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EP2753722B1 - Poudres cermet - Google Patents

Poudres cermet Download PDF

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Publication number
EP2753722B1
EP2753722B1 EP12756700.6A EP12756700A EP2753722B1 EP 2753722 B1 EP2753722 B1 EP 2753722B1 EP 12756700 A EP12756700 A EP 12756700A EP 2753722 B1 EP2753722 B1 EP 2753722B1
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EP
European Patent Office
Prior art keywords
powder
metal composition
matrix metal
cermet
matrix
Prior art date
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Active
Application number
EP12756700.6A
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German (de)
English (en)
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EP2753722A1 (fr
Inventor
Stefan Zimmermann
Benno Gries
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Hoganas Germany GmbH
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Hoganas Germany GmbH
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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/02—Making metallic powder or suspensions thereof using physical processes
    • B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/02—Making metallic powder or suspensions thereof using physical processes
    • B22F9/06—Making metallic powder or suspensions thereof using physical processes starting from liquid material
    • B22F9/08—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying
    • B22F9/082—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying atomising using a fluid
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/04—Making non-ferrous alloys by powder metallurgy
    • C22C1/05—Mixtures of metal powder with non-metallic powder
    • C22C1/051—Making hard metals based on borides, carbides, nitrides, oxides or silicides; Preparation of the powder mixture used as the starting material therefor
    • 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
    • C22C19/00—Alloys based on nickel or cobalt
    • C22C19/03—Alloys based on nickel or cobalt based on nickel
    • C22C19/05—Alloys based on nickel or cobalt based on nickel with chromium
    • C22C19/051—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W
    • C22C19/052—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W with the maximum Cr content being at least 40%
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C19/00—Alloys based on nickel or cobalt
    • C22C19/03—Alloys based on nickel or cobalt based on nickel
    • C22C19/05—Alloys based on nickel or cobalt based on nickel with chromium
    • C22C19/051—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W
    • C22C19/055—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W with the maximum Cr content being at least 20% but less than 30%
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
    • C22C29/02—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides
    • C22C29/06—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbides, but not containing other metal compounds
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
    • C22C29/02—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides
    • C22C29/06—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbides, but not containing other metal compounds
    • C22C29/067—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbides, but not containing other metal compounds comprising a particular metallic binder
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
    • C22C29/02—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides
    • C22C29/06—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbides, but not containing other metal compounds
    • C22C29/08—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbides, but not containing other metal compounds based on tungsten carbide
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C30/00—Alloys containing less than 50% by weight of each constituent
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/42—Ferrous alloys, e.g. steel alloys containing chromium with nickel with copper
    • 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
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/44—Ferrous alloys, e.g. steel alloys containing chromium with nickel with molybdenum or tungsten
    • 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
    • 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

Definitions

  • the present invention relates to cermet powder, a method for producing the cermet powder and the use of the cermet powder as a thermal spray powder for surface coating.
  • the invention relates to a method for producing a coated component, comprising the production of a coating by thermal spraying of the cermet powder and a coated component which is obtainable according to the method.
  • the invention also relates to the use of the coated component for wear protection under corrosive environmental conditions at pH values below 7.
  • Thermal spray powders are used to produce coatings on substrates.
  • powdery particles are introduced into a combustion or plasma flame which is directed at the (mostly metallic) substrate that is to be coated.
  • the particles melt completely or partially in the flame, hit the substrate, solidify there and form the coating in the form of solidified "splats".
  • Coatings made by thermal spraying can be made up to several mm thick. A frequent application of thermal spray powders is the production of wear protection layers.
  • Thermal spray powders are typically a subclass of cermet powders, which on the one hand contain hard materials, most frequently carbides such as tungsten, chromium and molybdenum carbides, and on the other hand a matrix consisting of metals such as cobalt and nickel , and their alloys with chromium, more rarely also iron-containing alloys. Thermal spray powders and spray coatings made from them are therefore composite materials.
  • coatings are characterized by empirically determinable properties. These include hardness (e.g. Vickers, Brinell, Rockwell and Knoop hardness), wear resistance (e.g. ASTM G65), cavitation resistance, but also the corrosion behavior in various media. Since many wear protection layers have to reliably exist in chemically aggressive environments under acidic conditions (examples are use in the oil and gas, paper, chemical, food and pharmaceutical industries, often with the exclusion of oxygen), corrosion resistance comes into play when choosing the pointed materials increasingly come to the fore. This is the case, for example, with valve spools and piston rods when acidic oil or natural gas is pumped in the presence of chlorides or seawater. There are also a large number of applications in the food industry and in the chemical industry, where wear and corrosion form a synergy in the negative sense and thus reduce the service life of wear protection coatings.
  • hardness e.g. Vickers, Brinell, Rockwell and Knoop hardness
  • wear resistance e.g. ASTM G65
  • thermal spray powders for the production of spray coatings for the above-mentioned applications, for example WC-CoCr 86/10/4 or WC-CoNiCr 86/9/1/4, WC-Cr3C2-Ni and Cr3C2-NiCr. All of the above have in common that they contain Cr in the matrix, as this ensures its corrosion resistance.
  • WC-NiMoCrFeCo 85/15 is commercially available as a thermal spray powder (Amperit® 529 from H. C. Starck GmbH, D). Its matrix consists of an alloy similar to Hastelloy® C. Although Hastelloy® C is used with good success in acidic media, this alloy lacks wear resistance. As a matrix alloy in the composite material "spray powder" or “spray layer”, however, poorer properties are found.
  • Fe-based matrix alloys for example derived from austenitic stainless steels such as 316 L, or based on FeCrAl 70/20/10 according to DE 10 2006 045 481 B3 , fail in an acidic environment at low pH values.
  • a sintered hard alloy is disclosed.
  • the sintered hard material alloy is made from 40 to 80% by weight of metal carbide, primarily titanium carbide, with up to 70% by weight of the titanium carbide being replaced by one or more of the carbides of tungsten, molybdenum, vanadium or chromium.
  • the remainder of an alloy is composed of (in each case weight percent) 4.5 to 19.5% nickel, 4.5 to 16.5% molybdenum, 4.5 to 16.5% cobalt, 2.0 to 6.0 % Copper, 2.0 to 6.0% aluminum, 0 to 0.1% carbon, 0 to 4.5% titanium, 0 to 1.4% boron, 0 to 4.5% niobium, 0 to 20.0 % Chromium, 0 to 4.0% manganese, remainder iron, the composition being adjusted so that the alloy has a nickel (soft) martensitic structure.
  • the EP 1 857 204 A1 relates to a non-magnetic material for the manufacture of parts or coatings that are adapted to high wear and corrosion-intensive applications.
  • the material includes preformed particles of tungsten carbide embedded in a metal phase of a Ni-based alloy. It is suggested that the weight fraction of the tungsten carbide particles be in the range between 30% by weight and 65% by weight and wherein the Ni-based alloy is a nickel-chromium-molybdenum alloy comprising: (in% by weight) : Cr: 11.0-30.0; Mo: 5.0-25.0; Fe: 0-10.0; B: 0-5.0; Co: 0-2.5.
  • the object of the invention is therefore to provide a cermet powder which is suitable as a thermal spray powder and which provides coatings that are resistant in all three media without serious losses in the mechanical characteristics of wear and cavitation resistance or in the resistance in the presence of chloride.
  • the object is achieved by a cermet powder according to claim 1.
  • the corrosion resistance is determined under real conditions in the form of emissions of the matrix metals instead of electrochemical methods such as potentiograms, which do not allow the service life to be quantified under real conditions.
  • cermet powder comprising one or more hard materials and a special matrix metal composition.
  • the cermet powders of the present invention are outstandingly suitable as thermal spray powders. These can be used for surface coating, in particular of metal substrates.
  • the cermet powders according to the invention can here, for example, be applied to a wide variety of components by thermal spraying processes, such as plasma spraying or high-speed flame spraying (HVOF), flame spraying, arc spraying, laser spraying or deposition welding, such as the PTA process, in order to give the respective component the desired surface properties .
  • thermal spraying processes such as plasma spraying or high-speed flame spraying (HVOF), flame spraying, arc spraying, laser spraying or deposition welding, such as the PTA process
  • the cermet powders according to the invention comprise one or more hard material (s) in an amount of 50 to 90% by weight, preferably in an amount of 60 to 89% by weight, in particular 70 to 88% by weight, each based on the total weight of the cermet powder.
  • the cermet powders according to the invention can have typical hard materials.
  • metal carbides are preferred as hard material, particularly preferably selected from the group consisting of WC, Cr 3 C 2 , VC, TiC, B 4 C, TiCN, SiC, TaC, NbC, Mo 2 C and mixtures thereof.
  • the hard materials WC and / or Cr 3 C 2 are particularly preferred.
  • Another essential component of the cermet powder according to the invention is the matrix metal composition, which is present in an amount of 10 to 50% by weight, preferably 11 to 40% by weight, in particular 12 to 30% by weight, each based on the total weight of the Cermet powder.
  • the matrix metal composition is decisive for the excellent properties of the cermet powder according to the invention.
  • the modifying agents are usually present in an amount of up to 5% by weight, based on the total weight of the matrix metal composition.
  • a matrix metal composition which comprises 15 to 50% by weight, preferably 20 to 45% by weight, iron.
  • the matrix metal composition more preferably comprises 15 to 50% by weight, more preferably 20 to 45% by weight, nickel.
  • the presence of chromium, molybdenum and copper in the matrix metal composition also plays a role plays an essential role in achieving the excellent properties of the cermet powder or the surface coatings made from it.
  • the matrix metal composition preferably has 20 to 33% by weight, more preferably 20 to 31% by weight, of chromium.
  • the matrix metal composition comprises 4 to 15 wt.% Molybdenum, in particular 5 to 10 wt.% Molybdenum.
  • the copper content plays an important role with regard to the corrosion properties.
  • Outstanding corrosion results could be achieved with a matrix metal composition which preferably comprises 0.7 to 3% by weight, in particular 0.9 to 2.0% by weight copper.
  • the weight ratio of iron to nickel in the matrix composition also contributes to the corrosion resistance of the cermet powder according to the invention.
  • the weight ratio of iron to nickel in the matrix metal composition is preferably 1: 2 to 2: 1, more preferably 1: 1.5 to 1.5: 1.
  • the cermet powders according to the invention are preferably used as thermal spray powders. Certain particle sizes have proven to be particularly suitable here.
  • the cermet powders according to the invention have an average particle size of 10 to 100 ⁇ m, determined by means of laser diffraction in accordance with ASTM C1070.
  • Another object of the present invention is a method for producing the cermet powder according to the invention.
  • step a) of the cermet powder production method according to the invention can be carried out, for example, by dispersing the powdery hardness carriers (hard materials) and the powdery matrix metal composition in a liquid. In the case of milling, this dispersion is then milled in a milling step, for example in a ball mill or an inlet gate.
  • the matrix metal composition is in the form of an alloy powder.
  • the cermet powder production method according to the invention is preferably characterized in that the mixing is followed by dispersing in a liquid, if necessary grinding, followed by a granulation step by separating off the liquid, which is more preferably carried out by spray drying.
  • the spray granulate can then be classified and sintered in a subsequent thermal process step to such an extent that the granulate has a mechanical strength that is sufficient that the granulate does not disintegrate during the thermal spraying process so that the thermal spraying process can be carried out reliably.
  • the powder mixture is preferably sintered under reduced pressure and / or in the presence of protective gases, preferably selected from the group consisting of hydrogen, argon, nitrogen and mixtures thereof, at any pressure.
  • sintering can also be carried out approximately in the range of normal pressure.
  • a powder is usually obtained or a loosely sintered cake which can easily be converted back into powder.
  • the powders obtained are similar in size. and appearance of the spray granulate.
  • Agglomerated / sintered spray powders are particularly advantageous because they offer a great deal of freedom in the choice of components (for example their contents and particle sizes) and, due to their good flowability, can be easily dosed in the spraying process.
  • very finely divided hardness carriers are used for the cermet powder according to the invention and in the context of the cermet powder production process according to the invention, which preferably have an average particle size below 20 ⁇ m, determined by means of laser diffraction in accordance with ASTM C1070.
  • the use of such finely divided hardening agents leads to very smooth wear surfaces, which in turn leads to low coefficients of friction and long service lives.
  • Sintered / broken cermet powders or wettable powders can be produced analogously, with the difference that the powder components are not necessarily mixed wet in dispersion, but can be mixed dry and, if appropriate, tabletted or compacted to form other shaped bodies.
  • the subsequent sintering step is analogous, but compact, solid sintered bodies are usually obtained, which must be converted back into powder form by the action of mechanical force.
  • the powders obtained with mean particle sizes between 10 and 100 ⁇ m are, however, typically of irregular shape in these cases the surface of fracture processes.
  • These thermal spray powders are clearly less fluid, which can be disadvantageous for a constant application rate in thermal spraying, but is still practicable.
  • the cermet powders according to the invention or the cermet powders obtainable by the cermet powder production method according to the invention can be used as thermal spray powders.
  • the present invention therefore also provides the use of the cermet powders according to the invention or the cermet powders obtainable by the cermet powder production process according to the invention as thermal spray powders.
  • the cermet powders according to the invention are outstandingly suitable for surface coating, in particular of metal substrates or components.
  • the present invention therefore also relates to the use of the cermet powders according to the invention or those according to the invention by the cermet powder production process available cermet powder as thermal spray powder for surface coating.
  • the surface coating is preferably carried out by thermal spraying processes, for example by plasma spraying or high-speed flame spraying or flame spraying or arc spraying or laser spraying or build-up welding.
  • the cermet powders according to the invention or cermet powders obtainable by the cermet powder production process according to the invention give the components coated therewith excellent properties, in particular with regard to wear protection under corrosive environmental conditions, for example at pH values below 7 and in the presence of any chloride ions.
  • the present invention therefore also provides a method for producing a coated component, comprising the application of a coating by thermal spraying of a cermet powder according to the invention or a cermet powder obtainable by the cermet powder production method according to the invention.
  • Another object of the present invention is a coated component obtainable by the production method according to the invention.
  • the component coated according to the invention is used in particular for wear protection under corrosive environmental conditions at pH values below 7 and in the presence of any chloride ions that may be present.
  • coated component is part of an apparatus which comes into contact with media which contain acids and / or chloride ions.
  • coated components of the present invention are valve spools or piston rods.
  • Wettable powders with compositions according to Table 1 were compacted at 1000 ° C. for 10 min by means of hot pressing to give compact moldings with the same specific surface area.
  • the outer layers were sanded off using SiC sandpaper.
  • the cylindrical moldings were then in 500 ml of the media (1-normal hydrochloric acid, 1-normal sulfuric acid and 1-normal citric acid - the latter corresponds to 1/3 mol / l) for 28 days 20 ° C and air access outsourced. Then 180 ml were removed and the content of those elements were determined from which the matrix consisted.
  • the mechanical characteristics of wear and cavitation resistance were determined on pointed layers.
  • the sprayed coatings were also subjected to the salt spray test according to ASTM B117 and the change was recorded after 1000 hours.
  • the weight data "Fe (%)” to “Cu (%)” relate to the total weight of the matrix composition.
  • the total content of matrix is given in the "Matrix (%)" line and relates to the total weight of the wettable powder.
  • the percentages of the carbides relate to the total weight of the wettable powder.
  • the matrix was in the form of an alloy, since the corresponding alloy powder was used to produce the wettable powder.
  • Example 7 corresponds to a preferred embodiment of FIG DE 10 2006 045 481 B3 .
  • the WC-Cr3C2-Ni 83/20/7 (example 3) is the only one that has sufficient resistance to hydrochloric acid and citric acid - but not to sulfuric acid. In general, the resistance of all wettable powders of Examples 1-7 to sulfuric acid is poor.
  • Spray powder example 4 with a matrix alloy similar to Hastelloy®C and example 6 also have good mechanical properties and good ones Resistance to citric acid, but are not resistant to mineral acids.
  • Wettable powder example 5 with stainless steel 316 L is very slightly 5 corrosion resistant and shows unacceptable discoloration in the salt spray test.
  • Example 2 (partly according to the invention, denoted there with * )
  • Example 10 Moldings and spray coatings were produced analogously to Example 1. 10
  • 2 alloy powders according to Examples 8 and 9 2 alloy powders of the same nominal composition, but from different manufacturing processes (atomization of the alloy from the melt and cooling of the melt droplets formed using injected water or argon) were used.
  • Example 10 contained an FeNi 50/50 alloy powder 15 as a matrix and a chromium metal powder as a further component used in the matrix. It can therefore be assumed that the matrix in the agglomerated / sintered spray powder was not completely and uniformly alloyed with Cr. Information in the table is given in percent by weight.
  • the weight data "Fe (%)” to “Cu (%)” relate to the total weight of the matrix composition.
  • the total content of matrix is given in the “Matrix (%)” line and relates to the total weight of the wettable powder.
  • the percentages of the carbides relate to the total weight of the wettable powder.
  • the iron and nickel-containing wettable powders 8 to 10 show comparatively good resistance to mineral acids, compared to those which have a matrix based on nickel, cobalt or even iron. This is surprising in that iron is much less noble than nickel. Even the incomplete alloying of the matrix with Cr in No. 10 leads to better results in sulfuric acid than those of all powders from Example 1. Hence FeNi alloys have better acid resistance than the edge members Ni and Fe, which is why the Acid resistance is obviously dependent on the Fe: Ni ratio, in addition to the elements that are still present.
  • the acid resistance of the FeNi matrix in the powders No. 8 and 9 is further improved by the chromium alloyed in the matrix in this case, and also by the additives Mo and Cu.
  • the high Mo contents in powders 4 and 6 do not lead to improved acid resistance, it can be concluded that, in addition to the Fe / Ni ratio, the copper content is largely responsible for the good corrosion results.
  • Example 3 comparative example, pure matrix alloys
  • the pure matrix alloys as wettable powders have no wear resistance due to the lack of hard materials.
  • Examples 8 and 9 according to the invention succeed in achieving the acid resistance of pure NiCr 80/20, combined with the wear resistance of commercially available spray materials, as described in Examples 1 to 3.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Plasma & Fusion (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Powder Metallurgy (AREA)
  • Coating By Spraying Or Casting (AREA)
  • Manufacture Of Metal Powder And Suspensions Thereof (AREA)

Claims (12)

  1. Poudre cermet comprenant
    a) 50 à 90 % en poids d'un ou plusieurs matériaux durs et
    b) 10 à 50 % en poids d'une composition de matrice métallique, dans laquelle les indications relatives au poids se rapportent au poids total de la poudre cermet, caractérisée en ce que
    la composition de matrice métallique consiste en ce qui suit :
    i) 40 à 75 % en poids de fer et de nickel,
    ii) 18 à 35 % en poids de chrome,
    iii) 3 à 20 % en poids de molybdène,
    iv) 0,5 à 4 % en poids de cuivre,
    facultativement
    v) jusqu'à 10 % en poids de cobalt,
    facultativement
    vi) jusqu'à 5 % en poids d'agent modifiant, choisi dans le groupe consistant en Al, Nb, Ti, Ta, V, Si, W et des mélanges quelconques de ceux-ci,
    dans laquelle les indications relatives au poids des métaux i) à vi), se rapportent respectivement au poids total de la composition de matrice métallique et dans laquelle le rapport en poids entre le fer et le nickel se situe dans la portée de 3:1 à 1:3.
  2. Poudre cermet selon la revendication 1, caractérisée en ce que la composition de matrice métallique comprend du cobalt en une quantité allant jusqu'à 10 % en poids, par rapport au poids total de la composition de matrice métallique.
  3. Poudre cermet selon la revendication 1 ou 2, caractérisée en ce que la composition de matrice métallique comprend un agent modifiant choisi dans le groupe consistant en Al, Nb, Ti, Ta, V, Si, W et des mélanges quelconques de ceux-ci, et dans laquelle
    la quantité de l'agent modifiant va jusqu'à 5 % en poids, par rapport au poids total de la composition de matrice métallique.
  4. Poudre cermet selon l'une quelconque ou plusieurs des revendications 1 à 3, caractérisée en ce que le matériau dur est un carbure métallique,
    est de préférence choisi dans le groupe consistant en WC, Cr3C2, VC, TiC, B4C, TiCN, SiC, TaC, NbC, Mo2C ainsi que leurs mélanges et
    est plus préférentiellement WC et/ou Cr3C2.
  5. Poudre cermet selon l'une quelconque ou plusieurs des revendications 1 à 4, caractérisée en ce que la poudre présente une dimension moyenne de particule de 10 à 100 µm, déterminée selon ASTM C 1070.
  6. Procédé de production de la poudre cermet selon l'une quelconque ou plusieurs des revendications 1 à 5 comprenant les étapes consistant à :
    a) mélanger ou broyer l'une ou les poudres de matériau dur avec la composition de matrice métallique pulvérulente,
    b) fritter le mélange de poudre et
    c) le cas échéant, pulvériser le mélange fritté à l'étape b).
  7. Procédé selon la revendication 6, caractérisé en ce que le mélange s'effectue à l'étape a) par dispersion dans un liquide et dans lequel une étape de granulation se rattache au mélange par dispersion dans un liquide par séparation du liquide, laquelle s'effectue de préférence par séchage par pulvérisation.
  8. Procédé selon l'une quelconque ou plusieurs des revendications 6 ou 7, caractérisé en ce qu'une poudre d'alliage est utilisée en tant que composition de matrice métallique.
  9. Utilisation de la poudre cermet selon l'une quelconque ou plusieurs des revendications 1 à 5 en tant que poudre pour pulvérisation thermique destinée au revêtement de surface.
  10. Procédé de production d'un élément de construction revêtu comprenant l'application d'un revêtement par pulvérisation thermique d'une poudre cermet selon l'une quelconque ou plusieurs des revendications 1 à 5.
  11. Élément de construction revêtu disponible selon le procédé selon la revendication 10.
  12. Utilisation de l'élément de construction revêtu selon la revendication 11
    destiné à la protection anti-usure dans des conditions environnementales corrosives à des valeurs de pH inférieures à 7 et le cas échéant en présence de sels de chlorure.
EP12756700.6A 2011-09-06 2012-09-04 Poudres cermet Active EP2753722B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US201161531136P 2011-09-06 2011-09-06
DE102011112435A DE102011112435B3 (de) 2011-09-06 2011-09-06 Cermetpulver, Verfahren zur Herstellung eines Cermetpulvers, Verwendung der Cermetpulver, Verfahren zur Herstellung eines beschichteten Bauteils, Beschichtetes Bauteil
PCT/EP2012/067210 WO2013034544A1 (fr) 2011-09-06 2012-09-04 Poudres cermet

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EP2753722A1 EP2753722A1 (fr) 2014-07-16
EP2753722B1 true EP2753722B1 (fr) 2020-08-12

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CN113618066B (zh) * 2021-07-27 2023-05-26 界首市汇珠渔具有限公司 一种可舍弃环保陶瓷复合材料渔坠的制备方法
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DE102011112435B3 (de) 2012-10-25
KR20140058673A (ko) 2014-05-14
US20140234548A1 (en) 2014-08-21
MX359657B (es) 2018-10-05
US9540715B2 (en) 2017-01-10
AU2012306492A1 (en) 2014-03-13
CN103781929A (zh) 2014-05-07
KR102032579B1 (ko) 2019-10-15
AU2012306492B2 (en) 2017-04-27
JP2014531509A (ja) 2014-11-27
CN103781929B (zh) 2018-01-19
EP2753722A1 (fr) 2014-07-16
JP6116569B2 (ja) 2017-04-19
RU2014113180A (ru) 2015-10-20
RU2608112C2 (ru) 2017-01-13
MX2014002409A (es) 2014-06-05
CA2845506C (fr) 2020-01-28
WO2013034544A1 (fr) 2013-03-14
CA2845506A1 (fr) 2013-03-14

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