食合金の各成分範囲を限定した理由を述べる。
 Moは、基質(マトリックス)となるNi固溶体に固溶して、塩酸耐食性を向上させる効果があるが、含有量が6.0質量%(以下、%と記す)未満では十分な効果が得られない。また、18.0%を超えるとPと金属間化合物を多量に形成して強度が低下し、目標とする抗折力(500N/mm2以上)が得られない。このため、Moの含有量は6.0~18.0%の範囲に定めた。
 Crは、Ni固溶体に固溶し、耐熱・耐酸化性や強度を向上させ、さらに融点の調整に寄与するが、10.0%未満では、目標とする材料強度が得られないほか、固相線温度が低くなり、固相線と液相線の温度幅が広がって、ろう接の時に溶け分かれが生じる。また、25.0%を超えると塩酸に対する耐食性が著しく低下するため、Crの含有量は10.0~25.0%の範囲に定めた。
 Siは、Niとの共晶反応により、合金の融点を低下させる効果があるが、含有量が0.5%未満では、十分な効果が得られず、目標の液相線温度(1130℃以下)を超える。また、5.0%を超えると過共晶となり、大幅に材料強度が低下して、目標とする抗折力が得られない。このため、Siの含有量は0.5~5.0%の範囲に定めた。
 PはSiと同様に、Niと共晶反応により、合金の融点を低下させ、さらに、ろう接性を向上させるが、4.5%未満では、融点やろう接性の面で十分な効果が得られない。また、8.0%を超えると過共晶となり、大幅に強度が低下して、目標とする抗折力が得られない。このため、Pの含有量は4.5~8.0%の範囲に定めた。
 さらにSi、Pに関しては、Si+Pの量を限定することで特に融点と材料強度を制御することができる。すなわち、Si+Pが6.5%未満では融点が高くなり、目標とする液相線温度を超える。また、Si+Pが10.5%を超えると、過共晶となり、大幅に強度低下して、目標とする抗折力が得られない。このため、Si+Pは6.5~10.5%の範囲に定めた。
 Cuは、Ni固溶体に固溶して耐食性を向上させるが、12.0%を超えると材料強度が低下して、目標とする抗折力が得られないため、Cuは12.0%以下とした。
 本発明のろう接用塩酸耐食合金において、物性に悪影響を及ぼさない添加元素として、Coを20.0%以下、Feを15.0%以下、Wを8.0%以下、Mnを5.0%以下、C、B、Al、Ti、Nbを合計で0.5%以下含むことができるが、塩酸耐食性、融点、材料強度、ろう接性を損なわないようにするため、Co、Fe、W、Mn、C、B、Al、Ti、Nbの合計量の上限値を20.0%に定めた。
 本発明のNiろう材は、以下の特徴を有しているので、塩酸耐食性を有したNiろう材として広範囲な用途への適応が可能となる。
(1) 液相線温度が1130℃以下であるので、汎用の産業用雰囲気炉を用いたろう接施工が可能である。
(2) 抗折力は500N/mm2以上を有しており、Niろう材として適度な強度を備えている。
(3) SUS304に対するろう付後の濡れ拡がり面積が110mm2以上で、ろう接時のろう材が基材表面で良く濡れ、流れ、拡がるため、ろう接における作業性が優れている。
(4) 10%塩酸(60℃)腐食試験において、腐食減量が3.0mg/m2・s以下であり、塩酸に対する耐食性が優れている。
 本発明の合金は、ベースとなるNiと、添加成分のMo、Cr、Si、Pを調整・配合し、必要に応じてCu、Fe、Co、Mnなどが所定の質量%になるように添加した地金を、溶解炉のルツボ内で完全に溶解した後、溶融合金をアトマイズ法や溶融粉砕法により粉末とするか、所定の型に鋳造して棒状や板状にして、得ることができる。
 特にアトマイズ法で製造した合金粉末は、目的の施工方法に適した粒度に調整されるが、ステンレス鋼基材に本発明ろう材を設置する方法として、基材面にバインダと粉末をふりかけ塗布(散布)する方法、バインダと粉末を混合したペースト状にして塗布する方法、シート状あるいは箔状に加工して設置する方法、粉末を溶射して設置する方法などが選択できる。
 上記のように調整・配合した本発明の実施例合金および比較例合金を溶製し、以下に示す方法で、融点(液相線温度)、抗折力、濡れ拡がり性、塩酸に対する耐食性を評価した。
(1)融点(液相線温度)測定;各合金の配合組成を有する100gの地金を、電気炉を用いアルゴン気流中で約1500℃まで加熱して溶解し、その後、炉内で自然冷却させながら合金の温度を連続的に測定する熱分析法により、融点温度を測定した。即ち、溶湯中央部に挿入した熱電対に連結する記録計に熱分析曲線を描かせ、その冷却曲線から液相線温度を読み取った。
(2)抗折力試験;上記(1)と同じ方法で地金を溶解し、その溶湯を石英ガラス管に鋳造した後、約φ5×35mmに機械加工して、試験片とした。次に、抗折力試験冶具(三点支持、支持間距離25.4mm(JIS Z 2511:2006「金属粉―抗折試験による圧粉体強さ測定方法に記載される冶具」)に試験片を設置し、万能試験機により荷重をかけて破断したときの荷重を測定し、試験片形状と破断荷重から合金の抗折力(N/mm2)を算出した。
(3)濡れ拡がり試験;上記(2)で得られた直径約5mmの丸棒を0.15g(約0.6mm厚さ)となるように切断し、試験片とした。次にアセトンにより脱脂したSUS304ステンレス鋼基材上に試験片を設置し、1150℃で30分間、10-3Pa領域の真空中でろう付熱処理を行った。ろう付熱処理後、ろう材が基材上に、濡れて流れ、拡がった面積を測定し、ろう接性(濡れ拡がり性)を評価した。
評価の指標を下記に示す。
 『ろう付熱処理後の面積≧110mm2:○』
 『ろう付熱処理後の面積<110mm2:×』
(4)10%塩酸における腐食試験;上記(1)と同じ方法で地金を溶解し、その溶湯をシェル鋳型内に鋳造した後、この鋳造片を約10×10×20mmに機械加工して、試験片とした。次に300ccビーカー内に10%塩酸水溶液を用意し、その中に試験片を入れて、全浸漬法による腐食試験を行った。試験条件は、試験温度60℃、試験時間6時間とした。そして、試験前後の単位面積、単位時間あたりの質量減少量を算出して腐食減量(mg/m2・s)とし、塩酸に対する耐食性を評価した。
評価の指標を下記に示す。
 『腐食減量≦3.0mg/m2・s:○』
 『腐食減量>3.0mg/m2・s:×』
 表1に本発明の実施例を、表2および表3に比較例を示す。
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000003
 表2に示す比較例合金の(a)~(o)は、本発明の請求範囲から外れた組成の合金である。比較例(a)はMoが請求範囲の下限を下回り、比較例(d)はCrが請求範囲の上限を上回ったもので、いずれも腐食減量が目標値を満足していない。比較例(b)はMoが請求範囲の上限を上回り、比較例(c)はCrが請求範囲の下限を下回ったもので、いずれも液相線温度が目標値を満足せず、比較例(b)は抗折力も低い。比較例(e)はSiが請求範囲の下限を下回り、且つSi+Pの合計が下限を下回ったもの、比較例(i)はPが請求範囲の上限を上回り、且つSi+Pの合計が上限を上回ったもので、いずれも液相線温度が目標値を満足せず、比較例(i)は抗折力も低い。比較例(f)、(j)は各添加元素は請求の範囲内だが、Si+Pの請求範囲を脱したもので、いずれも液相線温度が目標値を満足せず、比較例(f)は濡れ拡がり性が、比較例(j)は抗折力が目標を満たしていない。比較例(g)はSiが請求範囲の上限を上回り、抗折力が目標値を満足しない。比較例(h)はPが請求範囲の下限を下回り、且つNiの範囲が上限を上回ったもので、液相線温度が高く、濡れ拡がり性が目標値を満足しない。比較例(k)はCuが請求範囲の上限を上回り、抗折力が低い。比較例(l)~(o)はその他の添加元素が請求範囲の上限を上回り、且つ、比較例(l)はNiの範囲が下限を下回ったもので、液相線温度、抗折力、濡れ拡がり性のいずれかが目標値を満足していない。
 表3に示す比較例合金の(A)、(B)、(C)は、JIS Z 3265に規定された代表的なNiろう材であり、比較例合金(D)~(K)は、前記特許文献1、特許文献2、特許文献3にそれぞれ記載された合金である。比較例(A)は腐食減量と濡れ拡がり状態が目標値を満足しておらず、比較例(B)は液相線温度、腐食減量、濡れ拡がり性が目標値を満足していない。また、比較例(C)は抗折力が低い。そして、比較例(G)、(H)は抗折力が低いほか、比較例(D)~(K)の全ての合金は、いずれも腐食減量が目標値を満足していない。
 これに対して、本発明の実施例合金1~31は、表1からも明らかなように、液相線温度、抗折力、濡れ拡がり性と腐食減量のいずれも目標値を満足しており、ニッケルろう材として適度な融点、材料強度、ろう接性を有し、且つ優れた塩酸耐食性を備えている。
 なお、本発明の実施例合金はSUS304以外のオーステナイト系ステンレス鋼やフェライト系ステンレス鋼、マルテンサイト系ステンレス鋼、さらには、インコネルやハステロイなどのNi基耐熱合金・耐食合金に対しても良好なろう接性を示す。
 また、ろう付雰囲気は真空のほか、還元性の水素雰囲気や不活性のアルゴン雰囲気中、あるいは窒素雰囲気でも良好なろう接性を示す。
 さらに、実施例合金は塩酸のほか、硫酸や硝酸など各種の酸やアンモニア水などに対しても良好な耐食性を有しており、特にCuを添加した実施例合金では、硫酸に対する耐食性を著しく向上させる。
 以上、述べたように、本発明のNiろう材は融点、強度、耐食性に優れ、各種ステンレス鋼やNi合金部材のろう付において、ろう接性が良好であることから、EGRクーラーに限らず、広く環境・エネルギー関連の熱交換器や給湯部品などのろう付装置部品を製造するための接合材料として、広く活用できる。

Claims (3)

  1.  Moを6.0~18.0質量%、Crを10.0~25.0質量%、Siを0.5~5.0質量%、Pを4.5~8.0質量%含有し、残部が40.0~73.0質量%のNiおよび不可避不純物からなり、SiとPの合計が6.5~10.5質量%であることを特徴とするろう接用塩酸耐食合金。
  2.  さらにCuを12.0質量%以下の含有量にて含有することを特徴とする請求項1に記載のろう接用塩酸耐食合金。
  3.  特性に影響を及ぼさない元素として、Coを20.0質量%以下、Feを15.0質量%以下、Wを8.0質量%以下、Mnを5.0質量%以下、C、B、Al、Ti、Nbを合計で0.5質量%以下含有し、Co、Fe、W、Mn、C、B、Al、Ti、Nbの合計が20.0質量%以下であることを特徴とする請求項1又は2に記載のろう接用塩酸耐食合金。
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WO2015156066A1 (ja) * 2014-04-11 2015-10-15 福田金属箔粉工業株式会社 耐食性に優れたニッケルろう材
WO2015198790A1 (ja) * 2014-06-26 2015-12-30 日立金属株式会社 ろう付け用Ni基アモルファス合金薄帯、それを用いたステンレス鋼製接合物
JP2018511486A (ja) * 2015-02-17 2018-04-26 ホガナス アクチボラグ (パブル) スーパーオーステナイト鋼をろう付けするための高溶融範囲を有するニッケル基合金
JP2019135328A (ja) * 2019-04-09 2019-08-15 山陽特殊製鋼株式会社 合金粉末
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WO2022249701A1 (ja) * 2021-05-28 2022-12-01 福田金属箔粉工業株式会社 ぬれ広がり性に優れたニッケルろう材

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EP2617516A1 (en) 2013-07-24
KR20130137154A (ko) 2013-12-16
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US20130224069A1 (en) 2013-08-29
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