EP0480404B1 - Korrosionsbeständiger und wärmebeständiger Metall-Verbundwerkstoff und Verfahren zu seiner Herstellung - Google Patents

Korrosionsbeständiger und wärmebeständiger Metall-Verbundwerkstoff und Verfahren zu seiner Herstellung Download PDF

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EP0480404B1
EP0480404B1 EP91117218A EP91117218A EP0480404B1 EP 0480404 B1 EP0480404 B1 EP 0480404B1 EP 91117218 A EP91117218 A EP 91117218A EP 91117218 A EP91117218 A EP 91117218A EP 0480404 B1 EP0480404 B1 EP 0480404B1
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Prior art keywords
alloy
substrate
layer
sheet
metal composite
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French (fr)
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EP0480404A3 (en
EP0480404A2 (de
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Shinichiro Yahagi
Hiroshi Yamada
Kikuichi Funao
Fumio Iwane
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Daido Steel Co Ltd
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Daido Steel Co Ltd
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Priority claimed from JP27162790A external-priority patent/JP2959092B2/ja
Priority claimed from JP03077763A external-priority patent/JP3094491B2/ja
Priority claimed from JP3134258A external-priority patent/JP3030927B2/ja
Application filed by Daido Steel Co Ltd filed Critical Daido Steel Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
    • C23C28/321—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer with at least one metal alloy layer
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C26/00—Coating not provided for in groups C23C2/00 - C23C24/00
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
    • C23C28/345—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one oxide layer

Definitions

  • the present invention concerns a metal composite having both corrosion-resistant property and heat-resistant property.
  • the invention also concerns the method of producing the composite.
  • the inventors intended to meet the above demand, and tried to form a surface protecting layer of a corrosion-resistant and heat-resistant substance such as Al2O3 by coating it on a heater material made of FCH51 alloy or the like. It was found that, due to the difference in the thermal expansion coefficients of the materials, the coated layer falls off from the substrace after repeated cycles of heating and cooling. Then, they formed protecting layers by vapor-deposition of Al2O3 and succeeded in improving durability of the layers. However, the vapor-deposition operation is of low productivity and high costs, and therefore, they concluded that this technology is difficult to be widespread.
  • the inventors invented a material of improved corrosion resistance which is made by cladding an Al-foil on an alloy of a basic composition, 15Cr-3Al-Fe (so-called "Elemann's steel"), rolling the cladded sheet, annealing in vacuum and heating in an oxidizing atmosphere to oxidize the surface Al to Al2O3.
  • the Elemann's steel has good processability and the surface corrosion resistance is improved by the formation of the Al2O3.
  • the material was already proposed(Japanese Patent Application Hei 2-192090).
  • the inventors also establish the technology for improving high temperature corrosion resistance of electric heater material made of Ni or Ni-Cr alloy by cladding an Al foil thereon and subjecting the cladded sheet to the above mentioned annealing under vacuum and heating in an oxidizing atmosphere to form the Al2O3.
  • the technology was also proposed(Japanese Patent Application Hei 2-148158).
  • the heater material exhibits high durability.
  • the reason is considered to be that intermetallic compound, Ni3Al (partly, NiAl) is formed between the cladded Al layer and the substrate during the heat treatment, and that the intermetallic compound solidly coats the substrate.
  • US-A-4 535 034 relates to a high-Al heat resistant steel comprising a base steel containing not more than 0.7% C, not more than 3.0% Si, not more than 2.0% Mn, 10 to 40% Ni, 9 to 30% Cr, 2 to 8% Al, with the balance being Fe and unavoidable impurities, and an Al coating formed on the base steel.
  • the Al coating diffuses into the base steel to form an intermediate Al alloyed layer during the Al coating or by heating after the coating, which alloyed layer prevents the Al coating from spalling, thus providing excellent resistance to oxidation, corrosion, carburization, nitrization and sulphurdization at elevated temperatures.
  • Database WPIL, AN: 84-104408, Derwent Publication Ltd., London, GB; & JP-A-59 047 382 discloses a coated steel sheet with good heat and corrosion resistance which is coated with an intermetallic compound layer composed of FeAl2 and FeAl and a ceramic layer composed of preferably by weight 15 - 25% SiO2, 30 - 50% Cr2O3 and 35 - 45% Al2O3 which ceramic layer is applied by treating the diffusion treated Al hot-dip coated steel sheet with an aqueous solution containing the aforementioned compounds to form the said layer by heating.
  • EP-A-0 471 505 which is a document within the meaning of Article 54(3) EPC, discloses multilayer coated metallic substrates with a first coating of one or more metals, an optional second coating of a mixture of one or more ceramics and one or more metals or alloys, a third coating of one or more ceramics, and a fourth coating of one or more precious metals or alloys thereof, being substantially non-porous.
  • the first coating is an alloy of Ni 80 wt.% and Al 20 wt.%.
  • the ceramic of the second and third coatings is preferably alumina and is preferably of 99% purity.
  • the general object of the present invention is to provide a metal composite with high temperature corrosion resistance given by the Al2O3 coating, which composite having improved durability by utilizing formation of the above mentioned intermetallic compound such as Ni3Al and/or NiAl, as well as to provide a method of producing a metal composite, particularly, in the form of a sheet or a wire, having such good corrosion resistance and heat resistance.
  • a particular object of the invention is to provide a method of producing at a low cost a metal composite used at a high temperature, which consists of a substrate made of an Fe-based alloy and an Al2O3 protecting layer solidly adhered to the substrate, and thus, the corrosion resistance, particularly, high temperature oxidation resistance is heightened.
  • Another particular object of the invention is to provide a method of producing a metal composite used at a high temperature, which consists of a substrate made of an Fe-based alloy and an Al2O3 protecting layer solidly adhered to the substrate, and thus, in addition to the corrosion resistance such as high temperature oxidation resistance and chemical resistance are heightened.
  • Further particular object of the invention is to provide a metal composite used at a high temperature, which consists of a substrate made of Ni or an alloy containing more than 20 weight % of Ni and an Al2O3 protecting layer solidly adhered to the substrate, and thus, the corrosion-resistance, particularly, high temperature oxidation resistance as well as salt water-resistance are hightened.
  • a metal composite used at a high temperature which consists of a substrate made of Ni or an alloy containing more than 20 weight % of Ni and an Al2O3 protecting layer solidly adhered to the substrate, and thus, the corrosion-resistance, particularly, high temperature oxidation resistance as well as salt water-resistance are hightened.
  • the corrosion-resistant and heat-resistant metal composite of the present invention comprises, in the case of sheets as shown in Fig.1, and in the case of wire as shown in Fig.4, a metal substrate 1, internal layer 5 of at least one of the intermetallic compounds, NiAl, NbAl, FeAl, Ni3Al, Nb3Al and Fe3Al, and surface layer 6 of Al2O3.
  • the substrate may be of any metal which has heat resistance required for the respective use, and therefore, can be chosen from a wide range as noted below.
  • the internal layer 5 of the intermetallic compounds will be a mixed layer of Fe3Al and FeAl.
  • Fe-Cr alloys of FCH-series e.g., FCH51-alloy which consists of Cr 14.0 - 15.0 %, Al 2.80 - 3.30 %, C being up to 0.07%, Si up to 0.50% and Mn up to 0.60% and the balance of Fe
  • Other Fe-based alloys may be used as the substrate metal in accordance with the use of the metal composite. They may be Fe-based alloys in which Ni content is up to 20 weight %, for example, various structural steels, ferritic, austenitic and martensitic stainless steels.
  • the Fe-based alloys to be used as the substrate may further contain a component or components selected from B, Si, Mg, Cu, Ca, Mn, Y, Ti, Co, W, V, Zr and REMs so as to improve the properties of the alloy and to cause formation of the intermetallic compounds of Al and these components.
  • Another embodiment of the metal composite of the present invention comprises, as explained above in regard to the first case where an Fe-based alloy is used as the substrate in reference to Fig.1 and Fig.4, a substrate 1 of Ni or an alloy containing more than 20 weight % of Ni, an internal layer 5 in which intermetallic compounds, Ni3Al and NiAl, coexist, and a surface layer 6 of Al2O3.
  • the substrate may be pure Ni metal or an alloy containing more than 20 weight % of Ni, the latter including various Ni-based alloys and Fe-based alloys.
  • the examples of the alloys are as follows (% is by weight):
  • the method of producing the corrosion-resistant and heat-resistant metal composite in the form of a sheet according to the present invention comprises, as shown in Fig.2, cladding an Al sheet 3A and Ni (or Nb) sheet 2A on at least a part of the sheet of the metal substrate 1 (in the illustrated example, on one side of the sheet) in the manner that the latter is inside to form a cladded sheet shown in Fig.3, and annealing the cladded sheet under vacuum and then, heating in an oxidizing atmosphere to form, between the Al layer 3B and the Ni (or Nb) layer 2B, as shown in Fig.1, the internal layer 5 of intermetallic compound or compounds, Ni3Al (or Nb3Al) and/or NiAl (or NbAl), and to form the Al2O3 layer 6 at the surface.
  • cladded sheet of Al sheet 3A and Ni (or Nb) sheet 2B As shown in Fig.2 prior to cladding them on the metal substrate 1.
  • suitable thickness of the cladded sheet is 0.1 - 1.0 mm, in which the thickness of the Al layer is 0.001 - 0.5 mm.
  • it is operable to separately clad Ni and Al or Nb, or to firstly clad Ni (or Nb) sheet 2A on the metal substrate 1, and then, clad Al sheet 3A.
  • the method of producing the corrosion-resistant and heat-resistant metal composite in the form of a wire according to the present invention comprises, as shown in Fig.5, cladding an Al tube 3E and Ni (or Nb) tube 2E on the wire of the metal substrate 1 by inserting the wire in the tubes in the manner that the latter tube is inside and wire-drawing to form a cladded wire shown in Fig.5, and annealing the cladded wire under vacuum and then, heating in an oxidizing atmosphere to form, between the Al layer 3F and the Ni (or Nb) layer 2F, as shown in Fig.4, the internal layer 5 of intermetallic compound or compounds, Ni3Al (or Nb3Al) and/or NiAl (or NbAl), and to form the Al2O3 layer 6 at the surface.
  • diameter of the metal substrate wire is around 10 mm and the thickness of the covering Al tube and Ni tube (or Nb tube) are, similar to the cases of producing a sheet, 0.1 - 1.0 mm.
  • wire-drawing operation for several passes of drawing at a reduction of area of 30 - 50 % a cladded wire of a diameter of 0.5 - 3 mm will be obtained.
  • the wires may have any profile of section.
  • the section may be of not only the round circle as shown in Fig.4 but also a square, rectangular and so on.
  • a cladded wire of the section profile shown in Fig.7 can be obtained by rolling using profiled rolls, and then, the cladded wire can be further rolled to get the shape near the sheet.
  • This kind of products has a higher corrosion resistance in comparison with the products of Fig.2 and Fig.3, because not only the flat surfaces but also both the sides of the former products are covered with the protecting layers.
  • the method of producing a metal composite of the present invention using Ni or an alloy containing more than 20 weight % of Ni as the substrate comprises, as shown in Fig.8 and Fig.9, covering the surface of the metal substrate 1, which is made of Ni or an alloy containing more than 20 weight % of Ni, with a layer 3 of Al or Al-alloy; subjecting the covered material to annealing and heating under vecuum or in an inert gas atmosphere to form, as shown in Fig.1 and Fig.4, the layer 5 in which Ni3Al and NiAl coexist , and to form the surface protecting layer of Al2O3.
  • Preferable thickness of Al or Al-alloy foil to be cladded is 0.005 - 0.5 mm, and the thickness after the rolling will be 0.001 - 0.2 mm.
  • covering with Al or Al-alloy may be carried out by insering a substrate wire in a tube of a covering material and wire drawing or extrusion processing.
  • diameter of the metal substrate is around 10 mm
  • thickness of the Al or Al- alloy tube for covering it may be 0.1 - 1.0 mm as in the case of sheet products.
  • Wire drawing of several passes under a reduction of area of 30 - 50 % will give a cladded wire of a diameter of 0.5 -3 mm.
  • the other possible ways of covering the substrate with Al or Al-alloy are dipping the substrate in molten Al or Al-alloy, thermal-spray of Al or Al-alloy on the substrate surface, plasma powder welding, chemical plating and vapor-deposition.
  • the alloy may be such ones that further contain one or more of the additional components selected from B, Si, Mg, Cu, Ca, Mn, Y, Ti, Co, W, Zr, Ta, Nb, Sc and REMs so as to enjoy the benefit of improved properties of the Al-alloy depending on the kind of the additional components.
  • Annealing under vacuum or in an inert gas is carried out by heating to a temperature of 400 - 900°C, preferably 400 - 600 °C for 1 - 10 hours.
  • the subsequent heating in an oxidizing atmosphere is conducted, for example, at a temperature of 400 - 1000°C for 1 - 36 hours.
  • suitable thickness of the laminated sheet is 0.1 - 1.0 mm, and that of the Al part is 0.005 - 0.5 mm in total of both the sides. It is of course operable to clad the foils one by one, or to prepare a laminate of any two of the three foils and clad it with the remaining one foil.
  • sequence of cladding can be chosen arbitrarily.
  • Ni3Al and NiAl occur at the places in the direction of depth depending on the concentrations of Ni and Al. If the covering Al layer is thick, concentrations of the formed intermetallic compounds will have a gradient, however, if the layer is thin and the heat treatment is done thoroughly, the concentration gradient substantially disappears and a layer in which Ni3Al and NiAl uniformly coexist is formed.
  • the substrate is a steel such as a SUS
  • intermetallic compound, Fe3Ni occurs at the interface of the substrate and Ni layer.
  • the substrate Fe-based metal, Ni or an alloy thereof contains one or more of the above mentioned alloy elements which may form an intermetallic compound, i.e., B, Si, Mg, Cu, Ca, Mn, Y, Ti, Co, W, V, Zr, Ta, Nb, Sc and Rare Earth Metals (REMs), or in case where one or more of such components are contained in the cladded Al-alloy, an intermetallic compound or compounds between these elements and Al will occur instead of the Ni-Al intermetallic compounds.
  • an intermetallic compound or compounds between these elements and Al will occur instead of the Ni-Al intermetallic compounds.
  • the Al at the surface is oxidized by heating in an oxidizing atmosphere to form dense Al2O3. Crystals of this compound may grow in the form of whiskers to coat the surface.
  • Al2O3 diffuses into the substrate metal of Ni or an alloy containing more than 20 weight % of Ni to cause good adhesion at the interface of joint, and a portion of the Al is oxidized to form Al2O3.
  • the protecting layer of Al2O3 exists on the substrate with ankered roots in the substrate metal, and thus, strongly coats and protects the substrate.
  • the coating layer is usually a dense one, but it is inevitable that there are micropores in some places. Corrosive chemical liquid such as salt water may penetrate through the micropores and attack the substrate metal.
  • the metal composite according to the present invention generally has much better corrosion-resistance due to the Ni-Al intermetallic compounds.
  • the interfaces between the substrate and the first Al layer 2, the Al layer 2 and the Ni layer 3, and the Ni layer 3 and the second Al layer 2' adhere solidly due to the diffusions as explained above during the annealing under vacuum, and the diffusions further proceed during the subsequent heating in an oxidizing atmosphere.
  • layers in which Ni3Al and NiAl coexist depending on the concentrations of Ni and Al components are formed.
  • the processability of the product metal composite is very good, and therefore, the product can be easily processed even after formation of Al2O3 protecting layer.
  • the present metal composite which comprises the substrate metal of Fe-based alloy, Ni or Ni alloy containing more than 20 weight % or Ni, and the solid coating layer of Al2O3 on the surface of the substrate for protection, exhibits improved corrosion resistance represented by high temperature oxidation resistance and salt water-resistance.
  • the electric heater material a typical use of Fe-Cr alloy
  • the present metal composite can be understood as the product using FCH51-alloy which is less expensive and has good processability as the substrate and improving the high temperature corrosion resistance, which is low in this alloy.
  • the metal composite can find wide use not only for the above mentioned typical use, electric heater, but also various use in industrial apparatus and electric appliances.
  • the method of producing the metal composite of the present invention enables production of the above described products by employing the easy way of forming Al layer such as cladding and transformation of the Al to Al2O3. This method thus gives the product which is protected by an Al2O3 layer of a thickness chosen from a wide range and has roots ankered in the substrate for solid adhesion.
  • Al/Ni laminated sheet and an Al/Nb laminated sheet both having thickness of 0.1 mm, in which Al layer is 0.04 mm thick were prepared.
  • the laminated sheet were rolled on both sides of thin sheets of SUS430 in the manner that the Ni or Nb was inside, to produce cladded sheets of 0.05 mm thick. Thickness of the Al layers was 0.002 mm (per one side), and that of Ni or Nb layers was 0.004 mm (per one side).
  • the cladded sheets were slitted to ribbons of 6 mm wide and 200 m long, which were annealed under vacuum at 600°C for 2 minutes, and then heated in air at 600°C for 60 minutes.
  • a ribbon of SUS430 alone and a ribbon of SUS430 having Al layers 0.002 mm thick (the same as above) on both sides were prepared and heated in air at 600°C for 60 minutes.
  • test pieces are kept at a temperature of 800°C under a constant tension, and receive spray of 5%-NaCl solution once every 2 minutes, and the times of spraying until the test piece breaks is recorded.
  • the results are shown in Fig.13.
  • the layer structures of the test pieces of the examples and the controls were as follows:
  • test pieces are kept in air at a temperature of 1100°C, and the weight increase by passage of time (mg/cm2) is measured. The results are as shown in Fig.14.
  • Al foils 0.1 mm thick were cladded to both the sides of a thin FCH51 alloy of 0.2 mm thickness by rolling. By further rolling a cladded material with a thickness of 0.1 mm in total, in which the thickness of both the Al layers was 0.04 mm.
  • the cladded material was slitted to ribbons of 30 mm width, and the ribbons were heated in air to 600°C for 1 hour so as to cause the change of Al to Al2O3 and to grow the Al2O3 layer.
  • the ribbon of FCH51 alloy having the Al2O3 protecting layers was heated to 1100°C in air and the weight increase by oxidation was observed as the measure of the high temperature oxidation-resistance.
  • a ribbon of FCH51 alloy alone and a ribbon of FCH51 alloy on which Al layer was vapor-deposited and subjected to oxidation treatment for formation of Al2O3 protecting layer were also tested under the same conditions. The results are shown in Fig.15. From the graph of Fig.15 it can be seen that the Al2O3 protecting layer effectively improved the high temperature oxidation resistance of FCH51 heater material.
  • the Fe-based alloys of the alloy compositions (weight %, the balance being Fe) shown in Table 1 were used as the substrates.
  • Al foils of 0.015 mm thickness were cladded by rolling to give the covered material in the form of sheet, the total thickness of which was 0.05 mm and those of the two Al layers, 0.002 mm.
  • the product using the substrate of the alloy "A" in Table 1 was tested by bending test and tensile test.
  • the bending test comprises repeated cycles of bending to 90° and flattening, and the number of cycles until the test piece breaks is recorded. The number reached to 5. The elongation was 3 %.
  • Example 2 The salt water spray test as described in Example 1 was conducted on these samples to determine the high temperature corrosion resistance. The results are shown in Fig.19.
  • Laminated sheets of Al/Ni/Al three layers were prepared.
  • the thickness of the Al foils was 0.008 mm (0.004 mm a side) and the total thickness of the laminate was 0.1 mm.
  • the laminated sheets were rolled on a thin Ni sheet to produce a cladded material with 0.05 mm thickness (No.5).
  • thickness of the Al layers was (both the first and the second layers) 0.002 mm, and that of the Ni layer was 0.05 mm.
  • the material was slitted to ribbons 6 mm in width and 200 m in length, which ribbons were heated under vacuum to 600°C for 60 minutes.
  • the cladded material was subjected to annealing under vacuum at 600°C for 30 minutes to form the Ni-Al intermetallic compound, and then, heated in air to about 800°C for 3 hours to form the Al2O3 layer at the surface.
  • the product using No.8 metal as the substrate was tested by the bending test and the tensile test.
  • the bending test was described in Example 3.
  • the test results are shown in Figs. 21-23.
  • the plots in the Figures are the averaged data of the bending test on 5 samples of each composition.
  • the material was slitted to ribbons 6 mm wide and 200 m long, and a ribbon was heated under vacuum to 600°C for 60 minutes (No.12).
  • a ribbon of NCH2 alloy of the same dimensions was prepared (No.13).
  • the samples were tested by salt water dropping test to determine the high temperature corrosion resistance.
  • the salt water dropping test comprises, as in the salt water spray test, that the test piece is kept at 800°C under a constant tension, and 5%-NaCl water solution 0.5 cm3 is dropped once every 2 minutes on the test piece. The times of dropping the salt water until the break of the test piece is the measure of the corrosion resistance.
  • the test results are shown in Fig.24.
  • Thin sheets with 0.2 mm thickness were prepared using Ni-Al alloys which consist of Al 2 %, 4 %, 6 %, or 8 % and the balance of Ni. On both the sides of these substrates, Al foils 0.015 mm thick were rolled to obtain cladded materials. The thickness was 0.05 mm in total, and that of the Al layers was 0.02 mm.
  • the cladded materials were subjected to annealing under vacuum at 600°C for 2 minutes followed by heating in air to 600°C for 1 hour to form the Al2O3 protecting layer.
  • a metal composite of the present invention was produced by the same operation as those of Example 8.(No. 19)

Claims (16)

  1. Korrosionsbeständiger und hitzebeständiger Metallverbundwerkstoff, dadurch gekennzeichnet, daß der Verbundwerkstoff ein Substrat aus Ni oder einer Ni-Legierung, die mehr als 20 Gew.-% Ni enthält, eine innere Schicht, in der die intermetallischen Verbindungen Ni₃Al und NiAl gemeinsam vorliegen, und eine Oberflächenschicht aus Al₂O₃ umfaßt.
  2. Metallverbundwerkstoff nach Anspruch 1, dadurch gekennzeichnet, daß die Ni-Legierung, die mehr als 20 Gew.-% Ni enthält, eine Ni-Cr-Legierung ist, die aus Cr: 14,0 bis 23,5 %, C: bis zu 0,15 %, Mn: bis zu 2,5 % und zum Rest aus Ni besteht.
  3. Metallverbundwerkstoff nach Anspruch 1, dadurch gekennzeichnet, daß die Ni-Legierung, die mehr als 20 Gew-% Ni enthält, eine Legierung auf Ni-Basis ist, die aus einem oder mehreren von B: 0,08 bis 0,18 %, Re: 1 bis 3 %, Fe: 5 bis 20 % und Mn: 5 bis 20 % und zum Rest aus Ni besteht.
  4. Metallverbundwerkstoff nach Anspruch 1, dadurch gekennzeichnt, daß die Ni-Legierung, die mehr als 20 Gew.-% Ni enthält, eine Fe-Ni-Cr-Legierung ist, die aus Ni: 20 bis 72 %, Cr: 14 bis 35 % und zum Rest aus Fe besteht.
  5. Metallverbundwerkstoff nach Anspruch 1, dadurch gekennzeichnet, daß die Ni-Legierung, die mehr als 20 Gew.-% Ni enthält, eine Ni-Al-Legierung ist, die aus Al: 1 bis 6 % und zum Rest aus Ni besteht.
  6. Metallverbundwerkstoff nach Anspruch 1, dadurch gekennzeichnet, daß die Ni-Legierung, die mehr als 20 Gew.-% Ni enthält, eine Ni-Al-Be-Legierung ist, die aus Al: 1 bis 6 %, Be: 0,2 bis 3,0 % und zum Rest aus Ni besteht.
  7. Metallverbundwerkstoff nach Anspruch 1, dadurch gekennzeichnet, daß die Ni-Legierung, die mehr als 20 Gew.-% Ni enthält, eine Legierung von solcher Zusammensetzung ist, daß eines oder mehrere der Elemente B, Si, Mg, Cu, Ca, Mn, Y, Ti, Co, W, V, Zr, Ta, Nb, Sc und Seltenerdmetalle (REMs) dem Nickel oder den in den Ansprüchen 2 bis 6 definierten Legierungen zugesetzt wird bzw. zugesetzt werden.
  8. Verfahren zur Herstellung eines korrosionsbeständigen und hitzebeständigen Metallverbundwerkstoffs, dadurch gekennzeichnet, daß das Verfahren die Stufen des Beschichtens eines Metallsubstrats entweder aus einer Legierung auf Fe-Basis mit, wenn es enthalten ist, einem Ni-Gehalt von bis zu 20 Gew.-%, oder aus Ni oder einer Ni-Legierung, die mehr als 20 Gew.-% Ni enthält, mit Al oder einer Al-Legierung, des Vergütens bzw. des Anlassens des resultierenden beschichteten Materials unter Vakuum oder in einer Inertgasatmosphäre durch Erhitzen auf eine Temperatur von 400 bis 900°C für 1 bis 200 Minuten und des Erhitzens des Materials in einer oxidierenden Atmosphäre bei einer Temperatur von 400 bis 1000°C für 1 Minute bis 36 Stunden, um eine Schicht zu bilden, in der intermetallische Verbindungen, Fe₃Al und FeAl oder Ni₃Al und NiAl oder Nb₃Al und NbAl, auf dem Substrat coexistieren und um eine Al₂O₃-Schicht an der Oberfläche zu bilden, umfaßt.
  9. Verfahren nach Anspruch 8, dadurch gekennzeichnet, daß das Verfahren die Stufe des Plattierens eines Al-Blechs und entweder eines Ni-Blechs oder Nb-Blechs auf mindestens einem Teil eines Metallsubstratblechs in der Weise, daß das Ni-Blech oder das Nb-Blech sich zwischen dem Al-Blech und dem Substratblech befindet, Vergüten bzw. Anlassen des resultierenden plattierten Materials unter Vakuum, Erhitzen des plattierten Materials in einer oxidierenden Atmosphäre, um intermetallische Verbindungen, Ni₃Al (oder Nb₃Al) und/oder NiAl (oder NbAl) zwischen der Al-Schicht und der Ni-Schicht (oder Nb-Schicht) und Al₂O₃ an der Oberfläche zu bilden, umfaßt.
  10. Verfahren nach Anspruch 8, dadurch gekennzeichnet, daß das Verfahren die Stufen des Plattierens eines Al-Rohrs und entweder eines Ni-Rohrs oder eines Nb-Rohrs auf einen Metallsubstratdraht in der Weise, daß sich das Ni-Rohr oder das Nb-Rohr zwischen dem Al-Rohr und dem Substratdraht befindet, Vergüten bzw. Anlassen des resultierenden plattierten Materials unter Vakuum, Erhitzen des plattierten Materials in einer oxidierenden Atmosphäre, um intermetallische Verbindungen, Ni₃Al (oder Nb₃Al) und/oder NiAl (oder NbAl) zwischen der Al-Schicht und der Ni-Schicht (oder Nb-Schicht) und Al₂O₃ an der Oberfläche zu bilden, umfaßt.
  11. Verfahren nach Anspruch 8, dadurch gekennzeichnet, daß das Verfahren die Stufen des Bedeckens der Oberfläche eines Substrats aus Ni oder einer Ni-Legierung, die mehr als 20 Gew.-% Ni enthält, mit, in der Richtung von der Innenseite zur Außenseite, der ersten Al-Schicht, einer Ni- oder Ni-Legierungsschicht und der zweiten Al-Schicht, des Vergütens bzw. des Anlassens des beschichteten Materials unter Vakuum oder in einer Inertgasatmosphäre und des Erhitzens des Materials in einer oxidierenden Atmosphäre, um eine Schicht zu bilden, in der intermetallische Verbindungen, Ni₃Al und NiAl auf dem Substrat coexistieren und um eine Al₂O₃-Schicht an der Oberfläche zu bilden, umfaßt.
  12. Verfahren nach Anspruch 8, dadurch gekennzeichnet, daß das Substrat aus Ni oder einer Ni-Legierung, die mehr als 20 Gew.-% Ni enthält, in der Form eines Blechs vorliegt und daß man das Beschichten des Substrats mit Al oder einer Al-Legierung durch Plattierungswalzen durchführt.
  13. Verfahren nach Anspruch 8, dadurch gekennzeichnet, daß das Substrat aus Ni oder einer Ni-Legierung, die mehr als 20 Gew.-% Ni enthält, in der Form eines Drahtes vorliegt und daß man das Beschichten des Substrats mit Al oder einer Al-Legierung durch Einführen des Substratdrahtes in ein Rohr des beschichtenden Materials und Drahtziehen oder Extrudieren durchführt.
  14. Verfahren nach Anspruch 8, dadurch gekennzeichnet, daß man das Beschichten des Substrats mit Al oder einer Al-Legierung durch Eintauchen des Substrats in geschmolzenes Al oder eine geschmolzene Al-Legierung, durch thermisches Aufsprühen von Al oder einer Al-Legierung, Plasmapulverschweißen, chemisches Plattieren, Aufspritzen oder Aufdampfen durchführt.
  15. Verfahren nach Anspruch 8, dadurch gekennzeichnet, daß das Substrat aus Ni- oder einer Ni-Legierung, die mehr als 20 Gew.-% Ni enthält, in einer sperrigen Form vorliegt und daß man das Beschichten des Substrats mit Al oder einer Al-Legierung durch Eintauchen des Substrats in geschmolzenes Al oder eine geschmolzene Al-Legierung, durch thermisches Aufsprühen von Al oder einer Al-Legierung, Plasmapulverschweißen, chemisches Plattieren, Aufspritzen oder Aufdampfen durchführt.
  16. Verfahren nach Anspruch 8, dadurch gekennzeichnet, daß die Al-Legierung eine solche Zusammensetzung aufweist, daß eines oder mehrere der Elemente B, Si, Mg, Cu, Ca, Mn, Y, Ti, Co, W, V, Zr, Ta, Nb, Sc und Seltenerdmetalle (REMs) dem Al zugesetzt werden.
EP91117218A 1990-10-09 1991-10-09 Korrosionsbeständiger und wärmebeständiger Metall-Verbundwerkstoff und Verfahren zu seiner Herstellung Expired - Lifetime EP0480404B1 (de)

Applications Claiming Priority (6)

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JP27162790A JP2959092B2 (ja) 1990-10-09 1990-10-09 耐食耐熱性金属複合材とその製造方法
JP271627/90 1990-10-09
JP03077763A JP3094491B2 (ja) 1990-04-10 1991-04-10 シート状またはワイヤ状のヒーター材およびその製造方法
JP77763/91 1991-04-10
JP134258/91 1991-06-05
JP3134258A JP3030927B2 (ja) 1990-06-06 1991-06-05 高温耐食部材およびその製造方法

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EP0480404A3 EP0480404A3 (en) 1993-02-17
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DE502005007982D1 (de) * 2005-01-14 2009-10-08 Siemens Ag Schichtsystem mit Sperrschicht und Verfahren zur Herstellung
EP1762636A1 (de) * 2005-09-07 2007-03-14 Alcan Technology & Management Ltd. Verfahren zum Plattieren eines Profils aus einer Aluminiumlegierung
WO2008107000A1 (de) * 2007-03-08 2008-09-12 Alcan Technology & Management Ltd. Verfahren zum plattieren eines profils aus einer aluminiumlegierung
CN102069290B (zh) * 2010-12-09 2013-01-09 上海工程技术大学 扩散连接制备Fe3Al/Al复合结构的工艺
DE102014116335A1 (de) * 2014-11-10 2016-05-12 Thyssenkrupp Ag Verbundwerkstoff, Verbundwerkstoffprodukt, Verfahren zu deren Herstellung und Verwendungen dafür
CN113512702B (zh) * 2021-07-14 2023-02-28 北航（四川）西部国际创新港科技有限公司 一种单相β-NiAl粘结层及其制备方法
CN114192602B (zh) * 2021-12-14 2022-09-13 大连理工大学 一种高性能多元NiAl基合金管件迭覆级进成形方法
CN114558886B (zh) * 2022-03-10 2023-09-29 长沙市泰润粉末材料有限公司 一种侧边复合的铜铝复合板带材的制备方法

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