EP0576366B1 - Revêtements métalliques à base d'alliages amorphes résistant à l'usure et à la corrosion, procédé d'obtention et applications aux revêtements anti-usure pour matériel hydraulique - Google Patents

Revêtements métalliques à base d'alliages amorphes résistant à l'usure et à la corrosion, procédé d'obtention et applications aux revêtements anti-usure pour matériel hydraulique Download PDF

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Publication number
EP0576366B1
EP0576366B1 EP93420202A EP93420202A EP0576366B1 EP 0576366 B1 EP0576366 B1 EP 0576366B1 EP 93420202 A EP93420202 A EP 93420202A EP 93420202 A EP93420202 A EP 93420202A EP 0576366 B1 EP0576366 B1 EP 0576366B1
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EP
European Patent Office
Prior art keywords
resistant
wear
corrosion
alloys
amorphous metal
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
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EP93420202A
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German (de)
English (en)
French (fr)
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EP0576366A1 (fr
Inventor
Jean-Marie Dubois
Philippe Plaindoux
Jean-Pierre Houin
Jean-Marie Roman
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GE Hydro France SAS
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GEC Alsthom Neyrpic
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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
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
    • C23C4/06—Metallic material
    • C23C4/08—Metallic material containing only metal elements
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C45/00—Amorphous alloys
    • C22C45/008—Amorphous alloys with Fe, Co or Ni as the major constituent
    • 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
    • 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
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
    • C23C4/06—Metallic material
    • C23C4/073—Metallic material containing MCrAl or MCrAlY alloys, where M is nickel, cobalt or iron, with or without non-metal elements

Definitions

  • the present invention relates to metallic coatings based on wear-resistant and corrosion-resistant amorphous alloys, the processes for obtaining these coatings and their applications to the production of anti-wear coatings, in particular for hydraulic equipment.
  • One of the solutions for obtaining materials having a satisfactory compromise between these contradictory properties consists in using metal alloys of amorphous structure obtained by rapid cooling.
  • the amorphous alloys used to date are essentially in the form of small ribbons obtained by a casting method or in the form of very thin deposits obtained by electrochemical methods.
  • the thermal projection methods and for example that of the blown arc plasma have not so far made it possible to obtain completely amorphous alloys at the level of X-ray diffraction in the form of very thick powder deposits (> 0.5 mm) on surfaces up to several square meters.
  • the object of the present invention is to provide amorphous metallic coatings combining with high mechanical characteristics a certain ductility, a high crystallization temperature, a good ability to be released from the residual manufacturing constraints by means of a heat treatment of stress relaxation without causing a significant change in structure and brittleness, good corrosion resistance, including in the presence of halogens, made from alloys capable of being amorphizable for cooling rates of the around 105K / sec., these coatings can be obtained in thicknesses from 0.03 to 1.5 mm on large surfaces.
  • the inventors have discovered that the ease of amorphization can be obtained by combining the action of the different states of positive or negative size of certain constituent elements with respect to the basic constituent elements, and in particular by playing on the combined action of B and Zr on a matrix of Fe - Ni and and / or Co.
  • the powders of these alloys are obtained by atomization and, for grain sizes ⁇ 100 ⁇ m, the grains have a completely amorphous structure by X-ray diffraction.
  • the thermal spray deposition method allows reproducibility of deposition and structural conditions.
  • the alloys used for the amorphous metallic coatings resistant to wear and erosion according to the invention have many advantages compared to the alloys of the prior art. First of all, these are easily amorphizable alloys due to the simultaneous presence of boron, an element whose atomic dimension is smaller than that of T atoms, and of Zr, larger than T atoms.
  • the crystallization temperature of these alloys is remarkably high, when compared to that of alloys of the prior art, such as Fe-B alloys and derived alloys (such as Fe - B - C, Fe - B - Si ).
  • This effect which can be attributed to the presence of zirconium, can be further increased by the addition of refractory elements (such as Mo, Ti, V, Nb, Rh ...) or metalloids.
  • refractory elements such as Mo, Ti, V, Nb, Rh .
  • chromium and zirconium make it possible to obtain excellent resistance to corrosion, an effect which can be further reinforced by the addition of various elements, in particular Rh, Nb, Ti, rare earths and phosphorus.
  • these are essentially ductile metallic glasses in a sufficiently low metalloid concentration range, namely: b + g ⁇ 24 at%.
  • the alloys obtained then resist satisfactorily the embrittlement which usually follows in other alloys the heat treatments at the crystallization temperature.
  • Example 1 Elaboration of alloys corresponding to the general formulation of family (II)
  • Alloys corresponding to the formulation of family (II) have been prepared in the liquid state from the constituents, taken separately. For this, fragments of the elements, of commercial purity, were alloyed in the liquid state in a cold hearth furnace placed under helium. The components were heated by high frequency currents. After melting, these alloys are introduced into the inductor of a tape casting machine consisting of a copper wheel 250 mm in diameter having a tangential speed of 35 m / sec. The enclosure containing the wheel is in a helium atmosphere. The crucible is made of quartz with an orifice 0.8 mm in diameter. The injection pressure of the liquid metal is 0.5 bar. The temperature of the liquid metal is measured by optical pyrometry on the upper face of the liquid.
  • the concentration, in atom%, of the chemical elements is as follows: 50 ⁇ Ni ⁇ 75 0 ⁇ Mo ⁇ 5 5 ⁇ Cr ⁇ 25 0 ⁇ Hf ⁇ 5 5 ⁇ Zr ⁇ 15 0 ⁇ If ⁇ 5 5 ⁇ B ⁇ 15 0 ⁇ La ⁇ 4
  • the concentration, in atom%, of the chemical elements is as follows: 10 ⁇ Fe ⁇ 75 5 ⁇ Zr ⁇ 15 0 ⁇ Hf ⁇ 4 10 ⁇ Ni ⁇ 60 5 ⁇ B ⁇ 15 0 ⁇ Nb ⁇ 4 5 ⁇ Cr ⁇ 15 0 ⁇ Mo ⁇ 12 0 ⁇ La ⁇ 4 O ⁇ Ti ⁇ 10
  • Alloys corresponding to the formulation of family (IV) were developed and obtained in the form of ribbons in an identical manner to that which was done for obtaining the alloys of the preceding examples.
  • the concentration, in atom%, of the chemical elements is as follows: 50 ⁇ Co ⁇ 82 5 ⁇ B ⁇ 15 3 ⁇ Ni ⁇ 35 0 ⁇ Mo ⁇ 12 5 ⁇ Zr ⁇ 15 5 ⁇ Cr ⁇ 15 0 ⁇ La ⁇ 4
  • Alloys corresponding to the formulation of family (V) were developed and obtained in the form of ribbons in an identical manner to that which was done for obtaining the alloys of the preceding examples.
  • the concentration, in atom%, of the chemical elements is as follows: 10 ⁇ Fe ⁇ 65 5 ⁇ Cr ⁇ 15 10 ⁇ Co ⁇ 65 5 ⁇ B ⁇ 15 5 ⁇ Zr ⁇ 15 10 ⁇ Ni ⁇ 65 1 ⁇ C ⁇ 5 O ⁇ If ⁇ 5 1 ⁇ P ⁇ 9
  • Example 5 Elaboration of alloys corresponding to the general formulation of the family (V)
  • Alloys corresponding to the formulation of family (V) were developed and obtained in the form of ribbons in an identical manner to that which was done for obtaining the alloys of the preceding examples.
  • the concentration, in atom%, of the chemical elements is as follows: 10 ⁇ Fe ⁇ 50 5 ⁇ Cr ⁇ 15 10 ⁇ Co ⁇ 50 5 ⁇ B ⁇ 15 5 ⁇ Zr ⁇ 15 10 ⁇ Ni ⁇ 50 0 ⁇ C ⁇ 5 O ⁇ If ⁇ 17 0 ⁇ P ⁇ 9
  • the alloys powders of families (II) to (V) were deposited on various metallic substrates such as structural steel, stainless steels, copper-based alloys, by a thermal spraying method, and for example by the method of arc plasma blown under controlled atmosphere and temperature.
  • These projected powders have a particle size between 30 and 100 ⁇ m.
  • the thicknesses, deposited on a sanded substrate, are between 0.03 and 1.5 mm.
  • the coated surfaces are covered over several square meters.
  • the deposits are made under the conditions described in Example 9. However, according to one embodiment of the method according to the invention, instead of working in a controlled atmosphere, in order to prevent any oxidation during the spraying of the molten powders, the only path of the molten particles is protected by an annular jet of nitrogen, concentric with the jet of plasma carrying the particles, and of dimensions slightly greater than this. The deposits can then be carried out in the open air, under partial nitrogen protection.
  • the thermal mass of the part may be sufficient to provide cooling allowing the deposit to have an amorphous structure. This avoids the cryogenic cooling step.
  • the curves represented in FIG. 8 correspond to a composition in at%: Fe20; Ni28; Co20; Cr12; Zr10; B10.
  • Isothermal anneals define the stability domains of amorphous (A) and crystallized (C) structures for a given time and temperature.
  • the curve represented in FIG. 9 illustrates the results for the anisothermal anneals which define the start of the crystallization temperature as a function of the heating rate.
  • the deposits of thickness of the order of 0.5 mm obtained by the thermal spraying method according to the invention have, in the raw state of deposition, a percentage of porosity of the order of 8% measured by treatment d 'picture.
  • This porosity rate can be reduced to close to 0 by a shot peening of the deposit from carbon steel or stainless steel balls with a diameter between 1 and 1.6 mm for a defined peening intensity (Halmen de la Sté Metal Improvment) from 16 to 18 and a recovery rate (Metal Improvment method) of 600%.
  • the deposits were tested under conditions of wear by abrasive erosion identical to that occurring on the materials of hydraulic machines operating in an aqueous medium loaded with fine particles of solid material such as quartz.
  • the wear measured at room temperature for deposition is equivalent to ceramic wear such as, for example, Cr2O3 and is significantly lower than metal alloys such as stellite, stainless steels such as dupleix or martensito-ferritic, as well as commercial steels known as resistant to abrasion.
  • Dry abrasive erosion tests at angles of incidence ranging from 0 to 90 ° give better behavior of the amorphous alloys according to the invention compared to ceramics and other metal alloys.

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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)
  • Plasma & Fusion (AREA)
  • Physics & Mathematics (AREA)
  • Powder Metallurgy (AREA)
  • Coating By Spraying Or Casting (AREA)
  • Soft Magnetic Materials (AREA)
  • Physical Vapour Deposition (AREA)
  • Chemically Coating (AREA)
  • Manufacture Of Metal Powder And Suspensions Thereof (AREA)
  • Electroplating Methods And Accessories (AREA)
  • Supporting Of Heads In Record-Carrier Devices (AREA)
  • Magnetic Heads (AREA)
  • Analysing Materials By The Use Of Radiation (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Sampling And Sample Adjustment (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Glass Compositions (AREA)
  • Chemical Vapour Deposition (AREA)
  • Mechanical Operated Clutches (AREA)
  • Contacts (AREA)
  • Laminated Bodies (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
EP93420202A 1992-05-22 1993-05-18 Revêtements métalliques à base d'alliages amorphes résistant à l'usure et à la corrosion, procédé d'obtention et applications aux revêtements anti-usure pour matériel hydraulique Expired - Lifetime EP0576366B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR9206535A FR2691478B1 (fr) 1992-05-22 1992-05-22 Revêtements métalliques à base d'alliages amorphes résistant à l'usure et à la corrosion, rubans obtenus à partir de ces alliages, procédé d'obtention et applications aux revêtements antiusure pour matériel hydraulique.
FR9206535 1992-05-22

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EP0576366A1 EP0576366A1 (fr) 1993-12-29
EP0576366B1 true EP0576366B1 (fr) 1996-03-27

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US (2) US5376191A (es)
EP (1) EP0576366B1 (es)
JP (1) JPH0688175A (es)
KR (1) KR100271996B1 (es)
CN (1) CN1049457C (es)
AT (1) ATE136062T1 (es)
AU (1) AU664265B2 (es)
BR (1) BR9301937A (es)
CA (1) CA2096682A1 (es)
DE (1) DE69301965T2 (es)
DK (1) DK0576366T3 (es)
ES (1) ES2085132T3 (es)
FI (1) FI100891B (es)
FR (2) FR2691478B1 (es)
GR (1) GR3019445T3 (es)
MX (1) MX9302977A (es)
NO (1) NO300553B1 (es)
ZA (1) ZA933517B (es)

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US8075712B2 (en) 2005-11-14 2011-12-13 Lawrence Livermore National Security, Llc Amorphous metal formulations and structured coatings for corrosion and wear resistance

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CN103659050B (zh) * 2013-12-18 2016-01-06 江苏科技大学 一种耐裂纹高耐磨三偏心蝶阀等离子喷焊用粉末材料
CN103862055B (zh) * 2014-03-03 2015-10-21 同济大学 一种低磁高致密的铁基非晶涂层的制备方法
EP3175017A4 (en) * 2014-07-30 2018-02-21 Hewlett-Packard Development Company, L.P. Wear resistant coating
CN104357748B (zh) * 2014-10-31 2016-06-22 广东电网有限责任公司电力科学研究院 锅炉尾部受热面防护用铁基纳米晶复合涂层及其激光熔覆成型工艺
CN104313531B (zh) * 2014-11-04 2016-06-15 长安大学 一种锅炉管束用耐蚀耐磨铁基非晶涂层的制备方法
CN104775085A (zh) * 2015-04-21 2015-07-15 苏州统明机械有限公司 用于热喷涂的耐腐蚀铁基合金涂层及其制备方法
TWI532855B (zh) 2015-12-03 2016-05-11 財團法人工業技術研究院 鐵基合金塗層與其形成方法
CN105502060A (zh) * 2015-12-22 2016-04-20 常熟市复林造纸机械有限公司 一种卷纸机用耐腐蚀导纸辊
CN108950534A (zh) * 2018-08-16 2018-12-07 张家港市山牧新材料技术开发有限公司 一种耐蚀型合金涂层的制备方法
US11078560B2 (en) * 2019-10-11 2021-08-03 Cornerstone Intellectual Property, Llc System and method for applying amorphous metal coatings on surfaces for the reduction of friction
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8075712B2 (en) 2005-11-14 2011-12-13 Lawrence Livermore National Security, Llc Amorphous metal formulations and structured coatings for corrosion and wear resistance
US8778460B2 (en) 2005-11-14 2014-07-15 Lawrence Livermore National Security, Llc. Amorphous metal formulations and structured coatings for corrosion and wear resistance

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FR2691477B1 (fr) 1994-08-26
ES2085132T3 (es) 1996-05-16
DE69301965T2 (de) 1996-09-12
AU664265B2 (en) 1995-11-09
DK0576366T3 (da) 1996-07-29
US5421919A (en) 1995-06-06
US5376191A (en) 1994-12-27
DE69301965D1 (de) 1996-05-02
NO931800D0 (no) 1993-05-18
NO300553B1 (no) 1997-06-16
CN1088630A (zh) 1994-06-29
JPH0688175A (ja) 1994-03-29
MX9302977A (es) 1994-02-28
CA2096682A1 (en) 1993-11-23
ZA933517B (en) 1993-12-10
GR3019445T3 (en) 1996-06-30
EP0576366A1 (fr) 1993-12-29
FI932289A0 (fi) 1993-05-19
FI932289A (fi) 1993-11-23
KR100271996B1 (ko) 2000-12-01
ATE136062T1 (de) 1996-04-15
FR2691478B1 (fr) 1995-02-17
FR2691478A1 (fr) 1993-11-26
CN1049457C (zh) 2000-02-16
AU3867293A (en) 1993-11-25
KR930023483A (ko) 1993-12-18
NO931800L (no) 1993-11-23
FR2691477A1 (fr) 1993-11-26
FI100891B (fi) 1998-03-13
BR9301937A (pt) 1993-11-30

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