WO2012081346A1 - Nickel-based brazing filler metal with excellent heat resistance - Google Patents

Nickel-based brazing filler metal with excellent heat resistance Download PDF

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Publication number
WO2012081346A1
WO2012081346A1 PCT/JP2011/076277 JP2011076277W WO2012081346A1 WO 2012081346 A1 WO2012081346 A1 WO 2012081346A1 JP 2011076277 W JP2011076277 W JP 2011076277W WO 2012081346 A1 WO2012081346 A1 WO 2012081346A1
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Prior art keywords
mass
strength
temperature
heat resistance
nickel
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PCT/JP2011/076277
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French (fr)
Japanese (ja)
Inventor
勝則 乙部
敬 河原田
信一 西村
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福田金属箔粉工業株式会社
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Priority to JP2012548703A priority Critical patent/JP5846646B2/en
Publication of WO2012081346A1 publication Critical patent/WO2012081346A1/en

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
    • B23K35/24—Selection of soldering or welding materials proper
    • B23K35/30—Selection of soldering or welding materials proper with the principal constituent melting at less than 1550 degrees C
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
    • B23K35/24—Selection of soldering or welding materials proper
    • B23K35/30—Selection of soldering or welding materials proper with the principal constituent melting at less than 1550 degrees C
    • B23K35/3033—Ni as the principal constituent
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
    • B23K35/24—Selection of soldering or welding materials proper
    • B23K35/30—Selection of soldering or welding materials proper with the principal constituent melting at less than 1550 degrees C
    • B23K35/3033—Ni as the principal constituent
    • B23K35/304—Ni as the principal constituent with Cr as the next major constituent
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C19/00—Alloys based on nickel or cobalt
    • C22C19/03—Alloys based on nickel or cobalt based on nickel
    • C22C19/05—Alloys based on nickel or cobalt based on nickel with chromium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C19/00—Alloys based on nickel or cobalt
    • C22C19/03—Alloys based on nickel or cobalt based on nickel
    • C22C19/05—Alloys based on nickel or cobalt based on nickel with chromium
    • C22C19/051—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C19/00—Alloys based on nickel or cobalt
    • C22C19/03—Alloys based on nickel or cobalt based on nickel
    • C22C19/05—Alloys based on nickel or cobalt based on nickel with chromium
    • C22C19/051—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W
    • C22C19/056—Alloys 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%
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C19/00—Alloys based on nickel or cobalt
    • C22C19/03—Alloys based on nickel or cobalt based on nickel
    • C22C19/05—Alloys based on nickel or cobalt based on nickel with chromium
    • C22C19/051—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W
    • C22C19/057—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W with the maximum Cr content being less 10%
    • 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

Definitions

  • the present invention relates to a brazing material used for heat exchangers such as general-purpose heat exchangers, EGR (Exhaust Gas Recirculation) coolers, waste heat recovery devices, etc., and joining various stainless steel members.
  • the present invention relates to a heat-resistant brazing material applied to joining members requiring heat resistance.
  • nickel brazing materials (BNi-1 to BNi-13) described in AWSSA A5.8 / A5.8M: 2004 have been widely used for joining various stainless steel members that require heat resistance and corrosion resistance.
  • the nickel brazing material excluding BNi-5 and BNi-8 has B and P added as melting point depressing elements, so a low melting intermetallic compound is formed in the brazing layer and the material strength at high temperatures is increased.
  • BNi-5 is widely used for brazing of members that require heat resistance.
  • the operating temperature of the heat exchanger is 900.
  • the temperature may reach around 0 ° C., and BNi-5 has insufficient high-temperature strength.
  • the high temperature strength is primarily determined by the melting point of the material, BNi-8 has a low melting point (particularly the solidus temperature), so that sufficient strength cannot be obtained in a high temperature environment around 900 ° C.
  • the Ni—Cr—Si—Mn brazing material shown in Patent Documents 1 and 2 below can be expected to have high high-temperature strength, but since it contains 34 mass% or more of Cr and Mn in total, the liquid phase A composition with a linear temperature exceeding 1200 ° C is present, which makes it difficult to perform a healthy brazing heat treatment in an industrial general-purpose furnace, and it may react with Si to precipitate an intermetallic compound, thereby deteriorating high-temperature strength. .
  • nickel brazing materials used for industrial use are required to have functions such as heat resistance, corrosion resistance, brazing, bonding strength, and high temperature strength, but there is no brazing material having all of them. Therefore, nickel brazing materials are properly used according to the usage environment.
  • nickel brazing material having bonding strength, heat resistance, and corrosion resistance is widely used for bonding various heat exchangers.
  • One of the heat exchangers is a waste heat recovery device. In response to the recent environmental load reduction, adaptation to the waste heat recovery device is being promoted from the viewpoint of effective use of waste heat.
  • the nickel brazing material excellent in heat resistance according to the present invention satisfying all of the above target values (1) to (4) has a Cr content of 8.0 to 30.0 mass% and a Si content of 7.0 to 13.0 mass. %, W or / and Mo in a total amount of 1.0 to 10.0% by mass, with the balance being Ni and inevitable impurities.
  • the inevitable impurities are impurities that are inevitably mixed in the manufacturing process of each raw material, although not intentionally added. Examples of such impurities include Mg, S, O, and N. , V, Zr, etc. Sn and the like, the sum of these is usually 0.3 mass% or less, not enough affect the operation of the present invention.
  • the present invention also includes 8.0 to 30.0% by mass of Cr, 7.0 to 13.0% by mass of Si, and 5.0 to 30.0% by mass of Co, with the balance being Ni and inevitable impurities. It is also a nickel brazing material characterized by
  • the present invention provides 8.0 to 30.0% by mass of Cr, 7.0 to 13.0% by mass of Si, 1.0 to 10.0% by mass of W or / and Mo, and Co. It is also a nickel brazing material containing 5.0 to 30.0% by mass with the balance being Ni and inevitable impurities.
  • the present invention provides Fe that is 15% by mass or less, Mn and Cu are 5.0% by mass or less as elements that do not affect the characteristics, C, B, Al, Ti, and Nb are each included in an amount of 0.5% by mass or less, and the total of Fe, Mn, Cu, C, B, Al, Ti, and Nb is 20.0% by mass or less. is there.
  • Cr dissolves in a Ni solid solution serving as a substrate (matrix), improves heat resistance and strength, and contributes to the adjustment of the melting point. However, if it is less than 8.0% by mass, heat resistance cannot be obtained. If it exceeds 0.0 mass%, the solidus temperature and the liquidus temperature will rise, resulting in a decrease in high-temperature strength, melting and brazing during brazing heat treatment, and a healthy brazing layer. It becomes impossible. Therefore, the Cr content is set in the range of 8.0 to 30.0% by mass.
  • Si has the effect of lowering the melting point of the alloy due to the eutectic reaction with Ni, but if the content is less than 7.0% by mass, a sufficient effect cannot be obtained and the target liquidus temperature is exceeded. Moreover, when it exceeds 13.0 mass%, it will become a hypereutectic, material strength will fall significantly, and the target bending strength will not be obtained. For this reason, the Si content is set in the range of 7.0 to 13.0 mass%.
  • W and Mo are dissolved in the Ni solid solution and have the effect of improving the material strength, particularly the strength at high temperatures.
  • the total content of W and Mo is less than 1.0% by mass, a sufficient effect is obtained. Absent. Moreover, when it exceeds 10.0 mass%, it will become a hypereutectic composition, intensity
  • Co has an effect of increasing the melting point by dissolving in a solid solution of Ni, but if the content is less than 5.0% by mass, a sufficient effect cannot be obtained, and if it exceeds 30.0% by mass, the melting point increases. Over the target liquidus temperature. Therefore, the Co content is set in the range of 5.0 to 30.0% by mass.
  • Fe is 15.0% by mass or less
  • Mn is 5.0% by mass or less
  • Each of them can be contained in an amount of 0.5% by mass or less, but in order not to impair the melting point, material strength and brazing property, the upper limit of the total of Fe, Mn, Cu, C, B, Al, Ti, Nb is 20 0.0% by mass.
  • the nickel brazing material of the present invention has the following characteristics, it can be applied to a wide range of applications as a nickel brazing material that can be expected to have high-temperature strength.
  • the solidus temperature is 1050 ° C. or higher, it can be used even in a high temperature environment of around 900 ° C.
  • the liquidus temperature is 1200 ° C. or less, brazing using a general-purpose atmosphere furnace is possible.
  • the bending strength is 1000 N / mm 2 or more, and it has high material strength as a nickel brazing material.
  • the tensile fracture strength at 900 ° C. is higher than BNi-5 (70.5 MPa), and the material strength at high temperature is excellent.
  • the alloy of the present invention is prepared by adjusting and blending Ni as a base and additive components Cr, Si, W, Mo, Co, and adding Fe, Mn, Cu, 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 substrate, it is applied in the form of a paste in which a binder and powder are mixed. Or a method of printing, a method of applying (spreading) a binder and powder on the surface of a substrate, a method of processing and installing in a sheet or foil, a method of spraying and installing a powder, and the like.
  • Example alloys and comparative example alloys of the present invention prepared and mixed as described above are melted, and the melting point (solidus temperature, liquidus temperature), bending strength, and high temperature strength are evaluated by the following methods. did.
  • the indicators are as follows: “ ⁇ ”: Strength exceeding BNi-5 (75 MPa or more) “ ⁇ ”: same strength as BNi-5 (65 MPa or more and less than 75 MPa) “ ⁇ ”: Strength less than BNi-5 (less than 65 MPa)
  • Comparative Example (a) has Cr below the lower limit of the claims, (b) has Cr above the upper limit of the claims, (c) has Si below the lower limit of the claims, (d) Is that Si exceeds the upper limit of the claims, (e) is that both W and Co are below the lower limit of the claims, (f) is that Mo exceeds the upper limit of the claims, and (g) is Mo And Co are both below the lower limit of the claims, (h) is Co exceeds the upper limit of the claims, (i) is Fe exceeds the upper limit of the claims, (j) is Cu, (k) is the total amount of Fe and Fe, Mn and Ti, (l) is B, (m) is C and (n) is Al exceeding the upper limit of the claims, and the melting point (solid Any of the phase wire temperature, liquidus temperature), bending strength, and high temperature strength does not satisfy the target value.
  • (A) to (M) of the comparative example alloys shown in Table 3 are general-purpose nickel brazing materials defined in AWSA A5.8 / A5.8M: 2004, and the comparative alloys (N) to (P) are These are prior art alloys described in Patent Documents 1 and 2, respectively.
  • Comparative Examples (A) to (M), which are general-purpose nickel brazing materials, except for (E) and (I) the solidus temperature is low, and the high temperature strength is lower than the target value. Further, (I) satisfies the target value of the melting point but has a low bending strength, and (E) satisfies the target values of both the melting point and the bending strength, but does not have a high temperature strength higher than BNi-5.
  • Example Alloys 1 to 16 of the present invention have target values for melting point (solidus temperature, liquidus temperature), bending strength, and high-temperature strength. They are satisfied, have a suitable melting point, material strength, brazing property as a nickel brazing material, and have excellent high temperature strength.
  • the nickel brazing material of the present invention has an excellent melting point and material strength and maintains a high strength even in a high temperature environment of 900 ° C. Therefore, not only the waste heat recovery device but also the heat related to the environment and energy. It can be widely used as a joining material for producing brazing device parts such as exchangers and hot water supply parts.

Abstract

Provided is a heat-resistant brazing filler metal which is to be used in various kinds of heat exchangers and is suitable for joining stainless steel members or the like, particularly members that are required to be resistant to heat. A nickel-based brazing filler metal with excellent heat resistance, characterized by containing 8.0 to 30.0 mass% of Cr, 7.0 to 13.0 mass% of Si, and 1.0 to 10.0 mass% (in total) of W and/or Mo, with the balance being Ni and unavoidable impurities, and further containing, as elements having no influence on the characteristics, at most 15.0 mass% of Fe, at most 5.0 mass% of Mn, at most 5.0 mass% of Cu, and C, B, Al, Ti and Nb each in an amount of 0.5 mass% or less, the sum total of Fe, Mn, Cu, C, B, Al, Ti and Nb being 20.0 mass% or less.

Description

耐熱性に優れたニッケルろう材Nickel brazing material with excellent heat resistance
　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、廃熱回収装置などの熱交換器に用いられて、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、耐熱性が要求される部材の接合に適用される耐熱ろう材に関するものである。 The present invention relates to a brazing material used for heat exchangers such as general-purpose heat exchangers, EGR (Exhaust Gas Recirculation) coolers, waste heat recovery devices, etc., and joining various stainless steel members. In particular, the present invention relates to a heat-resistant brazing material applied to joining members requiring heat resistance.
　従来、耐熱性や耐食性が要求される各種ステンレス鋼部材の接合には、ＡＷＳＡ　Ａ５．８／Ａ５．８Ｍ：２００４に記載のニッケルろう材（ＢＮｉ－１～ＢＮｉ－１３）が広く適用されている。しかし、ＢＮｉ－５とＢＮｉ－８を除いたニッケルろう材は、融点降下元素としてＢやＰが添加されているため、ろう付層に低融点の金属間化合物が生成して、高温における材料強度が低いという問題を抱えている。こうしたことから、耐熱性が要求される部材のろう接にはＢＮｉ－５が広く使用されているが、近年の環境負荷低減や熱交換効率の向上要求を受け、熱交換器の使用温度が９００℃前後に達する場合もあり、ＢＮｉ－５においても高温強度が不十分となっている。また、高温強度は第一義的には材料の融点によって決まるため、ＢＮｉ－８は融点（特に固相線温度）が低いことから、９００℃前後の高温環境では十分な強度が得られない。 Conventionally, nickel brazing materials (BNi-1 to BNi-13) described in AWSSA A5.8 / A5.8M: 2004 have been widely used for joining various stainless steel members that require heat resistance and corrosion resistance. . However, the nickel brazing material excluding BNi-5 and BNi-8 has B and P added as melting point depressing elements, so a low melting intermetallic compound is formed in the brazing layer and the material strength at high temperatures is increased. Have the problem of low. For this reason, BNi-5 is widely used for brazing of members that require heat resistance. However, in response to recent demands for reducing environmental impact and improving heat exchange efficiency, the operating temperature of the heat exchanger is 900. The temperature may reach around 0 ° C., and BNi-5 has insufficient high-temperature strength. In addition, since the high temperature strength is primarily determined by the melting point of the material, BNi-8 has a low melting point (particularly the solidus temperature), so that sufficient strength cannot be obtained in a high temperature environment around 900 ° C.
　一方、下記の特許文献１や２に示されるＮｉ－Ｃｒ－Ｓｉ－Ｍｎ系のろう材は、高い高温強度が期待できるが、ＣｒとＭｎを合計で３４質量％以上含有することから、液相線温度が１２００℃を超える組成が存在して、工業用の汎用炉による健全なろう付熱処理が困難となるほか、Ｓｉと反応して金属間化合物を析出し、高温強度を劣化させる場合がある。 On the other hand, the Ni—Cr—Si—Mn brazing material shown in Patent Documents 1 and 2 below can be expected to have high high-temperature strength, but since it contains 34 mass% or more of Cr and Mn in total, the liquid phase A composition with a linear temperature exceeding 1200 ° C is present, which makes it difficult to perform a healthy brazing heat treatment in an industrial general-purpose furnace, and it may react with Si to precipitate an intermetallic compound, thereby deteriorating high-temperature strength. .
特開2005-224818号公報JP 2005-224818 特開2004-42091号公報JP 2004-42091 A
　現在、産業用に使用されている各種ニッケルろう材には、耐熱性、耐食性、ろう接性、接合強度と、高温強度などの機能が要求されるが、その全てを兼ね備えたろう材は存在しない。そこで、使用環境に応じてニッケルろう材は使い分けられている。 Currently, various types of nickel brazing materials used for industrial use are required to have functions such as heat resistance, corrosion resistance, brazing, bonding strength, and high temperature strength, but there is no brazing material having all of them. Therefore, nickel brazing materials are properly used according to the usage environment.
　一般に、接合強度と耐熱性および耐食性を備えたニッケルろう材は、各種の熱交換器の接合に広く用いられている。そして、その熱交換器のひとつに、廃熱回収装置が挙げられ、近年の環境負荷低減を受け、廃熱の有効利用の観点から廃熱回収装置への適応が進められている。 Generally, nickel brazing material having bonding strength, heat resistance, and corrosion resistance is widely used for bonding various heat exchangers. One of the heat exchangers is a waste heat recovery device. In response to the recent environmental load reduction, adaptation to the waste heat recovery device is being promoted from the viewpoint of effective use of waste heat.
　この廃熱回収装置用熱交換器には、特に耐熱性と高温強度が要求されるため、現在、ＢＮｉ－５が使用されている。しかしながら、この使用環境は近年厳しさを増しており、使用温度が９００℃前後に達していることから、ＢＮｉ－５でも高温強度が不十分となってきており、より耐熱性、高温強度に優れたニッケルろう材の開発が課題となっている。 Since this heat exchanger for waste heat recovery equipment is particularly required to have heat resistance and high temperature strength, BNi-5 is currently used. However, this environment has become increasingly severe in recent years, and since the operating temperature has reached around 900 ° C, the high-temperature strength has become insufficient even with BNi-5, and it is more excellent in heat resistance and high-temperature strength. The development of nickel brazing filler metal has become an issue.
　本発明では、耐熱性と高温強度に優れたニッケルろう材の開発を行うための合金組成の検討にあたり、下記の目標値を設定して、これを全て満足することを条件とした。
（目標値）
　(１) 固相線温度〔融点〕が１０５０℃以上であること
　(２) 液相線温度〔融点〕が１２００℃以下であること
　(３) 抗折力〔材料強度〕が１０００Ｎ/ｍｍ2以上であること
　(４) ９００℃における材料強度がＢＮｉ－５より優れていること In the present invention, in studying the alloy composition for developing a nickel brazing material excellent in heat resistance and high-temperature strength, the following target values were set, and all of them were satisfied.
(Target value)
(1) Solidus temperature [melting point] is 1050 ° C. or higher (2) Liquidus temperature [melting point] is 1200 ° C. or lower (3) Folding force [material strength] is 1000 N / mm 2 or higher (4) Material strength at 900 ° C is superior to BNi-5.
　上記の目標値(１)～(４)を全て満足する本発明の耐熱性に優れたニッケルろう材は、Ｃｒを８．０～３０．０質量％、Ｓｉを７．０～１３．０質量％ 、Ｗもしくは／およびＭｏを合計で１．０～１０．０質量％含み、残部がＮｉおよび不可避不純物からな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、これらの総和は通常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。 The nickel brazing material excellent in heat resistance according to the present invention satisfying all of the above target values (1) to (4) has a Cr content of 8.0 to 30.0 mass% and a Si content of 7.0 to 13.0 mass. %, W or / and Mo in a total amount of 1.0 to 10.0% by mass, with the balance being Ni and inevitable impurities.
Here, the inevitable impurities are impurities that are inevitably mixed in the manufacturing process of each raw material, although not intentionally added. Examples of such impurities include Mg, S, O, and N. , V, Zr, etc. Sn and the like, the sum of these is usually 0.3 mass% or less, not enough affect the operation of the present invention.
　また、本発明は、Ｃｒを８．０～３０．０質量％、Ｓｉを７．０～１３．０質量％ 、Ｃｏを５．０～３０．０質量％含み、残部がＮｉおよび不可避不純物からなることを特徴とするニッケルろう材でもある。 The present invention also includes 8.0 to 30.0% by mass of Cr, 7.0 to 13.0% by mass of Si, and 5.0 to 30.0% by mass of Co, with the balance being Ni and inevitable impurities. It is also a nickel brazing material characterized by
　また、本発明は、Ｃｒを８．０～３０．０質量％、Ｓｉを７．０～１３．０質量％ 、Ｗもしくは／およびＭｏを合計で１．０～１０．０質量％、Ｃｏを５．０～３０．０質量％含み、残部がＮｉおよび不可避不純物からなることを特徴とするニッケルろう材でもある。 Further, the present invention provides 8.0 to 30.0% by mass of Cr, 7.0 to 13.0% by mass of Si, 1.0 to 10.0% by mass of W or / and Mo, and Co. It is also a nickel brazing material containing 5.0 to 30.0% by mass with the balance being Ni and inevitable impurities.
　さらに、本発明は、上記の特徴を有する耐熱性に優れたニッケルろう材において、特性に影響を及ぼさない元素としてＦｅを１５質量％以下、Ｍｎ、Ｃｕをそれぞれ５．０質量％以下、Ｃ、Ｂ、Ａｌ、Ｔｉ、Ｎｂをそれぞれ０．５質量％以下含み、Ｆｅ、Ｍｎ、Ｃｕ、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ものでもある。 Furthermore, in the nickel brazing material having the above characteristics and excellent heat resistance, the present invention provides Fe that is 15% by mass or less, Mn and Cu are 5.0% by mass or less as elements that do not affect the characteristics, C, B, Al, Ti, and Nb are each included in an amount of 0.5% by mass or less, and the total of Fe, Mn, Cu, C, B, Al, Ti, and Nb is 20.0% by mass or less. is there.
　次に、本発明に係わる耐熱ろう材の各成分範囲を限定した理由を述べる。 Next, the reason why the component ranges of the heat-resistant brazing material according to the present invention are limited will be described.
　Ｃｒは、基質（マトリックス）となるＮｉ固溶体に固溶して、耐熱性や強度を向上させ、さらに融点の調整に寄与するが、８．０質量％未満では、耐熱性が得られず、３０．０質量％を超えると固相線温度の低下や液相線温度の上昇が生じて、高温強度の低下やろう付熱処理での溶け分れ、未溶融が生じ、健全なろう付層が得られなくなる。したがって、Ｃｒの含有量は８．０～３０．０質量％の範囲に定めた。 Cr dissolves in a Ni solid solution serving as a substrate (matrix), improves heat resistance and strength, and contributes to the adjustment of the melting point. However, if it is less than 8.0% by mass, heat resistance cannot be obtained. If it exceeds 0.0 mass%, the solidus temperature and the liquidus temperature will rise, resulting in a decrease in high-temperature strength, melting and brazing during brazing heat treatment, and a healthy brazing layer. It becomes impossible. Therefore, the Cr content is set in the range of 8.0 to 30.0% by mass.
　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７．０質量％未満では、十分な効果が得られず、目標の液相線温度を超える。また、１３．０質量％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７．０～１３．０質量％の範囲に定めた。 Si has the effect of lowering the melting point of the alloy due to the eutectic reaction with Ni, but if the content is less than 7.0% by mass, a sufficient effect cannot be obtained and the target liquidus temperature is exceeded. Moreover, when it exceeds 13.0 mass%, it will become a hypereutectic, material strength will fall significantly, and the target bending strength will not be obtained. For this reason, the Si content is set in the range of 7.0 to 13.0 mass%.
　ＷおよびＭｏは、Ｎｉ固溶体に固溶して、材料強度、特に高温における強度を向上させる効果があるが、ＷとＭｏの含有量が合計で１．０質量％未満では十分な効果が得られない。また、１０．０質量％を超えると過共晶組成となり、強度が低下し、目標とする抗折力が得られない。このため、Ｗ、Ｍｏの含有量は合計で１．０～１０．０質量％の範囲に定めた。 W and Mo are dissolved in the Ni solid solution and have the effect of improving the material strength, particularly the strength at high temperatures. However, if the total content of W and Mo is less than 1.0% by mass, a sufficient effect is obtained. Absent. Moreover, when it exceeds 10.0 mass%, it will become a hypereutectic composition, intensity | strength will fall, and the target bending strength will not be obtained. Therefore, the total content of W and Mo is set in the range of 1.0 to 10.0% by mass.
　Ｃｏは、Ｎｉ固溶体に固溶して、融点を上昇させる効果があるが、含有量が５．０質量％未満では、十分な効果が得られず、３０．０質量％を超えると融点が上昇し、目標の液相線温度を超える。このため、Ｃｏの含有量は５．０～３０．０質量％の範囲に定めた。 Co has an effect of increasing the melting point by dissolving in a solid solution of Ni, but if the content is less than 5.0% by mass, a sufficient effect cannot be obtained, and if it exceeds 30.0% by mass, the melting point increases. Over the target liquidus temperature. Therefore, the Co content is set in the range of 5.0 to 30.0% by mass.
　本発明の耐熱ろう材においては、物性に悪影響を及ぼさない添加元素として、Ｆｅを１５．０質量％以下、Ｍｎ、Ｃｕをそれぞれ５．０質量％以下、Ｃ、Ｂ、Ａｌ、Ｔｉ、Ｎｂをそれぞれ０．５質量％以下含むことができるが、融点や材料強度、ろう接性を損なわないようにするため、Ｆｅ、Ｍｎ、Ｃｕ、Ｃ、Ｂ、Ａｌ、Ｔｉ、Ｎｂの合計の上限を２０．０質量％に定めた。 In the heat-resistant brazing material of the present invention, as additive elements that do not adversely affect the physical properties, Fe is 15.0% by mass or less, Mn, Cu is 5.0% by mass or less, C, B, Al, Ti, Nb, respectively. Each of them can be contained in an amount of 0.5% by mass or less, but in order not to impair the melting point, material strength and brazing property, the upper limit of the total of Fe, Mn, Cu, C, B, Al, Ti, Nb is 20 0.0% by mass.
　本発明のニッケルろう材は、以下の特徴を有しているので、高温強度が期待できるニッケルろう材として広範囲な用途への適応が可能となる。
　(１) 固相線温度が１０５０℃以上であるので、９００℃前後の高温環境においても対応が可能である。
　(２) 液相線温度が１２００℃以下であるので、汎用の雰囲気炉を用いたろう接施工が可能である。
　(３) 抗折力は１０００Ｎ／ｍｍ2以上を有しており、ニッケルろう材として高い材料強度を備えている。
　(４) ９００℃における引張破断強度がＢＮｉ－５（７０．５ＭＰａ）より高く、高温における材料強度に優れている。 Since the nickel brazing material of the present invention has the following characteristics, it can be applied to a wide range of applications as a nickel brazing material that can be expected to have high-temperature strength.
(1) Since the solidus temperature is 1050 ° C. or higher, it can be used even in a high temperature environment of around 900 ° C.
(2) Since the liquidus temperature is 1200 ° C. or less, brazing using a general-purpose atmosphere furnace is possible.
(3) The bending strength is 1000 N / mm 2 or more, and it has high material strength as a nickel brazing material.
(4) The tensile fracture strength at 900 ° C. is higher than BNi-5 (70.5 MPa), and the material strength at high temperature is excellent.
　本発明の合金は、ベースとなるＮｉと、添加成分のＣｒ、Ｓｉ、Ｗ、Ｍｏ、Ｃｏを調整・配合し、必要に応じてＦｅ、Ｍｎ、Ｃｕ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。 The alloy of the present invention is prepared by adjusting and blending Ni as a base and additive components Cr, Si, W, Mo, Co, and adding Fe, Mn, Cu, 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. .
　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、バインダと粉末を混合したペースト状にして塗布や印刷する方法、基材面にバインダと粉末をふりかけて塗布（散布）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。 In particular, 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 substrate, it is applied in the form of a paste in which a binder and powder are mixed. Or a method of printing, a method of applying (spreading) a binder and powder on the surface of a substrate, a method of processing and installing in a sheet or foil, a method of spraying and installing a powder, and the like.
　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（固相線温度、液相線温度）、抗折力、高温強度を評価した。 Example alloys and comparative example alloys of the present invention prepared and mixed as described above are melted, and the melting point (solidus temperature, liquidus temperature), bending strength, and high temperature strength are evaluated by the following methods. did.
(１) 固相線温度測定；各合金の配合組成を有する１００ｇの地金を、電気炉を用いてアルゴンガス気流中で約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、その冷却曲線から固相線温度を読み取った。 (1) Measurement of solidus temperature: 100 g of metal having a composition of each alloy is melted by heating to about 1500 ° C. in an argon gas 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 molten metal, and the solidus temperature was read from the cooling curve.
(２) 液相線温度測定；上記(１)と同様の方法で熱分析曲線を得、液相線温度を読み取った。 (2) Liquid phase line temperature measurement: A thermal analysis curve was obtained in the same manner as in (1) above, and the liquidus temperature was read.
(３) 抗折力測定；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　Ｚ２５１１：２００６記載の冶具)）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を算出した。 (3) Measurement of bending strength: After the metal was melted by the same method as (1) above, the molten metal was cast into a quartz glass tube and then machined to about φ5 × 35 mm to obtain a test piece. Next, a test piece is placed on a bending strength test jig (three-point support, distance between supports 25.4 mm (a jig described in JIS Z2511: 2006)), and the load when the load is broken by a universal testing machine is measured. Measured, and the bending strength of the alloy was calculated from the shape of the specimen and the breaking load.
(４) 高温引張強度測定；上記(１) と同じ方法で地金を溶解し、その溶湯を黒鉛鋳型に鋳造し、６５０℃で５ｈｒ歪除去の熱処理を実施した後、ＪＩＳ４号に準拠した形状に機械加工して、試験片とした。次に高温用大気炉を併設した島津製作所（株）製オートグラフ試験機を用いて、９００℃における引張試験を行い、破断時の強度と試験片断面積より、引張破断強度を測定した。
指標は以下の通り
　「○」：BNi-5を超える強度（７５ＭＰａ以上）
　「△」：BNi-5と同程度の強度（６５ＭＰａ以上７５ＭＰａ未満）
　「×」：BNi-5未満の強度（６５ＭＰａ未満） (4) High temperature tensile strength measurement: Melting the metal in the same manner as in (1) above, casting the molten metal into a graphite mold, performing heat treatment for removing strain for 5 hours at 650 ° C, and then conforming to JIS No. 4 To obtain a test piece. Next, a tensile test at 900 ° C. was performed using an autograph tester manufactured by Shimadzu Corporation equipped with a high-temperature atmospheric furnace, and the tensile strength at break was measured from the strength at break and the cross-sectional area of the test piece.
The indicators are as follows: “◯”: Strength exceeding BNi-5 (75 MPa or more)
“△”: same strength as BNi-5 (65 MPa or more and less than 75 MPa)
“×”: Strength less than BNi-5 (less than 65 MPa)
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
　表２に示す比較例合金の(ａ)～(ｎ)は、本発明の請求範囲外組成の合金である。比較例(ａ)はＣｒが請求範囲の下限を下回ったもの、(ｂ)はＣｒが請求範囲の上限を超えたもの、(ｃ)はＳｉが請求範囲の下限を下回ったもの、(ｄ)はＳｉが請求範囲の上限を超えたもの、(ｅ)はＷとＣｏが共に請求範囲の下限を下回ったもの、(ｆ)はＭｏが請求範囲の上限を超えたもの、(ｇ)はＭｏとＣｏが共に請求範囲の下限を下回ったもの、(ｈ)はＣｏが請求範囲の上限を超えたもの、(ｉ)はＦｅが請求範囲の上限を超えたもの、(ｊ)はＣｕが、(ｋ)はＦｅ且つＦｅとＭｎとＴｉの合計量が、(ｌ)はＢが、(ｍ)はＣが、(ｎ)はＡｌが請求範囲の上限を超えたものであり、融点（固相線温度、液相線温度）、抗折力、高温強度のいずれかが目標値を満足していない。 (A) to (n) of comparative example alloys shown in Table 2 are alloys having compositions outside the scope of claims of the present invention. Comparative Example (a) has Cr below the lower limit of the claims, (b) has Cr above the upper limit of the claims, (c) has Si below the lower limit of the claims, (d) Is that Si exceeds the upper limit of the claims, (e) is that both W and Co are below the lower limit of the claims, (f) is that Mo exceeds the upper limit of the claims, and (g) is Mo And Co are both below the lower limit of the claims, (h) is Co exceeds the upper limit of the claims, (i) is Fe exceeds the upper limit of the claims, (j) is Cu, (k) is the total amount of Fe and Fe, Mn and Ti, (l) is B, (m) is C and (n) is Al exceeding the upper limit of the claims, and the melting point (solid Any of the phase wire temperature, liquidus temperature), bending strength, and high temperature strength does not satisfy the target value.
　表３に示す比較例合金の(Ａ)～(Ｍ)は、ＡＷＳＡ　Ａ５．８／Ａ５．８Ｍ：２００４に規定された汎用のニッケルろう材であり、比較例合金(Ｎ)～(Ｐ)は、前記特許文献１及び２にそれぞれ記載された先行技術合金である。汎用ニッケルろう材である比較例(Ａ)～(Ｍ)は、(Ｅ)と(Ｉ)を除き固相線温度が低いほか、いずれも高温強度が目標値より低い。また、(Ｉ)は融点の目標値を満足するが抗折力は低く、(Ｅ)は融点、抗折力ともに目標値を満足するが、ＢＮｉ－５以上の高温強度を有しない。一方、先行技術合金の比較例(Ｎ)～(Ｐ)のうち、(Ｎ)については抗折力を満足するが、いずれの合金も液相線温度が目標値より高く、(Ｏ)及び(Ｐ)は、高温強度が低い。 (A) to (M) of the comparative example alloys shown in Table 3 are general-purpose nickel brazing materials defined in AWSA A5.8 / A5.8M: 2004, and the comparative alloys (N) to (P) are These are prior art alloys described in Patent Documents 1 and 2, respectively. In Comparative Examples (A) to (M), which are general-purpose nickel brazing materials, except for (E) and (I), the solidus temperature is low, and the high temperature strength is lower than the target value. Further, (I) satisfies the target value of the melting point but has a low bending strength, and (E) satisfies the target values of both the melting point and the bending strength, but does not have a high temperature strength higher than BNi-5. On the other hand, among the comparative examples (N) to (P) of the prior art alloys, although (N) satisfies the bending strength, the liquidus temperature of each alloy is higher than the target value, and (O) and ( P) has low high-temperature strength.
　これに対して、本発明の実施例合金１～１６は、表１からも明らかなように、融点（固相線温度、液相線温度）、抗折力、高温強度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、且つ優れた高温強度を備えている。 On the other hand, as is clear from Table 1, Example Alloys 1 to 16 of the present invention have target values for melting point (solidus temperature, liquidus temperature), bending strength, and high-temperature strength. They are satisfied, have a suitable melting point, material strength, brazing property as a nickel brazing material, and have excellent high temperature strength.
　以上に述べたように、本発明のニッケルろう材は融点、材料強度に優れ、９００℃の高温環境においても高い強度を維持することから、廃熱回収装置に限らず、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、広く活用することが可能である。 As described above, the nickel brazing material of the present invention has an excellent melting point and material strength and maintains a high strength even in a high temperature environment of 900 ° C. Therefore, not only the waste heat recovery device but also the heat related to the environment and energy. It can be widely used as a joining material for producing brazing device parts such as exchangers and hot water supply parts.

Claims (4)

  1. 　Ｃｒを８．０～３０．０質量％、Ｓｉを７．０～１３．０質量％ 、Ｗもしくは／およびＭｏを合計で１．０～１０．０質量％含み、残部がＮｉおよび不可避不純物からなることを特徴とする耐熱性に優れたニッケルろう材。 Containing 8.0 to 30.0% by mass of Cr, 7.0 to 13.0% by mass of Si, 1.0 to 10.0% by mass in total of W or / and Mo, and the balance from Ni and inevitable impurities Nickel brazing material with excellent heat resistance, characterized by
  2. 　Ｃｒを８．０～３０．０質量％、Ｓｉを７．０～１３．０質量％、Ｃｏを５．０～３０．０質量％含み、残部がＮｉおよび不可避不純物からなることを特徴とする耐熱性に優れたニッケルろう材。 It contains 8.0 to 30.0% by mass of Cr, 7.0 to 13.0% by mass of Si, 5.0 to 30.0% by mass of Co, and the balance is made of Ni and inevitable impurities. Nickel brazing material with excellent heat resistance.
  3. 　Ｃｒを８．０～３０．０質量％、Ｓｉを７．０～１３．０質量％、Ｗもしくは／およびＭｏを合計で１．０～１０．０質量％、Ｃｏを５．０～３０．０質量％含み、残部がＮｉおよび不可避不純物からなることを特徴とする耐熱性に優れたニッケルろう材。 8.0 to 30.0% by mass of Cr, 7.0 to 13.0% by mass of Si, 1.0 to 10.0% by mass of W or / and Mo, and 5.0 to 30. A nickel brazing material excellent in heat resistance, characterized by containing 0% by mass and the balance comprising Ni and inevitable impurities.
  4. 　特性に影響を及ぼさない元素として、Ｆｅを１５．０質量％以下、Ｍｎ、Ｃｕをそれぞれ５．０質量％以下、Ｃ、Ｂ、Ａｌ、Ｔｉ、Ｎｂをそれぞれ０．５質量％以下含み、Ｆｅ、Ｍｎ、Ｃｕ、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１～３のいずれか１項に記載の耐熱性に優れたニッケルろう材。 As an element that does not affect the characteristics, Fe is 15.0% by mass or less, Mn and Cu are each 5.0% by mass or less, C, B, Al, Ti, and Nb are each 0.5% by mass or less, Fe The nickel braze having excellent heat resistance according to any one of claims 1 to 3, wherein a total of Mn, Cu, C, B, Al, Ti, and Nb is 20.0 mass% or less Wood.
PCT/JP2011/076277 2010-12-16 2011-11-15 Nickel-based brazing filler metal with excellent heat resistance WO2012081346A1 (en)

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CN104191099A (en) * 2014-07-09 2014-12-10 哈尔滨正德科技开发有限公司 WC particle reinforced composite brazing filler metal used for brazing hard alloy and preparation method thereof
CN104233002A (en) * 2013-06-20 2014-12-24 沈阳大陆激光技术有限公司 Nickel base alloy powder for laser repair of supercharger air outlet housing of internal combustion engine
CN104745881A (en) * 2013-12-27 2015-07-01 新奥科技发展有限公司 A nickel based alloy and applications thereof
CN105555452A (en) * 2013-09-26 2016-05-04 阿尔法拉瓦尔股份有限公司 Method for joining metal parts
CN105562965A (en) * 2014-05-17 2016-05-11 江苏图南合金股份有限公司 Method for preparing nickel-based alloy welding wire
CN106493485A (en) * 2016-11-15 2017-03-15 张金水 Welding material containing tungsten, molybdenum, titanium, nickel, nobelium and constantan and preparation method thereof
CN107223079A (en) * 2015-02-17 2017-09-29 霍加纳斯股份有限公司 The nickel-base alloy with high melting range suitable for soldering super austenitic steel
KR20170117891A (en) * 2016-04-14 2017-10-24 지멘스 에너지, 인코포레이티드 Methods of brazing wide gaps in nickel base superalloys without substantial degredation of properties
US10576587B2 (en) 2013-09-26 2020-03-03 Alfa Laval Corporate Ab Brazing concept
CN111215787A (en) * 2018-11-23 2020-06-02 中国科学院金属研究所 Nickel-based foil brazing filler metal for high-temperature alloy connection and preparation method and application thereof
CN111451593A (en) * 2020-04-08 2020-07-28 无锡市普尔换热器制造有限公司 Technology for effectively controlling core deformation of light titanium alloy plate-fin heat exchanger
EP4065301A4 (en) * 2019-11-26 2023-12-13 Oerlikon Metco (US) Inc. Low melting nickel-manganese-silicon based braze filler metals for heat exchanger applications
JP7442238B1 (en) 2023-06-09 2024-03-04 東京ブレイズ株式会社 Brazing filler metals, brazing materials, and methods of manufacturing them

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Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104233002A (en) * 2013-06-20 2014-12-24 沈阳大陆激光技术有限公司 Nickel base alloy powder for laser repair of supercharger air outlet housing of internal combustion engine
US10180292B2 (en) 2013-09-26 2019-01-15 Alfa Laval Corporate Ab Plate heat exchanger
CN105555452A (en) * 2013-09-26 2016-05-04 阿尔法拉瓦尔股份有限公司 Method for joining metal parts
US10576587B2 (en) 2013-09-26 2020-03-03 Alfa Laval Corporate Ab Brazing concept
US10323890B2 (en) 2013-09-26 2019-06-18 Alfa Laval Corporate Ab Method for joining metal parts
CN104745881A (en) * 2013-12-27 2015-07-01 新奥科技发展有限公司 A nickel based alloy and applications thereof
CN105562965A (en) * 2014-05-17 2016-05-11 江苏图南合金股份有限公司 Method for preparing nickel-based alloy welding wire
CN105562964A (en) * 2014-05-17 2016-05-11 江苏图南合金股份有限公司 Method for preparing thin welding wires from nickel-based alloy with designation of Cr28Ni48W5
CN105562963A (en) * 2014-05-17 2016-05-11 江苏图南合金股份有限公司 Method for preparing nickel-based alloy welding wires with high qualified product ratio
CN104191099A (en) * 2014-07-09 2014-12-10 哈尔滨正德科技开发有限公司 WC particle reinforced composite brazing filler metal used for brazing hard alloy and preparation method thereof
CN107223079A (en) * 2015-02-17 2017-09-29 霍加纳斯股份有限公司 The nickel-base alloy with high melting range suitable for soldering super austenitic steel
KR20170117891A (en) * 2016-04-14 2017-10-24 지멘스 에너지, 인코포레이티드 Methods of brazing wide gaps in nickel base superalloys without substantial degredation of properties
CN106493485A (en) * 2016-11-15 2017-03-15 张金水 Welding material containing tungsten, molybdenum, titanium, nickel, nobelium and constantan and preparation method thereof
CN111215787A (en) * 2018-11-23 2020-06-02 中国科学院金属研究所 Nickel-based foil brazing filler metal for high-temperature alloy connection and preparation method and application thereof
CN111215787B (en) * 2018-11-23 2021-09-24 中国科学院金属研究所 Nickel-based foil brazing filler metal for high-temperature alloy connection and preparation method and application thereof
EP4065301A4 (en) * 2019-11-26 2023-12-13 Oerlikon Metco (US) Inc. Low melting nickel-manganese-silicon based braze filler metals for heat exchanger applications
CN111451593A (en) * 2020-04-08 2020-07-28 无锡市普尔换热器制造有限公司 Technology for effectively controlling core deformation of light titanium alloy plate-fin heat exchanger
JP7442238B1 (en) 2023-06-09 2024-03-04 東京ブレイズ株式会社 Brazing filler metals, brazing materials, and methods of manufacturing them

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