WO2012081346A1 - Métal d'apport de brasage fort à base de nickel présentant une excellente résistance à la chaleur - Google Patents

Métal d'apport de brasage fort à base de nickel présentant une excellente résistance à la chaleur 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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WIPO (PCT)
Prior art keywords
mass
strength
temperature
heat resistance
nickel
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Application number
PCT/JP2011/076277
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English (en)
Japanese (ja)
Inventor
勝則 乙部
敬 河原田
信一 西村
Original Assignee
福田金属箔粉工業株式会社
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Priority to JP2012548703A priority Critical patent/JP5846646B2/ja
Publication of WO2012081346A1 publication Critical patent/WO2012081346A1/fr

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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.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Pressure Welding/Diffusion-Bonding (AREA)

Abstract

L'invention porte sur un métal d'apport de brasage fort résistant à la chaleur destiné à être utilisé dans divers types d'échangeurs de chaleur et qui est approprié pour unir des éléments en acier inoxydable ou similaires, en particulier des éléments qui doivent être résistants à la chaleur. Le métal d'apport de brasage fort à base de nickel présentant une excellente résistance à la chaleur est caractérisée en ce qu'il contient 8,0 à 30,0 % en masse de Cr, 7,0 à 13,0 % en masse de Si et 1,0 à 10,0 % en masse (au total) de W et/ou Mo, le reste étant du Ni et des impuretés inévitables, et en ce qu'il contient en outre, comme éléments n'ayant pas d'incidence sur les caractéristiques, au maximum 15,0 % en masse de Fe, au maximum 5,0 % en masse de Mn, au maximum 5,0 % en masse de Cu et du C, B, Al, Ti et Nb chacun en une quantité inférieure ou égale à 0,5 % en masse, la somme totale de Fe, Mn, Cu, C, B, Al, Ti et Nb étant inférieure ou égale à 20,0 % en masse.
PCT/JP2011/076277 2010-12-16 2011-11-15 Métal d'apport de brasage fort à base de nickel présentant une excellente résistance à la chaleur WO2012081346A1 (fr)

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JP2012548703A JP5846646B2 (ja) 2010-12-16 2011-11-15 耐熱性に優れたニッケルろう材

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JP2010280284 2010-12-16
JP2010-280284 2010-12-16

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Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104191099A (zh) * 2014-07-09 2014-12-10 哈尔滨正德科技开发有限公司 用于硬质合金钎焊的wc颗粒增强的复合钎料及其制备方法
CN104233002A (zh) * 2013-06-20 2014-12-24 沈阳大陆激光技术有限公司 一种用于内燃机增压器出气壳激光修复的镍基合金粉末
CN104745881A (zh) * 2013-12-27 2015-07-01 新奥科技发展有限公司 一种镍基合金及其应用
CN105555452A (zh) * 2013-09-26 2016-05-04 阿尔法拉瓦尔股份有限公司 接合金属部件的方法
CN105562963A (zh) * 2014-05-17 2016-05-11 江苏图南合金股份有限公司 成材率较高的制备镍基合金焊丝方法
CN106493485A (zh) * 2016-11-15 2017-03-15 张金水 含有钨、钼、钛、镍、锘和康铜的焊接材料及其制备方法
CN107223079A (zh) * 2015-02-17 2017-09-29 霍加纳斯股份有限公司 适于钎焊超级奥氏体钢的具有高熔程的镍基合金
KR20170117891A (ko) * 2016-04-14 2017-10-24 지멘스 에너지, 인코포레이티드 특징들의 실질적인 저하 없이 니켈 초합금들의 와이드 갭들을 브레이징하는 방법들
US10576587B2 (en) 2013-09-26 2020-03-03 Alfa Laval Corporate Ab Brazing concept
CN111215787A (zh) * 2018-11-23 2020-06-02 中国科学院金属研究所 一种高温合金连接用镍基箔带钎料及其制备方法和应用
CN111451593A (zh) * 2020-04-08 2020-07-28 无锡市普尔换热器制造有限公司 一种有效控制轻型钛合金板翅式换热器的芯体变形工艺
EP4065301A4 (fr) * 2019-11-26 2023-12-13 Oerlikon Metco (US) Inc. Métaux d'apport de brasage à base de nickel-manganèse-silicium à bas point de fusion pour applications d'échangeur de chaleur
JP7442238B1 (ja) 2023-06-09 2024-03-04 東京ブレイズ株式会社 ろう材及びろう付用部材、並びにそれらの製造方法

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CN105499834A (zh) * 2016-01-27 2016-04-20 江苏科技大学 一种用于钎焊钼铼合金的钎料和制备方法及钎焊方法

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Cited By (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104233002A (zh) * 2013-06-20 2014-12-24 沈阳大陆激光技术有限公司 一种用于内燃机增压器出气壳激光修复的镍基合金粉末
US10180292B2 (en) 2013-09-26 2019-01-15 Alfa Laval Corporate Ab Plate heat exchanger
CN105555452A (zh) * 2013-09-26 2016-05-04 阿尔法拉瓦尔股份有限公司 接合金属部件的方法
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 (zh) * 2013-12-27 2015-07-01 新奥科技发展有限公司 一种镍基合金及其应用
CN105562963A (zh) * 2014-05-17 2016-05-11 江苏图南合金股份有限公司 成材率较高的制备镍基合金焊丝方法
CN105562964A (zh) * 2014-05-17 2016-05-11 江苏图南合金股份有限公司 将牌号为Cr28Ni48W5的镍基合金制成较细焊丝的方法
CN105562965A (zh) * 2014-05-17 2016-05-11 江苏图南合金股份有限公司 制备镍基合金焊丝的方法
CN104191099A (zh) * 2014-07-09 2014-12-10 哈尔滨正德科技开发有限公司 用于硬质合金钎焊的wc颗粒增强的复合钎料及其制备方法
CN107223079A (zh) * 2015-02-17 2017-09-29 霍加纳斯股份有限公司 适于钎焊超级奥氏体钢的具有高熔程的镍基合金
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
KR20170117891A (ko) * 2016-04-14 2017-10-24 지멘스 에너지, 인코포레이티드 특징들의 실질적인 저하 없이 니켈 초합금들의 와이드 갭들을 브레이징하는 방법들
CN106493485A (zh) * 2016-11-15 2017-03-15 张金水 含有钨、钼、钛、镍、锘和康铜的焊接材料及其制备方法
CN111215787A (zh) * 2018-11-23 2020-06-02 中国科学院金属研究所 一种高温合金连接用镍基箔带钎料及其制备方法和应用
CN111215787B (zh) * 2018-11-23 2021-09-24 中国科学院金属研究所 一种高温合金连接用镍基箔带钎料及其制备方法和应用
EP4065301A4 (fr) * 2019-11-26 2023-12-13 Oerlikon Metco (US) Inc. Métaux d'apport de brasage à base de nickel-manganèse-silicium à bas point de fusion pour applications d'échangeur de chaleur
CN111451593A (zh) * 2020-04-08 2020-07-28 无锡市普尔换热器制造有限公司 一种有效控制轻型钛合金板翅式换热器的芯体变形工艺
JP7442238B1 (ja) 2023-06-09 2024-03-04 東京ブレイズ株式会社 ろう材及びろう付用部材、並びにそれらの製造方法

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