EP1897650A2 - Matériau de brasage à base de nickel et de fer et procédé de brasage - Google Patents

Matériau de brasage à base de nickel et de fer et procédé de brasage Download PDF

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Publication number
EP1897650A2
EP1897650A2 EP07115281A EP07115281A EP1897650A2 EP 1897650 A2 EP1897650 A2 EP 1897650A2 EP 07115281 A EP07115281 A EP 07115281A EP 07115281 A EP07115281 A EP 07115281A EP 1897650 A2 EP1897650 A2 EP 1897650A2
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EP
European Patent Office
Prior art keywords
brazing
atom
amorphous
parts
solder
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP07115281A
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German (de)
English (en)
Other versions
EP1897650A3 (fr
Inventor
Thomas Hartmann
Dieter Nützel
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Vacuumschmelze GmbH and Co KG
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Vacuumschmelze GmbH and Co KG
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Filing date
Publication date
Application filed by Vacuumschmelze GmbH and Co KG filed Critical Vacuumschmelze GmbH and Co KG
Publication of EP1897650A2 publication Critical patent/EP1897650A2/fr
Publication of EP1897650A3 publication Critical patent/EP1897650A3/fr
Withdrawn legal-status Critical Current

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    • 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
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/08—Ferrous alloys, e.g. steel alloys containing nickel
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C45/00—Amorphous alloys
    • C22C45/02—Amorphous alloys with iron as the major constituent
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C45/00—Amorphous alloys
    • C22C45/04—Amorphous alloys with nickel or cobalt as the major constituent

Definitions

  • the invention relates to a brazing alloy based on nickel-iron and a method for brazing two or more parts.
  • Soldering is a process for joining metallic or ceramic parts using a molten filler material called solder.
  • solder a molten filler material
  • soft soldering and brazing, wherein the processing temperature is typically 10 ° C to 60 ° C above the liquidus temperature of the solder.
  • Soft solders are processed at temperatures below 450 ° C and brazing alloys at temperatures above 450 ° C. Brazing alloys are used in applications where high mechanical strength of the braze joint and / or high mechanical strength at elevated operating temperatures is desired.
  • Brazing alloys are typically processed at temperatures of about 1200 ° C. For some base materials, however, a lower soldering or processing temperature is often sought in order to avoid a temperature-induced change in the base material.
  • brazing precipitation-hardened Ni-base alloys When brazing precipitation-hardened Ni-base alloys, a low brazing temperature is also desired since, in addition to massive grain coarsening, processing temperatures above approximately 1050 ° C. result in an irreversible worsening of the creep rupture strength, which can not be restored by further heat treatments.
  • brazing alloys can be made in various forms, such as solder paste and ductile films, thus broadening the scope of the brazing alloys.
  • brazing pastes based on nickel-iron-chromium are from the US 4,402,742 known.
  • the liquidus temperature of these brazes is well above 1000 ° C.
  • the processing temperature is 10 ° C to 60 ° C above these temperatures and is therefore too high for some base materials.
  • the total metalloid content of B and Si is high, so these alloys can not be made into ductile films.
  • the object of the invention is therefore to provide a brazing alloy based on nickel, which can be prepared in the form of a solder paste and as a ductile film.
  • a brazing filler is provided with a composition consisting essentially of Fe a Ni residue Si b B c M d with 5 ⁇ a ⁇ 35 atom%; 1 ⁇ b ⁇ 15 atom%; 5 ⁇ c ⁇ 15 atom%; 0 ⁇ d ⁇ 4 atom%; Residual Ni and incidental impurities exist and with a liquidus temperature T L ⁇ 1025 ° C.
  • M is one or more of the elements Co, Cr, Mn, Nb, Mo, Ta, Cu, Ag, Pd or C.
  • This iron addition leads to a lowering of the liquidus and solidus temperature compared to the iron-free Ni-Si-B system.
  • the iron content of the brazing alloy according to the invention is selected such that the brazing alloy has a liquidus temperature T L ⁇ 1025 ° C., preferably less than 1000 ° C., even less than 980 ° C.
  • the processing temperature may thus be 1050 ° C or lower.
  • M may be one or more of Co, Cr, Mn, Nb, Mo, Ta, Cu, Ag, Pd, or C, preferably Nb, Mn, Cr, or Mo.
  • the composition of the brazing alloy is selected such that the brazing alloy has a liquidus temperature T L ⁇ 1025 ° C, preferably less than 1000 ° C, even less than 980 ° C.
  • the processing temperature may thus be 1050 ° C or lower.
  • a low liquidus temperature is desired when the maximum soldering temperature is limited. This is the case, for example, in some industrial soldering processes, in particular for the joining of stainless steel base materials, since from a temperature of 1000 ° C. an undesired coarse grain formation of the base material occurs. This undesirable coarse grain formation leads to a lowering of the mechanical strength of the base material, which is critical for some technical applications, such as in heat exchangers. This problem is significantly reduced by the brazing alloy according to the invention having a liquefaction temperature T L of ⁇ 1025 ° C.
  • a nickel-iron based braze is provided, the braze having an Fe content of 5 ⁇ a ⁇ 30 atom%, preferably 10 ⁇ a ⁇ 30 atom%.
  • the raw material costs of brazing alloys with an increased iron content are reduced because the nickel content is partly replaced by iron.
  • brazing alloys can be produced as powder or solder paste as well as by means of rapid solidification technology as amorphous, ductile foil. These brazes are also phosphorus free, so that the formation of very brittle intermetallic phosphides is avoided.
  • the field of application of the brazing alloys according to the invention is expanded and the brazing seams which are produced from these brazing alloys are reliable in use.
  • the elements boron and silicon are metalloids and glass-forming elements and allow the production of the braze as an amorphous, ductile film. A higher content of these elements leads to a reduction in the melting or liquidus temperature. On the one hand, if the content of the glass-forming elements is too low, the films solidify in crystalline form and are very brittle. On the other hand, if the content of the glass-forming elements is too high, the films are brittle and can not be processed for technical processes.
  • the content of the metalloids is selected so that the alloys can be produced by the rapid solidification technology as at least partially amorphous ductile films.
  • the brazing alloy has an Si content of 6 ⁇ b ⁇ 13 atom% and / or a B content of 8 ⁇ c ⁇ 14 atom%.
  • the brazing alloy according to the invention has a liquidus temperature T L ⁇ 1000 ° C., preferably ⁇ 980 ° C.
  • braze to be used reliably in industrial applications with a maximum brazing temperature limited to 1050 ° C, and can be used to braze parts made from temperature-sensitive materials such as precipitation-hardened Ni superalloys, such as IN718, and brazing high-grade stainless steels.
  • temperature-sensitive materials such as precipitation-hardened Ni superalloys, such as IN718, and brazing high-grade stainless steels.
  • the brazing alloy according to the invention can be produced as a powder and as an amorphous, ductile film, for example by means of rapid solidification processes.
  • the brazing material according to one of the preceding embodiments may be provided in the form of a solder paste as well as in the form of an amorphous, ductile brazing foil. These brazing alloys can thus be produced in various forms, which can be adapted to different applications and used in a broader range.
  • the brazing foil is up to 50% amorphous, preferably at least 80% amorphous.
  • the brazing foils according to the invention can be produced in thicker strip thicknesses and larger widths than ductile foils.
  • the braze alloys according to the invention are thus outstandingly suitable, with thicknesses of more than 20 ⁇ m, preferably of 20 ⁇ m ⁇ D ⁇ 100 ⁇ m, preferably of 40 ⁇ m ⁇ D ⁇ 100 ⁇ m and with widths of more than 20 mm or of 20 mm ⁇ B ⁇ 200 mm, which is very limited in those known from the prior art brazing alloys based on nickel.
  • a heat exchanger having at least one solder joint made with a braze having a composition consisting essentially of Fe a Ni balance Si b B c M d with 5 ⁇ a ⁇ 35 atom%; 1 ⁇ b ⁇ 15 atom%; 5 ⁇ c ⁇ 15 atom%; 0 ⁇ d ⁇ 4 atom%; Residual Ni and incidental impurities persist.
  • the liquidus temperature T L is ⁇ 1025 ° C.
  • M is one or more of the elements Co, Cr, Mn, Nb, Mo, Ta, Cu, Ag, Pd or C.
  • this braze seam is made from a braze having this composition, which has been made in the form of an amorphous ductile brazing foil.
  • the heat exchanger may comprise at least one solder seam made from a brazing alloy or from an amorphous ductile brazing foil according to any one of the preceding embodiments.
  • the solder seam, which was produced with an amorphous, ductile brazing foil has a thickness of at least 20 ⁇ m.
  • solder seam of an amorphous, ductile brazing foil differs from a braze made by crystalline powder in the size of the B and Si hard phases.
  • a method for integrally joining two or more parts comprising the following steps.
  • a brazing filler metal according to one of the previous embodiments is introduced between two or more metal parts to be joined.
  • the parts to be joined have a higher melting temperature than the brazing alloy and can be made of stainless steel, a Ni alloy, a Co alloy, copper or a Cu alloy be.
  • the solder composite is heated to a temperature above the liquidus temperature of the braze and cooled to form a braze joint between the parts to be joined.
  • Another method for integrally joining two or more parts has the following steps.
  • An amorphous, ductile brazing foil according to one of the previous embodiments is introduced between two or more metal parts to be joined.
  • the parts to be joined have a higher melting temperature than the brazing foil and may be made of stainless steel, a precipitation-hardened Ni-base alloy, a Ni alloy, a Co alloy, copper or a Cu alloy.
  • the solder composite is heated to a temperature above the liquidus temperature of the brazing foil and cooled to form a braze joint between the parts to be joined.
  • the parts to be joined are preferably parts of a heat exchanger or components of a fuel cell or a mold or injection mold.
  • brazing alloys according to the invention as well as brazing foils can be used to produce one or more brazing seams in an article.
  • the brazed article may be a heat exchanger, a component of a fuel cell or an internal combustion engine, or a die or injection mold.
  • the brazing alloys according to the invention are produced in one embodiment of the method as amorphous, homogeneous and ductile brazing foils by means of rapid solidification.
  • a molten metal of a melt consisting of Fe a Ni rest Si b B c M d with 5 ⁇ a ⁇ 35 atom%; 1 ⁇ b ⁇ 15 atom%; 5 ⁇ c ⁇ 15 atom%; 0 ⁇ d ⁇ 4 atom%; Residual Ni and incidental impurities persist.
  • M is one or more of the elements Co, Cr, Mn, Nb, Mo, Ta, Cu, Ag, Pd or C.
  • This melt is injected through a pouring nozzle onto at least one rapidly rotating casting wheel or casting drum and at a cooling rate of more than 10 5 ° C / sec cooled.
  • the cast strip is then typically peeled from the casting wheel at a temperature between 100 ° C and 300 ° C and wound directly into a so-called coil or bobbin to indicate an amorphous, ductile brazing foil having a liquidus temperature T L ⁇ 1025 ° C.
  • the liquidus temperature of the brazing alloys according to the invention may be less than 1000 ° C., preferably 980 ° C.
  • metal parts especially from low and medium alloyed steels, stainless steel and / or nickel alloys, precipitation hardened Ni-base alloys and / or Co-alloys add materially, in which an undesirable thermally induced change, such as a coarse grain occurs at temperatures above 1000 ° C. The associated deterioration of the mechanical strength of these base materials can thus be avoided.
  • Ni-based brazing foils having various compositions are prepared by the rapid solidification technology.
  • the base composition is N rest Fe x Si 10 B 12 and films having an iron content of 0, 6, 11, 16, 21, 26, 31 and 52 atom% were prepared.
  • the films each have a width of 25 mm and a thickness of 25 ⁇ m and are ductile and at least partially amorphous.
  • brazing alloys do not melt at a melting point, but by their composition show a melting interval which is limited by the solidus temperature at which the solder begins to melt and the liquidus temperature at which the solder is completely molten , Typically, the ideal processing and thus soldering temperature of the brazing alloy is 10 ° C to 60 ° C above the liquidus temperature.
  • the solidus temperature and the liquidus temperature of the brazing foils are determined by means of a differential scanning calorimetry (DSC) method and the values are shown in FIG. 1 and in Table 1.
  • the comparative film without iron has a liquidus temperature of 1036 ° C. With an iron content in the range of about 5 at% to about 35 at%, the solidus temperature and the liquidus temperature are lowered.
  • the alloys 2 to 7 of Table 1 have a Liquiudemperatur of less than 1025 ° C and an iron content in the range of 6 at% to 31 at%.
  • the solidus temperature is 958 ° C. and the liquidus temperature is 973 ° C.
  • the solidus temperature is 955 ° C. and the liquidus temperature is 976 ° C.
  • the solidus temperature is 968 ° C and the liquidus temperature is 976 ° C.
  • the low liquidus temperature of the films with an iron content in the range of 5 to 35 atom% allows a lower processing temperature, so that these Hartlotfolien at temperature-sensitive Base materials such as stainless steels and precipitation hardened Ni superalloys can be used.
  • a nickel-based brazing sheet having a lower processing temperature than the processing temperature of the non-ferrous sheet may be given.
  • the raw material costs of the films are also reduced because of the partial replacement of nickel with iron.
  • a higher content of B and Si is avoided in order to reduce the liquidus and processing temperature, so that a brittle solder seam, which may occur due to a high metalloid content, is avoided.
  • These brazing alloys are also phosphorus free, so that the formation of unwanted brittle intermetallic phosphides are avoided in the braze.
  • the alloys of the second embodiment are made by rapid solidification technology, and the films produced thereby have a width of 25 mm and a thickness of 25 ⁇ m, and are ductile and at least partially amorphous.
  • the liquidus temperature of the films is determined by a DSC method. In FIG. 2 and in Table 2, the liquidus temperature of two foils is shown.
  • the first film has a composition of Ni 52 Fe 26 Si 10 B 12 and is thus chromium-free.
  • the second film has a composition of Ni 49 Fe 24 Cr 5 Si 10 B 12 and thus 5 atom% of chromium.
  • the liquidus temperature The first brazing foil without chromium is at 975 ° C. and the liquidus temperature of the second brazing foil with 5 atom% chromium is 1075 ° C.
  • a liquidus temperature of 1075 ° C leads to a processing temperature, which already leads during the joining process in many materials to be soldered to serious changes in properties, such as coarse grain formation and lower mechanical strength.
  • brazing foils of the composition Ni remainder Fe 25 Si 11 B 11 M 1 prepared by the rapid solidification technology, wherein M is one of the elements Nb, Mn, Cr and Mo is. Films of 1.0 atom% each of Nb, Mn, Cr and Mo were prepared. A comparative film having a composition of Ni balance Fe 25 Si 11 B 11 was also prepared. The films each have a width of 25 mm and a thickness of 25 ⁇ m and are ductile and at least partially amorphous.
  • the solidus temperature and the liquidus temperature of the brazing foils are determined by a differential scanning calorimetry (DSC) method and the values are shown in Table 3.
  • the liquidus temperature of the four alloys 2 to 5 is each less than 1000 ° C.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Pressure Welding/Diffusion-Bonding (AREA)
  • Fuel Cell (AREA)
  • Ceramic Products (AREA)
  • Conductive Materials (AREA)
  • Laminated Bodies (AREA)
EP07115281A 2006-09-08 2007-08-30 Matériau de brasage à base de nickel et de fer et procédé de brasage Withdrawn EP1897650A3 (fr)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DE200610042792 DE102006042792A1 (de) 2006-09-08 2006-09-08 Hartlot auf Nickel-Eisen-Basis sowie Verfahren zum Hartlöten

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EP1897650A2 true EP1897650A2 (fr) 2008-03-12
EP1897650A3 EP1897650A3 (fr) 2008-05-14

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101780611B (zh) * 2009-01-19 2011-09-07 中国科学院金属研究所 一种NiMnCoNbFeSiB带状钎焊材料
CN103060707A (zh) * 2013-01-01 2013-04-24 北京工业大学 一种替代镀硬铬的涂层材料及其激光熔覆制备方法
WO2016034395A1 (fr) * 2014-09-05 2016-03-10 Vacuumschmelze Gmbh & Co. Kg Procédé de brasage fort et utilisation d'une feuille de brasage fort pour brasage par induction
CN114101970A (zh) * 2021-11-04 2022-03-01 杭州华光焊接新材料股份有限公司 一种镍基非晶钎料带材及其制备方法

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1216019A (fr) * 1959-01-13 1960-04-21 Coast Metals Alliages fer-nickel à bas point de fusion
US3303024A (en) * 1963-12-23 1967-02-07 Coast Metals Inc Nickel-base brazing alloys
US4302515A (en) * 1979-02-01 1981-11-24 Allied Corporation Nickel brazed articles
EP0042525A1 (fr) * 1980-06-24 1981-12-30 Kabushiki Kaisha Toshiba Alliage magnétique amorphe
EP0057935A2 (fr) * 1981-02-10 1982-08-18 Kabushiki Kaisha Toshiba Alliage amorphe magnétique, sensible à la température
EP0066356A1 (fr) * 1981-03-31 1982-12-08 Masumoto Tsuyoshi Procédé pour la fabrication de fils métalliques fins et amorphes
EP0127894A1 (fr) * 1983-06-01 1984-12-12 GTE Products Corporation Alliages de brasage de nickel-fer contenant du carbone
JPH0280533A (ja) * 1988-09-14 1990-03-20 Tdk Corp 高透磁率微細結晶合金及びその製造方法
DE19610539A1 (de) * 1996-03-18 1997-09-25 Vacuumschmelze Gmbh Durch Rascherstarrung herstellbare, duktile Lötfolie

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0051461A1 (fr) * 1980-10-30 1982-05-12 Allied Corporation Feuilles de brasage ductiles homogènes
DE4234961C2 (de) * 1992-10-16 1996-07-25 Innova Zug Ag Verfahren zur Herstellung eines Formwerkzeuges für die Herstellung von Kunststofformteilen

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1216019A (fr) * 1959-01-13 1960-04-21 Coast Metals Alliages fer-nickel à bas point de fusion
US3303024A (en) * 1963-12-23 1967-02-07 Coast Metals Inc Nickel-base brazing alloys
US4302515A (en) * 1979-02-01 1981-11-24 Allied Corporation Nickel brazed articles
EP0042525A1 (fr) * 1980-06-24 1981-12-30 Kabushiki Kaisha Toshiba Alliage magnétique amorphe
EP0057935A2 (fr) * 1981-02-10 1982-08-18 Kabushiki Kaisha Toshiba Alliage amorphe magnétique, sensible à la température
EP0066356A1 (fr) * 1981-03-31 1982-12-08 Masumoto Tsuyoshi Procédé pour la fabrication de fils métalliques fins et amorphes
EP0127894A1 (fr) * 1983-06-01 1984-12-12 GTE Products Corporation Alliages de brasage de nickel-fer contenant du carbone
JPH0280533A (ja) * 1988-09-14 1990-03-20 Tdk Corp 高透磁率微細結晶合金及びその製造方法
DE19610539A1 (de) * 1996-03-18 1997-09-25 Vacuumschmelze Gmbh Durch Rascherstarrung herstellbare, duktile Lötfolie

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
DATABASE CA [Online] CHEMICAL ABSTRACTS SERVICE, COLUMBUS, OHIO, US; 28. Juni 2000 (2000-06-28), RABINKIN, A.: "Optimization of brazing technology, structural integrity, and performance of multi-channeled, three dimensional metallic structures" XP002463219 gefunden im STN Database accession no. 2000:432500 & ADVANCED BRAZING AND SOLDERING TECHNOLOGIES, INTERNATIONAL BRAZING & SOLDERING CONFERENCE PROCEEDINGS, ALBUQUERQUE, NM, UNITED STATES, APR. 2-5, 2000 , 437-444. EDITOR(S): VIANCO, PAUL T.; SINGH, MRITYUNJAY. PUBLISHER: AMERICAN WELDING SOCIETY, MIAM, 2000, *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101780611B (zh) * 2009-01-19 2011-09-07 中国科学院金属研究所 一种NiMnCoNbFeSiB带状钎焊材料
CN103060707A (zh) * 2013-01-01 2013-04-24 北京工业大学 一种替代镀硬铬的涂层材料及其激光熔覆制备方法
CN103060707B (zh) * 2013-01-01 2014-11-26 北京工业大学 一种替代镀硬铬的涂层材料及其激光熔覆制备方法
WO2016034395A1 (fr) * 2014-09-05 2016-03-10 Vacuumschmelze Gmbh & Co. Kg Procédé de brasage fort et utilisation d'une feuille de brasage fort pour brasage par induction
CN114101970A (zh) * 2021-11-04 2022-03-01 杭州华光焊接新材料股份有限公司 一种镍基非晶钎料带材及其制备方法

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EP1897650A3 (fr) 2008-05-14

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