EP0996752B1 - Alloy for corrosion-resistant coatings or surface coatings - Google Patents

Alloy for corrosion-resistant coatings or surface coatings Download PDF

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Publication number
EP0996752B1
EP0996752B1 EP98929635A EP98929635A EP0996752B1 EP 0996752 B1 EP0996752 B1 EP 0996752B1 EP 98929635 A EP98929635 A EP 98929635A EP 98929635 A EP98929635 A EP 98929635A EP 0996752 B1 EP0996752 B1 EP 0996752B1
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EP
European Patent Office
Prior art keywords
metal
alloy
yttrium
main group
cobalt
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.)
Expired - Lifetime
Application number
EP98929635A
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German (de)
French (fr)
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EP0996752A1 (en
Inventor
Nelso Antolotti
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Turbocoating SpA
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Turbocoating SpA
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Publication date
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Publication of EP0996752A1 publication Critical patent/EP0996752A1/en
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Classifications

    • 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
    • C23C30/00—Coating with metallic material characterised only by the composition of the metallic material, i.e. not characterised by the coating process
    • 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
    • C22C19/07—Alloys based on nickel or cobalt based on cobalt

Definitions

  • the present invention relates to an alloy for anti-corrosive coatings or surface coatings which are resistant up to 1100°C.
  • Such surface coatings can be obtained by the following thermal spraying methods:
  • Said alloy is resistant to corrosion and guarantees a service life of 1000 hours if used for the coating of components which operate in the presence of sodium-, vanadium-, sulphur- and chlorine-containing hydrocarbon combustion products.
  • a first disadvantage is that this alloy does not guarantee sufficient corrosion resistance if employed at temperatures above 700°C.
  • Said second alloy is used for coating components with a superalloy material.
  • the presence of silicon in the coating matrix provides resistance against the formation of oxides and sulphides on the surface layer.
  • this second alloy has a low yttrium content, which is insufficient for ensuring corrosion resistance in the presence of products containing substantial amounts of sulphur, chlorine and vanadium.
  • a third alloy is known from US 4,585,481, which describes an alloy based on cobalt and containing chromium, aluminium, yttrium and silicon in the following proportions: Chromium (Cr) 5.0 - 40.0% Aluminium (Al) 8.0 - 35.0% Yttrium (Y) 0.1 - 2.0% Silicon (Si) 0.1 - 7.0% Cobalt (Co) remaining percentage.
  • this alloy results in a reduction of the plasticity of the coating, making it impossible to use it for the coating of apparatuses or objects which must withstand substantial changes in temperature.
  • a further disadvantage is that, during application of the coating or surface coating by the plasma method, oxidation of yttrium and silicon may take place.
  • This third alloy is unable to guarantee the corrosion resistance required in the presence of combustion products containing substantial amounts of sulphur, chlorine and vanadium.
  • the alloys mentioned above can usually be used at temperatures not exceeding 900°C. since all of them are based on cobalt.
  • RU-A-2051196 teaches an alloy for corrosion-resistant coatings or surface coatings, containing of cobalt, chromium, aluminium, yttrium, silicon, and a metal from the second main group, together with the corresponding oxide, in the following proportions: Chromium (Cr) 26.0 - 30.0% Aluminium (Al) 6.0 - 8.0% Yttrium (Y) 0.3 - 1.5% Silicon (Si) 1.5 - 4.5% Metal from the second main group (magnesium, calcium, barium, strontium) 0.1 - 0.5% Oxide of the corresponding metal from the second main group 0.1 - 1.0% Cobalt (Co) remaining percentage.
  • This alloy resists only up to 800°C.
  • the object of the present invention is to eliminate the abovementioned disadvantages and provide an alloy with excellent performance even at high temperatures, in particular even above 1000°C.
  • alloy for corrosion-resistant coatings or surface coatings and which is characterized by the composition defined in claim 1, with preferred embodiments in claims 2 and 3.
  • the Applicant has realized that the disadvantages of the known alloys based on cobalt and containing chromium, aluminium, yttrium and silicon can be avoided by adding one the metals from the second main group (magnesium, calcium, barium, strontium), both in free form and in the form of the oxide.
  • the alloy according to the present invention is an alloy for anti-corrosive surface coatings which is based on cobalt and contains chromium, aluminium, yttrium, silicon, and a metal from the second main group, together with the. corresponding oxide, in the following proportions: Chromium (Cr) 22.0 - 31.0% Aluminium (Al) 5.5 -13.0% Yttrium (Y) 0.3 - 1.5% Silicon (Si) 1.5 - 10.0% Metal from the second main group (Mg, Ca, Ba, Sr) 0.1 - 2.0% Oxide of the corresponding metal (Mg, Ca, Ba, Sr) from the second main group 0.1 - 2.0% Tantalum (Ta) 0.5 - 4.0% Me remaining percentage where Me denotes a metal which can be nickel (Ni) or iron (Fe) or cobalt (Co) or a composition consisting of Ni-Fe-Co, Ni-Fe, Fe-Co, NI-Co.
  • rhenium (Re) is envisaged as being present in a percentage of 2.0 - 11.0.
  • yttrium (Y) by an yttrium/hafnium (Y/Hf) composition having the same percentage (0.3 -1.5%), relative to the total of the components, achieves better adhesion of the alumina, Al 2 O 3 , to the surface of the coating.
  • the combination of silicon with the metal from the second main group and its oxide makes it possible to maintain the operational capacity of the surface coating obtained when applied by plasma spraying in air or by high-velocity flame spraying.
  • the presence of the metal from the second main group (Mg, Ca, Ba, Sr) in the proportions mentioned prevents the yttrium and silicon from being oxidized during application of the coating or surface coating.
  • a lower content of silicon, of the metal from the second main group and its oxide in the alloy based on nickel, iron and cobalt according to the present invention does not increase the corrosion resistance of the coating.
  • a higher content of silicon, yttrium, metal from the second main group and its oxide in the alloy according to the present invention produces a deterioration in the mechanical characteristics of the coating obtained, increases the fragility, reduces the coefficient of thermal expansion, and thus causes the coating to form cracks and to flake and therefore lowers the protection with respect to corrosion caused by sulpho-oxidation.
  • the addition of tantalum and/or rhenium furthermore results in a significantly improved performance at oxidation temperature levels above temperatures of 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)
  • Chemical Kinetics & Catalysis (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)
  • Coating By Spraying Or Casting (AREA)
  • Physical Vapour Deposition (AREA)
  • Chemically Coating (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)

Abstract

The invention falls within the field of anti-corrosive alloys and relates in particular to an alloy containing cobalt, chromium, aluminium, yttrium, silicon, a metal from the second main group, together with the corresponding oxide, in the following proportions: chromium (Cr) 26.0-30 %; aluminium (A1) 5.5-13.0 %; yttrium (Y) 0.3-1.5 %; silicon (Si) 1.5-4.5 %; metal from the second main group (magnesium, calcium, barium, strontium) 0.1-2.0 %; oxide of the corresponding metal from the second main group 0.1-2.0 %; cobalt (Co) remaining percentage. Preferably, tantalum (Ta) is also added in a proportion of 0.5-4.0 %, and the remaining percentage of cobalt is replaced by a remaining percentage of Me, Me being understood to mean a metal which may be nickel (Ni) or iron (Fe) or cobalt (Co) or a composition comprising Ni-Fe-Co, Ni-Fe, Ni-Co, Co-Fe.

Description

The present invention relates to an alloy for anti-corrosive coatings or surface coatings which are resistant up to 1100°C.
Such surface coatings can be obtained by the following thermal spraying methods:
  • plasma spraying in vacuo, plasma spraying in air, HVOF (High-Velocity Oxygen Fuel) or high-velocity oxygen flame.
    • In the field of metallurgy, and in particular in the field of alloys used as coatings for gas turbines against corrosion caused by sulpho-oxidation, an alloy based on cobalt and also containing chromium, aluminium and yttrium in the following proportions:
    Chromium (Cr) 8.0 - 30.0%
    Aluminium (Al) 5.0 - 15.0%
    Yttrium (Y) 0 - 1.0%
    Cobalt (Co) remaining percentage
    is already known.
    Said alloy is resistant to corrosion and guarantees a service life of 1000 hours if used for the coating of components which operate in the presence of sodium-, vanadium-, sulphur- and chlorine-containing hydrocarbon combustion products.
    A first disadvantage is that this alloy does not guarantee sufficient corrosion resistance if employed at temperatures above 700°C.
    Furthermore, if said alloy is applied by a thermal spraying method (APS, VPS, HVOF), oxidation of yttrium and aluminium occurs, thus resulting in the loss of the working property of the coating.
    A second alloy based on cobalt and containing chromium, aluminium, yttrium and silicon in the following proportions:
    Chromium (Cr) 12.5 - 20.0%
    Aluminium (Al) 2.0 - 8.0%
    Yttrium (Y) 0- 0.25%
    Silicon (Si) 2.0 - 6.0%
    Cobalt (Co) remaining percentage
    is also known.
    Said second alloy is used for coating components with a superalloy material. The presence of silicon in the coating matrix provides resistance against the formation of oxides and sulphides on the surface layer.
    However, this second alloy has a low yttrium content, which is insufficient for ensuring corrosion resistance in the presence of products containing substantial amounts of sulphur, chlorine and vanadium.
    A third alloy is known from US 4,585,481, which describes an alloy based on cobalt and containing chromium, aluminium, yttrium and silicon in the following proportions:
    Chromium (Cr) 5.0 - 40.0%
    Aluminium (Al) 8.0 - 35.0%
    Yttrium (Y) 0.1 - 2.0%
    Silicon (Si) 0.1 - 7.0%
    Cobalt (Co) remaining percentage.
    However, this alloy results in a reduction of the plasticity of the coating, making it impossible to use it for the coating of apparatuses or objects which must withstand substantial changes in temperature.
    A further disadvantage is that, during application of the coating or surface coating by the plasma method, oxidation of yttrium and silicon may take place.
    This third alloy is unable to guarantee the corrosion resistance required in the presence of combustion products containing substantial amounts of sulphur, chlorine and vanadium.
    The alloys mentioned above can usually be used at temperatures not exceeding 900°C. since all of them are based on cobalt.
    RU-A-2051196 teaches an alloy for corrosion-resistant coatings or surface coatings, containing of cobalt, chromium, aluminium, yttrium, silicon, and a metal from the second main group, together with the corresponding oxide, in the following proportions:
    Chromium (Cr) 26.0 - 30.0%
    Aluminium (Al) 6.0 - 8.0%
    Yttrium (Y) 0.3 - 1.5%
    Silicon (Si) 1.5 - 4.5%
    Metal from the second main group (magnesium, calcium, barium, strontium) 0.1 - 0.5%
    Oxide of the corresponding metal from the second main group 0.1 - 1.0%
    Cobalt (Co) remaining percentage.
    This alloy resists only up to 800°C.
    The object of the present invention is to eliminate the abovementioned disadvantages and provide an alloy with excellent performance even at high temperatures, in particular even above 1000°C.
    Said objects are fully achieved by the alloy, according to the present invention, for corrosion-resistant coatings or surface coatings and which is characterized by the composition defined in claim 1, with preferred embodiments in claims 2 and 3.
    After numerous studies, the Applicant has realized that the disadvantages of the known alloys based on cobalt and containing chromium, aluminium, yttrium and silicon can be avoided by adding one the metals from the second main group (magnesium, calcium, barium, strontium), both in free form and in the form of the oxide.
    The alloy according to the present invention is an alloy for anti-corrosive surface coatings which is based on cobalt and contains chromium, aluminium, yttrium, silicon, and a metal from the second main group, together with the. corresponding oxide, in the following proportions:
    Chromium (Cr) 22.0 - 31.0%
    Aluminium (Al) 5.5 -13.0%
    Yttrium (Y) 0.3 - 1.5%
    Silicon (Si) 1.5 - 10.0%
    Metal from the second main group (Mg, Ca, Ba, Sr) 0.1 - 2.0%
    Oxide of the corresponding metal (Mg, Ca, Ba, Sr) from the second main group 0.1 - 2.0%
    Tantalum (Ta) 0.5 - 4.0%
    Me remaining percentage
    where Me denotes a metal which can be nickel (Ni) or iron (Fe) or cobalt (Co) or a composition consisting of Ni-Fe-Co, Ni-Fe, Fe-Co, NI-Co.
    Moreover, according to a variant, in addition to tantalum or in place of tantalum, rhenium (Re) is envisaged as being present in a percentage of 2.0 - 11.0.
    The addition of one of the metals from the second main group (magnesium, calcium, barium, strontium), both in free form and in the form of the oxide, in the abovementioned proportions, does indeed avoid the disadvantages of the cobalt-based alloys of the prior art.
    The predominant presence of the metal denoted by Me and the content of chromium and aluminium in the percentages given ensure that the coating obtained exhibits a base and two phases: the γ-phase matrix on top of an Me-Cr base and the free Me-Al β-phase.
    The presence of aluminium on the surface of the coating in the abovementioned percentage results in the formation of a protective Al2O3 layer which gives the coating obtained improved corrosion resistance.
    The presence of yttrium in the proportions mentioned prevents the coating from developing cracks and from flaking.
    Moreover, the Applicant has found that replacing yttrium (Y) by an yttrium/hafnium (Y/Hf) composition having the same percentage (0.3 -1.5%), relative to the total of the components, achieves better adhesion of the alumina, Al2O3, to the surface of the coating.
    The presence of silicon and of a metal from the second main group in free form and in the form of the oxide in the proportions mentioned increases the corrosion resistance of the γ-matrix of the surface of the coating obtained on the article which operates in a temperature range of between 700°C and 850°C.
    The combination of silicon with the metal from the second main group and its oxide makes it possible to maintain the operational capacity of the surface coating obtained when applied by plasma spraying in air or by high-velocity flame spraying.
    The presence of the metal from the second main group (Mg, Ca, Ba, Sr) in the proportions mentioned prevents the yttrium and silicon from being oxidized during application of the coating or surface coating.
    A lower content of silicon, of the metal from the second main group and its oxide in the alloy based on nickel, iron and cobalt according to the present invention does not increase the corrosion resistance of the coating.
    A higher content of silicon, yttrium, metal from the second main group and its oxide in the alloy according to the present invention produces a deterioration in the mechanical characteristics of the coating obtained, increases the fragility, reduces the coefficient of thermal expansion, and thus causes the coating to form cracks and to flake and therefore lowers the protection with respect to corrosion caused by sulpho-oxidation.
    Increasing the content of the oxide of the metal from the second main group, relative to the abovementioned percentages, ensures that the effect that the corrosion-promoting components present in the fuel (Na2SO4 and V2O5) have on the coating is diminished owing to the formation of thermodynamically stable sulphates and vanadates. The addition of tantalum and/or rhenium furthermore results in a significantly improved performance at oxidation temperature levels above temperatures of 1000°C.

    Claims (3)

    1. Alloy for corrosion-resistant coatings or surface coatings, comprising chromium, aluminium, yttrium, hafnium, silicon, and a metal from the second main group, together with the corresponding oxide, tantalum (if necessary) and one or more metals from Ni, Fe and Co, in the following proportions in weight: Chromium (Cr) 22.0 - 31.0% Aluminium (Al) 5.5 - 13.0% Yttrium+Hafnium composition (Y+Hf) 0.3 - 1.5% Silicon (Si) 1.5 - 10.0% Metal from the second main group Mg, Ca, Ba, Sr 0.1 - 2.0% Oxide of the corresponding metal Mg, Ca, Ba, Sr from the second main group 0.1 - 2.0% with the addition of Tantalum (Ta) 0.5 - 4.0% and/or Rhenium (Re) 2.0 - 11.0% Me remaining percentage in weight
      where Me is a metal which can be nickel (Ni) or iron (Fe) or cobalt (Co) or a composition consisting of Ni-Fe-Co, Ni-Fe, Ni-Co, Fe-Co.
    2. Alloy according to Claim 1, wherein the alloy can be applied through plasma spraying in air (APS) or in vacuum (VPS).
    3. Protective anticorrosive coating, characterized in that it is prepared by using an alloy according to any one of the preceding claims.
    EP98929635A 1997-07-10 1998-06-19 Alloy for corrosion-resistant coatings or surface coatings Expired - Lifetime EP0996752B1 (en)

    Applications Claiming Priority (3)

    Application Number Priority Date Filing Date Title
    ITPR970039 1997-07-10
    IT97PR000039A IT1294098B1 (en) 1997-07-10 1997-07-10 CORROSION RESISTANT ALLOY OR COATINGS.
    PCT/IT1998/000167 WO1999002745A1 (en) 1997-07-10 1998-06-19 Alloy for corrosion-resistant coatings or surface coatings

    Publications (2)

    Publication Number Publication Date
    EP0996752A1 EP0996752A1 (en) 2000-05-03
    EP0996752B1 true EP0996752B1 (en) 2002-05-02

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    EP98929635A Expired - Lifetime EP0996752B1 (en) 1997-07-10 1998-06-19 Alloy for corrosion-resistant coatings or surface coatings

    Country Status (5)

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    EP (1) EP0996752B1 (en)
    AT (1) ATE217032T1 (en)
    DE (1) DE69805179T2 (en)
    IT (1) IT1294098B1 (en)
    WO (1) WO1999002745A1 (en)

    Families Citing this family (6)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    DE19926669A1 (en) * 1999-06-08 2000-12-14 Abb Alstom Power Ch Ag Coating containing NiAl beta phase
    US6346134B1 (en) * 2000-03-27 2002-02-12 Sulzer Metco (Us) Inc. Superalloy HVOF powders with improved high temperature oxidation, corrosion and creep resistance
    JP4166977B2 (en) * 2001-12-17 2008-10-15 三菱重工業株式会社 High temperature corrosion resistant alloy material, thermal barrier coating material, turbine member, and gas turbine
    RU2301284C2 (en) * 2002-01-18 2007-06-20 Альстом Текнолоджи Лтд High-temperature protective layer
    EP1790746B1 (en) * 2005-11-24 2010-11-10 Siemens Aktiengesellschaft Alloy, protective layer and component
    KR101753094B1 (en) * 2015-08-25 2017-07-04 한국기계연구원 Co-Cr BASED DENTAL ALLOY WITH EXCELLENT MACHINABILITY, OXIDATION RESISTANCE AND AESTHETICS

    Family Cites Families (5)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    US4585481A (en) * 1981-08-05 1986-04-29 United Technologies Corporation Overlays coating for superalloys
    DE3246504A1 (en) * 1982-12-16 1984-06-20 BBC Aktiengesellschaft Brown, Boveri & Cie., Baden, Aargau HIGH TEMPERATURE PROTECTIVE LAYER
    DE3842300A1 (en) * 1988-12-16 1990-06-21 Asea Brown Boveri HIGH TEMPERATURE PROTECTIVE LAYER
    RU2051196C1 (en) * 1993-11-26 1995-12-27 Совместное Российско-Итальянское предприятие "Интеркоут Турбинсервис" Cobalt-based alloy
    WO1996012049A1 (en) * 1994-10-14 1996-04-25 Siemens Aktiengesellschaft Protective layer for protecting parts against corrosion, oxidation and excessive thermal stresses, as well as process for producing the same

    Also Published As

    Publication number Publication date
    WO1999002745A1 (en) 1999-01-21
    DE69805179D1 (en) 2002-06-06
    DE69805179T2 (en) 2002-11-14
    IT1294098B1 (en) 1999-03-22
    ITPR970039A0 (en) 1997-07-10
    ATE217032T1 (en) 2002-05-15
    ITPR970039A1 (en) 1999-01-10
    EP0996752A1 (en) 2000-05-03

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