WO2013077113A1 - Matière de brasage à base de ni-cr ayant d'excellentes aptitude au mouillage/aptitude à l'étalement et une excellente résistance à la corrosion - Google Patents

Matière de brasage à base de ni-cr ayant d'excellentes aptitude au mouillage/aptitude à l'étalement et une excellente résistance à la corrosion Download PDF

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Publication number
WO2013077113A1
WO2013077113A1 PCT/JP2012/076635 JP2012076635W WO2013077113A1 WO 2013077113 A1 WO2013077113 A1 WO 2013077113A1 JP 2012076635 W JP2012076635 W JP 2012076635W WO 2013077113 A1 WO2013077113 A1 WO 2013077113A1
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Prior art keywords
mass
less
brazing
content
corrosion resistance
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PCT/JP2012/076635
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English (en)
Japanese (ja)
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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Publication of WO2013077113A1 publication Critical patent/WO2013077113A1/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
    • 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
    • B23K35/3053—Fe as the principal constituent
    • B23K35/3066—Fe as the principal constituent with Ni as next major 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
    • 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
    • C22C30/00—Alloys containing less than 50% by weight of each constituent
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C30/00—Alloys containing less than 50% by weight of each constituent
    • C22C30/02—Alloys containing less than 50% by weight of each constituent containing copper

Definitions

  • the present invention is used for various heat exchanger applications such as general-purpose heat exchangers, EGR coolers, waste heat recovery devices, etc., and relates to a brazing material for joining members such as various stainless steels, and particularly excellent in corrosion resistance.
  • the present invention relates to a nickel brazing material having good wetting and spreading properties for ferritic stainless steel.
  • nickel brazing materials used for joining various stainless steel members include BNi-2, BNi-5, and BNi-7 defined in JIS Z 3265 “Nickel brazing”.
  • BNi-2 has an appropriate melting point and bonding strength, but has poor corrosion resistance and does not provide good wetting and spreading properties.
  • B when it brazes, B will approach into the grain boundary of the stainless steel used as a base material, and the intensity
  • BNi-5 has moderate bonding strength and excellent corrosion resistance, it has poor wetting and spreading properties, so that the molten brazing material does not flow and may cause bonding failure.
  • Patent Documents 1 to 6 show brazing materials containing Ni as a main component and containing Cr, Si, P, etc. (hereinafter referred to as Ni-based brazing materials in the prior art). These have an appropriate melting point and bonding strength, but cannot achieve both corrosion resistance and wettability with respect to ferritic stainless steel. Furthermore, the brazing materials containing Ni, Cr, Si, P, etc. mainly composed of Fe shown in Patent Documents 7 to 10 (hereinafter referred to as Fe-based brazing materials in the prior art) have an appropriate melting point and bonding strength. However, since Fe is the main component, it has poor wettability with respect to various stainless steels, and corrosion resistance is not sufficient.
  • brazing materials used in industrial use have various functions such as heat resistance / oxidation resistance, corrosion resistance, appropriate melting point, bonding strength, and various stainless steels. However, since there is no brazing material that has all of them, brazing materials are properly used depending on applications and environments.
  • nickel brazing filler metal has bonding strength, heat resistance, and corrosion resistance, and has been widely used for bonding materials such as various heat exchangers based on austenitic stainless steel.
  • ferritic stainless steel base materials not containing Ni have been actively applied for the purpose of cost reduction.
  • the EGR cooler used for exhaust gas reduction measures for diesel engine vehicles contributes to the improvement of fuel efficiency when it is installed.
  • the temperature of exhaust gas is higher in gasoline engine vehicles than in diesel engine vehicles. Therefore, when austenitic stainless steel is applied to the base material, there is a concern about deterioration of corrosion resistance and strength due to sensitization. Therefore, application of ferritic stainless steel has been studied. Therefore, the development of a brazing material having excellent wettability for ferritic stainless steel is required.
  • Target value (1) Liquidus temperature (melting point) ⁇ 1120 ° C or less (2) Fracture strength (material strength) ⁇ 700N / mm 2 or more (3) Brazing (wet spread test for SUS444) ⁇ Area after brazing 750 mm 2 or more (4) Sulfuric acid corrosion resistance (corrosion loss in 30% sulfuric acid) ⁇ 1.0 mg / m 2 ⁇ s or less
  • the alloy of the present invention (Ni-Cr brazing filler metal) satisfying all the above target values is excellent in wetting spreadability and corrosion resistance, Fe 0-35.0 mass%, Cr 18.0-35.0 mass%, Si 1.0- 4.0 mass%, P 6.5-9.5 mass%, Si and P in total 9.2-11.8 mass%, Cu 0.3-5.0 mass%, Al, Ca, Y, Misch metal (alloy containing multiple rare earth elements) ) Is contained in an amount of 0.01 to 0.10% by mass, the balance is made of Ni and inevitable impurities, and the total amount of Cr and Fe is 6.5 times or less of the P content.
  • 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, Sn, etc., and the sum of these is usually 0.3% by mass or less, and does not affect the function of the present invention.
  • the Ni-Cr brazing filler metal of the present invention has a Si content of 0 to less than 1.0% by mass, Fe of 10.0 to 45.0% by mass, Cr of 10.0 to 30.0% by mass, and P of 8.5 to 10.8% by mass.
  • Si and P in total 9.0 to 11.0% by mass, Cu 0.3 to 5.0% by mass, Al, Ca, Y, and one or more kinds of misch metal 0.01 to 0.10% by mass, the balance being Ni and inevitable impurities
  • the total amount of Cr and Fe is not more than 6.5 times the P content.
  • the present invention provides at least one element selected from Co, Mo, W, Mn, C, B, and Ti as an element that does not affect the characteristics of the Ni—Cr brazing material having the above characteristics.
  • the Co and / or Mo content is 15.0 mass% or less
  • the W and / or Mn content is 5.0 mass% or less
  • the total content of C, B, and Ti is 0.3 mass% or less.
  • the total content of Co, Mo, W, Mn, C, B, and Ti is 15.0% by mass or less.
  • brazing material having excellent wettability and corrosion resistance according to the present invention is limited
  • the Fe dissolves in the Ni solid solution to improve the material strength.
  • the addition amount increases, the function of P is inhibited and the wet spreading property is lowered.
  • the upper limit was defined as 35.0% by mass so as not to reduce the wetting and spreading property.
  • the Fe content may be 0% by mass.
  • the lower limit of the Fe content is specified to 10.0% by mass to provide material strength.
  • the upper limit value of Fe was set to 45.0% by mass so as not to lower the wet spreading property.
  • the total amount of Cr and Fe is specified to be 6.5 times or less of P because the function of P is inhibited and the wetting and spreading property is lowered when the total amount of Cr is increased.
  • Cr dissolves in a Ni solid solution serving as a substrate (matrix) to impart corrosion resistance and heat resistance, but if the content is less than 10.0% by mass, sufficient effects cannot be obtained. On the other hand, if it exceeds 35.0% by mass, a large amount of P and an intermetallic compound are formed, and the material strength is lowered and the wetting and spreading property is also lowered. Therefore, Cr is set in the range of 10.0 to 35.0% by mass.
  • the Cr content must be adjusted according to the content of Si and P contained in the brazing filler metal of the present invention.
  • the Si content is 1.0 to 4.0% by mass and the P content is 6.5 to 9.5% by mass. In this case, the Cr content must be set in the range of 18.0 to 35.0% by mass. When the Si content is 0 to less than 1.0% by mass and the P content is 8.5 to 10.8% by mass, the Cr content is It is necessary to set it in the range of 10.0 to 30.0% by mass.
  • Si dissolves in Ni to form a eutectic phase, contributing to the melting point drop of the brazing filler metal.
  • the content exceeds 4.0 mass%, the liquidus temperature rises and exceeds the target value. It is necessary to adjust the liquidus temperature by reducing the P content, and as a result, the wet spreading property is deteriorated. Therefore, the Si content is 4.0% by mass or less. Si may be 0% by mass depending on the P content.
  • P dissolves in Ni to form a eutectic phase, which contributes to lowering the melting point of the brazing material and improves wetting spreadability, but wetting spreadability with a content of less than 6.5% by mass Becomes worse.
  • the content exceeds 10.8% by mass, hypereutectic is formed, and the strength is greatly reduced, so that the target bending strength cannot be obtained.
  • the P content must be adjusted according to the Si content.
  • the Si content is 1.0 to 4.0 mass%
  • the P content is in the range of 6.5 to 9.5%
  • the Si content is In the case of 0 to less than 1.0% by mass, the P content was set in the range of 8.5 to 10.8% by mass.
  • the melting point and material strength can be controlled in particular. That is, when the Si content is 1.0 to 4.0% by mass, the melting point increases when the total amount of Si and P is less than 9.2% by mass, exceeding the target liquidus temperature. On the other hand, when the total amount of Si and P exceeds 11.8% by mass, hypereutectic is formed, and the material strength is significantly reduced, so that the target bending strength cannot be obtained. For this reason, the total amount of Si and P is set in the range of 9.2 to 11.8% by mass. When the Si content is 0 to less than 1.0% by mass, the melting point increases when the total amount of Si and P is less than 9.0%, exceeding the target liquidus temperature.
  • the total amount of Si and P exceeds 11.0% by mass, hypereutectic is formed, the material strength is significantly reduced, and the target bending strength cannot be obtained. For this reason, the total amount of Si and P is set in the range of 9.0 to 11.0% by mass.
  • Cu is a solid solution in Ni solid solution and improves the corrosion resistance especially against sulfuric acid, but its effect is insufficient with a content of less than 0.3% by mass, and when it exceeds 5.0% by mass, wetting spreadability and material strength decrease. Therefore, the Cu content is set in the range of 0.3 to 5.0% by mass.
  • Al, Ca, Y, and misch metal contribute to the deoxidation action of the molten brazing filler metal and have an effect of improving wet spreadability, but if it is less than 0.01% by mass, the effect is small, and if it exceeds 0.1% by mass
  • the total amount of Al, Ca, Y, and misch metal was determined to be in the range of 0.01 to 0.1% by mass because the viscosity of the molten brazing material was lowered and the wet spreadability was deteriorated.
  • Examples of the misch metal that can be used in the present invention include high-purity Nd and In, as well as La-52Ce-15Nd-6Pr alloy and Pr-25Nd alloy.
  • Co is 15.0 mass% or less
  • Mo is 15.0 mass% or less
  • W is 5.0 mass% or less
  • Mn is 5.0 mass% or less
  • C, B Ti
  • the upper limit of the total of Co, Mo, W, Mn, C, B, and Ti is included. It was set to 15.0% by mass.
  • the brazing filler metal of the present invention has the following characteristics, it can be applied to a wide range of applications as a nickel brazing filler metal having excellent corrosion resistance, wettability and material strength.
  • the liquidus temperature is 1120 ° C or less, and brazing can be performed using a general-purpose industrial atmospheric furnace.
  • ⁇ Because the bending strength is 700N / mm 2 or more, it has moderate bonding strength as a nickel brazing material.
  • For-wetting area after brazing for SUS444 substrate has a 750 mm 2 or more, wet well the ferritic stainless steel, spread flow, has excellent brazing workability.
  • ⁇ In 30% H 2 SO 4 (60 ° C) corrosion test corrosion weight loss is 1.0mg / m 2 ⁇ s or less, so it has excellent corrosion resistance to sulfuric acid.
  • the brazing filler metal of the present invention is prepared by adjusting and blending Ni as a base and the components Fe, Cr, Si, P, Cu, Al, etc., and Mo, Co, Mn, etc. at a predetermined mass% if necessary. After the molten metal is completely melted in the crucible of the melting furnace, the molten alloy is powdered by the atomizing method or melt pulverization method, or cast into a predetermined mold to obtain a rod shape or plate shape be able to.
  • 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, a method of applying a paste in which a binder and powder are mixed, a method of installing by processing into a sheet or foil, a method of spraying and installing a powder, and the like can be selected.
  • Example brazing material and comparative example brazing material of the present invention prepared and mixed as described above, and melted (liquidus temperature), bending strength, wetting spreadability, corrosion resistance to sulfuric acid by the following methods Evaluated.
  • 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 (b) the total amount of Cr and Fe exceeded 6.5 times the content of P, and in Comparative Example (d), the total amount of P and Si and P was below the lower limit of the claims, comparison Example (f) shows the total amount of Cu and Co and Mn exceeding the upper limit of the claims, Comparative Example (g) shows that Al exceeds the upper limit of the claims, and Comparative Example (h) shows a combination of Ca and Y. The total amount exceeded the upper limit of the claims, and in all cases, the wet spreadability did not satisfy the target. In Comparative Example (c), Si exceeded the upper limit of the claim, B exceeded the upper limit of the claim, and Comparative Example (m), Mn exceeded the upper limit of the claim. Not meeting the goal of wettability.
  • Comparative Example (e) and Comparative Example (i) the total amount of P and Si and P exceeded the upper limit of the claims, and none of them satisfied the liquidus temperature and bending strength targets.
  • Comparative Example (j) Cr and Cu are below the lower limit of the claims, and the corrosion resistance against sulfuric acid does not satisfy the target.
  • Comparative Example (l) the total amount of P and Si and P is below the lower limit of the claims, and the total amount of Fe and Cr exceeds 6.5 times the P content. Sex does not meet the goal.
  • the comparative brazing materials (A), (B), and (C) shown in Table 3 are typical nickel brazing materials defined in JIS Z 3265, and the comparative brazing materials (D) to (W) are “ Patent No. 3168158 ”,“ Patent No. 3349522 ”,“ JP 2009-202198 ”,“ JP 2010-269347 ”,“ JP 2007-75867 ”,“ JP 2011-110575 ”,“ WO 2009/128174 ”
  • the brazing filler metals 1 to 15 of the present invention satisfy all the target values of the liquidus temperature, the bending strength, the wetting spreadability and the corrosion resistance against sulfuric acid, as is clear from Table 1.
  • a brazing material it has an appropriate melting point, material strength, brazing property, and excellent corrosion resistance.
  • the brazing filler metal of the embodiment of the present invention shows good brazing properties against various stainless steels other than SUS444, nickel-base heat-resistant alloys and corrosion-resistant alloys such as Inconel and Hastelloy.
  • the brazing atmosphere exhibits good brazing properties even in a reducing hydrogen atmosphere, an inert argon atmosphere, or a nitrogen atmosphere.
  • the brazing filler metal of Example has good corrosion resistance against sulfuric acid, various acids such as nitric acid and ammonia water.
  • the nickel brazing material of the present invention has an appropriate melting point, excellent material strength and corrosion resistance, and has good wetting and spreading properties in ferritic stainless steel, and austenitic stainless steel and nickel alloy members. Because brazing is good in brazing, not only EGR coolers, but also a wide range of brazing equipment parts such as environment- and energy-related heat exchangers, waste heat recovery equipment, and hot water supply parts Can be widely used as a bonding material.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
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Abstract

L'invention concerne une matière de brasage à base de Ni-Cr ayant d'excellentes aptitude au mouillage/aptitude à l'étalement et une excellente résistance à la corrosion, qui peut être brasée à une température réalisable (1150°C ou au-dessous) lorsqu'elle est utilisée pour assembler un acier inoxydable ferritique par brasage, et a une bonne propriété de brasage, une bonne résistance de joint et une bonne résistance à la corrosion à l'encontre d'un métal de base. La matière de brasage est caractérisée comme comprenant, en % en masse, 45,0 % ou moins de Fe, 10,0 à 35,0 % de Cr, 4,0 % ou moins de Si, 6,5 à 10,8 % de P, Si et P étant présents dans la quantité totale de 9,0 à 11,8 %, 0,3 à 5,0 % de Cu, 0,01 à 0,10 % d'au moins l'un choisi parmi Al, Ca, Y et un mischmétal, et le reste étant composé par Ni et les impuretés inévitables, la quantité totale de Cr et Fe étant de 6,5 fois ou moins plus grande que la teneur de P. La matière de brasage peut en outre contenir, comme éléments qui n'affectent pas les propriétés de la matière de brasage, Co et/ou Mo dans une quantité de 15,0 % ou moins, W et/ou Mn dans une quantité de 5,0 % ou moins, et C, B et Ti dans la quantité totale de 0,3 % ou moins, la quantité totale de Co, Mo, W, Mn, C, B et Ti étant de 15,0 % en masse ou moins.
PCT/JP2012/076635 2011-11-24 2012-10-15 Matière de brasage à base de ni-cr ayant d'excellentes aptitude au mouillage/aptitude à l'étalement et une excellente résistance à la corrosion WO2013077113A1 (fr)

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Cited By (15)

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Publication number Priority date Publication date Assignee Title
WO2015019876A1 (fr) * 2013-08-06 2015-02-12 山陽特殊製鋼株式会社 MATÉRIAU ALLIÉ DE BRASAGE À BASE DE Ni-Cr-Fe ADDITIONNÉ DE Cu
WO2015198790A1 (fr) * 2014-06-26 2015-12-30 日立金属株式会社 Ruban d'alliage amorphe à base de nickel pour brasage et objet en acier inoxydable assemblé utilisant ce dernier
JP2016088170A (ja) * 2014-10-30 2016-05-23 日本車輌製造株式会社 鉄道車両構体
EP3009223A4 (fr) * 2014-04-11 2016-06-22 Fukuda Metal Foil Powder Métal d'apport de brasage de nickel présentant une exceptionnelle résistance à la corrosion
JP2017088012A (ja) * 2015-11-12 2017-05-25 日本車輌製造株式会社 鉄道車両用ブロック結合構造及びそれを用いた鉄道車両用構体
CN108356440A (zh) * 2017-12-29 2018-08-03 安徽宝辰机电设备科技有限公司 一种提高钨电极与低价合金钢焊接接口强度的方法
WO2018198906A1 (fr) 2017-04-25 2018-11-01 山陽特殊製鋼株式会社 Matériau de brasage en alliage à base de ni-cr contenant une quantité de trace de v
EP3441492A4 (fr) * 2016-03-30 2019-09-25 Hitachi, Ltd. Alliage à deux phases à base de chrome et produit utilisant ledit alliage à deux phases
CN111673314A (zh) * 2014-10-08 2020-09-18 舒瑞普国际股份公司 用于钎焊奥氏体不锈钢物品的钎焊材料及其应用
EP3753669A1 (fr) * 2014-03-18 2020-12-23 Metglas, Inc. Alliages de brasage nickel-fer-phosphore
CN114054758A (zh) * 2021-11-07 2022-02-18 北京工业大学 一种原位生成腐蚀润滑剂的自适应钎焊耐磨涂层及制备
US11318566B2 (en) 2016-08-04 2022-05-03 Honda Motor Co., Ltd. Multi-material component and methods of making thereof
US11339817B2 (en) 2016-08-04 2022-05-24 Honda Motor Co., Ltd. Multi-material component and methods of making thereof
US11511375B2 (en) 2020-02-24 2022-11-29 Honda Motor Co., Ltd. Multi component solid solution high-entropy alloys
US11535913B2 (en) * 2016-08-04 2022-12-27 Honda Motor Co., Ltd. Multi-material component and methods of making thereof

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US20190134761A1 (en) * 2013-08-06 2019-05-09 Sanyo Special Steel Co., Ltd. Cu-Added Ni-Cr-Fe-Based Alloy Brazing Material
JP2015051459A (ja) * 2013-08-06 2015-03-19 山陽特殊製鋼株式会社 Ｃｕを添加したＮｉ−Ｃｒ−Ｆｅ基合金ろう材
CN105473275A (zh) * 2013-08-06 2016-04-06 山阳特殊制钢株式会社 添加有Cu的Ni-Cr-Fe基合金钎料
US10543571B2 (en) 2013-08-06 2020-01-28 Sanyo Special Steel Co., Ltd. Cu-added Ni—Cr—Fe-based alloy brazing material
CN110039221A (zh) * 2013-08-06 2019-07-23 山阳特殊制钢株式会社 添加有Cu的Ni-Cr-Fe基合金钎料
WO2015019876A1 (fr) * 2013-08-06 2015-02-12 山陽特殊製鋼株式会社 MATÉRIAU ALLIÉ DE BRASAGE À BASE DE Ni-Cr-Fe ADDITIONNÉ DE Cu
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