EP2330228B1 - Composition pour revêtement par projection à chaud, ainsi que cylindre doté d'une couche deposée par projection à chaud - Google Patents

Composition pour revêtement par projection à chaud, ainsi que cylindre doté d'une couche deposée par projection à chaud Download PDF

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Publication number
EP2330228B1
EP2330228B1 EP10189151.3A EP10189151A EP2330228B1 EP 2330228 B1 EP2330228 B1 EP 2330228B1 EP 10189151 A EP10189151 A EP 10189151A EP 2330228 B1 EP2330228 B1 EP 2330228B1
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EP
European Patent Office
Prior art keywords
spray material
accordance
spray
zno
powder
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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.)
Not-in-force
Application number
EP10189151.3A
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German (de)
English (en)
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EP2330228A1 (fr
Inventor
Gerard Barbezat
Peter Ernst
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Oerlikon Metco AG
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Oerlikon Metco AG
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Priority to EP10189151.3A priority Critical patent/EP2330228B1/fr
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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
    • 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
    • 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
    • C23C4/10—Oxides, borides, carbides, nitrides or silicides; Mixtures thereof
    • C23C4/11—Oxides

Definitions

  • the invention relates to a spray material for the thermal coating of a substrate, in particular for the thermal coating of a tread of a cylinder of a reciprocating internal combustion engine, a thermal spray coating, and a cylinder with a thermal spray coating according to the preamble of the independent claim of the respective category.
  • the EP 0 167 723 A1 describes a spray material that has ZnO in the range of 1% to 8% of the weight of the spray material.
  • the EP 1 340 834 A2 suggests a cylinder tread layer for reciprocating engines having embedded FeO and Fe30 4 crystals to form solid lubricants.
  • the US 2007/099015 A1 discloses a cylinder liner coating material comprising stainless steel, iron and titanium oxides.
  • the US 4 256 811 A describes a spray material that has ZnO in the range of 1% to 20% of the weight of the spray material.
  • the DE 10 2004 025672 A1 refers to a spray material that has a Mo metal phase.
  • Thermal spray applied coatings have long been known for a variety of applications.
  • surfaces of oil-lubricated cylinder liners in vehicle engines have been coated by plasma spraying for some time, among other things, the layer being significantly reduced in friction coefficient between piston rings and cylinder wall, thereby significantly reducing the wear of piston rings and cylinders , which leads to an increase in the mileage of the engine, an extension of the maintenance intervals, for example when changing the oil and not least to a significant increase in engine performance.
  • such layers may be lubricated for oil Containers of dry lubricants in a base matrix, wherein in the base matrix in addition pores of a predeterminable size can be provided, which act as oil pockets and thus significantly reduce the friction between piston rings and cylinder wall together with the relatively soft embedded dry lubricants.
  • the basic matrix itself which in particular contains the dry lubricants and the pores among other constituents, is composed of a hard matrix material which guarantees a long service life of the cylinder surfaces and piston rings.
  • Such a modern high-performance cylinder tread is for example in the EP 1 340 834 described in detail.
  • thermal spraying surfaces include coating turbine parts with anti-wear and thermal barrier coatings, components lubricated by oil-lubricated bearings, e.g. the coating of crank bearings or other workpieces subjected to particular physical, chemical or thermal stresses.
  • components lubricated by oil-lubricated bearings e.g. the coating of crank bearings or other workpieces subjected to particular physical, chemical or thermal stresses.
  • very specific materials are used, usually in the form of spray powders or sprayed wires, which have the necessary specific properties and composition in order to generate the required properties of the surface layer to be sprayed.
  • the powder material price plays a decisive role in terms of the cost effectiveness of the coating, in particular in the coating of cylinder surfaces by means of the plasma spraying process APS, especially in the case of the coating of larger engines (truck diesel, for example).
  • the production costs of the powder are, on the one hand, dependent on the raw material prices and, on the other hand, on the processing effort required to process the raw materials into a usable material which is suitable for carrying out the chosen process.
  • grinding and sieving generally also apply, even in the case of larger quantities in the case of ceramic spray materials of metallic oxides.
  • certain materials minerals in the powder can be processed without additional melting.
  • the iron-titanate FeTiO 3 which is also known as ilmenite, was previously considered as a potential material for cylinder surfaces.
  • Ilmenite is formed from approximately 53% TiO 2 and 47% FeO, and crystallizes in a hexagonal crystal system.
  • the hardness of ilmenite crystals is approx. 650 HV, ie in the layers values of 400 to 500 HV are possible with optimized parameters.
  • PCT / EP2009 / 058565 proposed a significantly improved iron-based spray material for thermal coating of cylinder treads of reciprocating internal combustion engines with FeTiO 3 as the base material.
  • the improved spray material according to PCT / EP2009 / 058565 comprises at least a first solid lubricant of a sulfide and a second solid lubricant of a fluoride.
  • spray materials based on iron titanate ie based on the so-called ilmenite with the chemical formula FeTiO 3
  • the ilmenite at least one sulfide and a fluoride Solid lubricant is added.
  • the layers produced therewith are characterized in particular by an excellent resistance to adhesion wear.
  • solid lubricants in addition to a sulfide and a fluoride in particular, for example, additionally relate to a nitride, which allows, inter alia, a significant increase in the wall temperature of the cylinder surfaces in the operating state, so that these layers are particularly well suited for use in adiabatic engines ,
  • the tribological performance of the iron titanate FeTiO 3 layers can be significantly improved by the targeted addition of solid lubricants.
  • the properties of these lubricants are based inter alia on the special crystal structure and the low propensity for chemical bonds or reactions with metallic and ceramic materials.
  • the specific class of solid lubricants is selected according to the invention according to the expected temperature loads. In the case of internal cylinder coatings in internal combustion engines, the highest wall temperature, for example in the contact zone of the cylinder running surface / piston ring, is advantageously considered for this purpose.
  • the solid lubricants based on sulfides, for example MoS 2 and / or WS 2 can be used in an oxidizing atmosphere without problems up to a temperature of 350 ° C.
  • hot contact points for example, between the cylinder surface and piston rings can form, wherein the local temperature can be significantly higher than 350 ° C. Therefore, according to PCT / EP2009 / 058565
  • at least one other type of solid lubricants used which has an increased temperature resistance and at the same time is chemically resistant under the aggressive chemical conditions in the combustion chamber and the adhesion and hardness of the coating additionally positively influenced.
  • a thermal spray material is proposed with a very high zinc content of at least 70% zinc, but only under certain low pressure conditions of less than 100mbar, preferably even only between 1 mbar and 10mbar gas pressure in a process chamber while maintaining very large spray distances of at least 400mm to the substrate can be sprayed.
  • the spray material of the EP 1 790 752 A1 and the spraying method also proposed therein to replace in the field of corrosion protection the valid as environmentally harmful galvanizing. Therefore, the zinc content must be at least 70%, so that a sufficient effect of the zinc coating against corrosion is achieved.
  • the spray material of the EP 1 790 752 A1 Due to the high vapor pressure of zinc, the spray material of the EP 1 790 752 A1
  • the process chamber must have a sufficient size, so that a minimum spray distance to the substrate to be coated of at least 400mm is adjustable.
  • the pressure in the process chamber itself plays an important role, but it must also be set a pressure ratio of about 1 to 40 between a pressure in the interior of the coating jet and the actual gas pressure of the gas atmosphere in the process chamber. That is, the pressure within the coating jet must be greater than the pressure of the gas atmosphere in the process chamber.
  • pure zinc comes as a spray material additive for thermal spraying, which are not carried out in a process chamber under low pressure atmosphere, so for example for that internal coating of cylinders with rotating spray guns for the expert out of the question.
  • layers of pure zinc do not have the necessary mechanical strength or temperature resistance for applications as a cylinder surface.
  • the object of the invention is to provide a new spray material in the form of a powder material or in the form of a sprayed wire, in particular spray filler wire for thermal coating of a substrate, with which using conventional spray methods, but preferably not necessary under ambient atmosphere, that is preferably not under a reduced Gas pressure thermally sprayed layers can be produced, which have excellent tribological properties at the same time in different temperature ranges, so that the powder material is particularly suitable for forming friction-optimized running surfaces on cylinders of reciprocating internal combustion engine, which are operated even under changing load conditions.
  • the surface layers formed with the spray material should also be sufficiently resistant to corrosion and have excellent hardness and at the same time be easily machinable, especially when honing the sprayed layers.
  • the invention thus relates to a spray material for the thermal coating of a substrate, in particular for the thermal coating of a running surface of a cylinder of a reciprocating internal combustion engine.
  • the spray material comprises a solid lubricant of ZnO, wherein the volume fraction of ZnO in the spray material is in the range of 0.1% to 15% of the volume of the spray material.
  • the invention relates to a spray material for thermal coating of a substrate, in particular for thermal coating of a tread of a cylinder of a reciprocating internal combustion engine, wherein the spray material comprises a solid lubricant of ZnO, and the volume fraction of ZnO in the spray material in the range of 0.1% to 15% the volume of the spray material is.
  • the spray material additionally contains one or more elements of the elements consisting of the group of elements C, Cr, Ti, O, Mn, Mo, Fe, S, W, B, Ba, Ca and F.
  • the spray material contains one or more materials from the material group consisting of the materials MoS 2 , WS 2 , BN, CrN, CaF 2 , BaF 2 , TiO 2 , FeTiO 3 , Fe 1 Cl 1 Cr 1 Mn, Fe 13 Cr 2 Mo 0.5 C, XPT-512, alpha-Fe, iron carbide, wustite and magnetite.
  • spray materials containing ZnO are particularly well suited for the thermal coating of internal combustion engine components, if Zn is not used in pure form but bound as ZnO in the spray material and the volume fraction of ZnO in the spray material is in the range of 0.1% to about 15% of the volume of the spray material.
  • the material zinc oxide ZnO shows a real potential for use as solid lubricant, especially in combination with thermal spray coatings.
  • the hexagonal crystal structure (wurtzite)
  • the relatively low hardness Mohs 4,5 corresponds to about 350HV
  • the high vapor pressure of the zinc oxides are of particular importance.
  • the solid lubricant ZnO is mixed or agglomerated, for example, with the powder XPT-512 (low-alloyed carbon steel).
  • the particle size should preferably be from a few micrometers up to 15 micrometers.
  • a microstructure of the layer of alpha-Fe forms with fine iron carbides, Wustite FeO, Magnetite Fe 3 O 4 , and according to the invention of zinc oxide ZnO.
  • the amount of ZnO in the spray material is conveniently between 4% and 10% volume% in many applications, and in some cases may be slightly lower or higher. In practice, optimization tests, for example by means of friction tests and engine test series, for determining the optimum amount of ZnO for the specific application will usually be necessary. The same procedure can also be used with the corrosion resistant (13 weight% Cr steel) material.
  • ceramic layers can be changed or improved by the addition of ZnO, for example in the case of iron titanate FeTiO 3 (ilmenite).
  • ZnO iron titanate FeTiO 3
  • Addition of ZnO significantly improves the machinability during honing.
  • zinc oxides reduces the risk of dreaded scuffing in case of insufficient lubrication and corresponding elevated local temperatures.
  • ZnO as an additive for thermal spray materials is also important from an economic point of view, since zinc oxide is automatically obtained as a waste product in the industrial production of brass (in foundries in the production of semi-finished products) and thus very cost-effectively as a raw material for the production of the inventive spray material is available.
  • Table 2 lists further particularly preferred spray materials of the present invention, while at the same time giving preferred application examples in the field of automotive engineering for different types of engines and types of loads.
  • Table 2 ⁇ / u> Typical application examples of spraying materials according to the invention with the solid lubricant ZnO in layers of cylinder running surface of reciprocating internal combustion engines.
  • OTTO engines 4-stroke Fe 1C 1Cr 1Mn + 5 vol.% ZnO Higher speeds
  • Regular power Water cooling Sports car with automat OTTO engines 4-stroke Fe 1C 1Cr 1Mn + 10% by volume ZnO Higher speeds
  • OTTO engines 4-stroke Fe 1C 1Cr 1Mn + 10% by volume ZnO Higher speeds
  • Changing power Water cooling Racing engines Engines for hybrid vehicles Diesel engine 2-4 stroke Iron titanate FeTiO3 + 12% by volume ZnO Regular speeds Regular power Ship diesel power generator Diesel engine 4-stroke Fe 13Cr 2Mo 0.5C + 10 Vol.% ZnO Strong change. Power and speeds.
  • Truck and car OTTO engines 4-stroke Titanium oxide (rutile) TiO2 + 10% by volume ZnO Very high speeds, up to over 20,000 rpm. Strong change. Power and speeds. Water cooled. Racing engines for extreme conditions
  • high loads can also occur at relatively even and / or low speeds, for example, in large engines for ships or generators for generating electrical energy, in which not infrequently several thousand horsepower per cylinder can be generated.
  • the layers can be further adapted to specific requirements such as temperature fluctuations, Dry Attacks by acids, corrosion, oxidation, etc. are optimally adapted.
  • the above table 2 also provides information about these possibilities.
  • the tribological performance of the inventive layers can be significantly improved by the targeted addition of solid lubricants.
  • the properties of these lubricants are based inter alia on the special crystal structure and the low propensity for chemical bonds or reactions with metallic and ceramic materials.
  • the specific class of solid lubricants is selected according to the invention according to the expected different types of stress. In the case of internal cylinder coatings in internal combustion engines, for example, the highest wall temperature, for example, in the contact zone cylinder surface / piston ring is considered.
  • solid lubricants based on sulfide can be added.
  • MoS 2 and / or WS 2 can be used in an oxidizing atmosphere without problems up to a temperature of 350 ° C.
  • hot contact points for example, between the cylinder surface and piston rings can form, wherein the local temperature can be significantly higher than 350 ° C. Therefore, additionally at least one other type of solid lubricants can be used, which has an increased temperature resistance and at the same time is chemically resistant under the aggressive chemical conditions in the combustion chamber and the adhesion and hardness of the coating additionally positively influenced.
  • solid lubricants based on nitrogen for example, hexagonal BN or CrN particularly advantageous in question, as these functions as a solid lubricant up to the highest temperatures of 950 ° C, even under oxidizing conditions meet such high temperatures, for example, often occur only locally in cylinders of internal combustion engines.
  • Certain fluorine-based solid lubricants are capable of reliably ensuring lubrication even under these critical conditions.
  • calcium fluorides CaF 2 and barium fluoride BaF 2 can reliably ensure lubrication even at locally occurring temperatures of more than 1200 ° C.
  • the eutectic formed from 62% by weight of BaF 2 and 38% by weight of CaF 2 has proven to be particularly effective, which ensures significantly improved lubrication already from 500 ° C.
  • the thermally sprayed layers are advantageously post-processed in a manner known per se by diamond honing after the thermal spraying.
  • the volume fraction of ZnO in the spray material is in the range of 0.5% to 12%, preferably in the range of 4% to 12% of the volume of the spray material.
  • the spray material according to the invention comprises a carbon steel, in particular an atomized carbon steel, a chromium steel, in particular a ferritic and / or martensitic chromium steel and / or TiO 2 , and / or Mn and / or Mo or further advantageous components.
  • the spray material may comprise a ceramic material.
  • the ceramic material is particularly preferred except for impurities FeTiO 3 .
  • the ZnO in the spray material may be present as ZnO powder with a predefinable particle size and / or the spray material may be formed by agglomeration and / or mixing with the ZnO powder.
  • a particle size in the range between 1 ⁇ m and 25 ⁇ m preferably in the range between 5 ⁇ m and 15 ⁇ m has been found to be particularly advantageous.
  • a particle of the ZnO powder may also be mixed and / or agglomerated with a metal powder and / or a ceramic powder and / or a particle of the ZnO powder may be mixed with a powder of a low-alloyed carbon steel and / or agglomerated.
  • a particle of the ZnO powder is mixed and / or agglomerated and / or coated with a powder of a corrosion-resistant chromium steel and / or with a ceramic powder of FeTiO 3 .
  • a thermal spray coating is produced from a spray material of the present invention by a thermal plasma spraying process or a flame spraying process, in particular by a high-speed flame spraying process (HVOF process), the thermal spraying material preferably being used as powder, but also in the form of a sprayed wire, can be present in particular in the form of a cored wire.
  • HVOF process high-speed flame spraying process
  • the invention finally also relates to a cylinder for a reciprocating internal combustion engine which is coated with a thermal spray coating made of a spray material of the present invention.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Plasma & Fusion (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Coating By Spraying Or Casting (AREA)
  • Cylinder Crankcases Of Internal Combustion Engines (AREA)

Claims (14)

  1. Matériau de projection pour le revêtement thermique d'un substrat, en particulier pour le revêtement thermique d'une surface de glissement du cylindre d'un moteur à pistons et à combustion interne, dans lequel le matériau de projection comprend un lubrifiant solide en ZnO, et la fraction de volume de ZnO dans le matériau de projection est de 0,1% à 15% du volume de matériau de projection, dans lequel le matériau de projection comprend en outre un ou plusieurs éléments des éléments composés du groupe des éléments C, Cr, Ti, O, Mn, Mo, Fe, S, W, B, Ba, Ca et F
    caractérisé en ce que
    le matériau de projection comprend un acier carbone.
  2. Matériau de projection selon la revendication 1, dans lequel le matériau de projection comprend un ou plusieurs matériaux du groupe de matériau composé des matériaux MoS2, WS2, BN, CrN, CaF2, BaF2, TiO2, FeTiO3, Fe1 C1 Cr1 Mn, Fe13Cr2Mo0.5C, XPT-512, alpha-Fe, carbure de fer, wustite et magnétite.
  3. Matériau de projection selon l'une des revendications 1 ou 2, dans lequel la fraction de volume de ZnO dans le matériau de projection est de 0.5% à 12%, préféré de 4% à 12% du volume de matériau de projection.
  4. Matériau de projection selon l'une des revendications précédentes, dans lequel le matériau de projection comprend un acier carbone atomisé.
  5. Matériau de projection selon l'une des revendications précédentes, dans lequel le matériau de projection comprend un acier chromé.
  6. Matériau de projection selon l'une des revendications précédentes, dans lequel le matériau de projection comprend un matériau céramique.
  7. Matériau de projection selon la revendication 6, dans lequel le matériau céramique est FeTiO3 à des impuretés près.
  8. Matériau de projection selon l'une des revendications précédentes, dans lequel ZnO est présent sous forme de poudre dans le matériau de projection avec une taille des particules prédeterminable et / ou le matériau de projection est formé par agglomération et / ou mélange et / ou rechargement avec le poudre ZnO.
  9. Matériau de projection selon la revendication 8, dans lequel la taille des particules du poudre ZnO est de 1µm et 25 µm, préféré entre 5 µm et 15 µm.
  10. Matériau de projection selon l'une des revendications 8 ou 9, dans lequel une particule du poudre ZnO est mélangée et / ou agglomérée et / ou formée au moyen de rechargement avec une poudre métallique et / ou une poudre céramique et / ou dans lequel une particule du poudre ZnO est mélangée et / ou agglomérée avec une poudre d'un acier carbone faiblement allié.
  11. Matériau de projection selon l'une des revendications 8 à 10, dans lequel une particule du poudre ZnO est mélangée et / ou agglomérée et / ou formée au moyen de rechargement avec une poudre d'un acier chromé anti-corrosif, en particulier d'un acier chromé ferritique et / ou martensitique.
  12. Matériau de projection selon l'une des revendications 8 à 11, dans lequel une particule du poudre ZnO est mélangée et / ou agglomérée et / ou formée au moyen de rechargement avec une poudre céramique en FeTiO3.
  13. Couche de projection thermique d'un matériau de projection selon l'une des revendications 1 à 12.
  14. Cylindre pour un moteur à pistons et à combustion interne revêtu avec une couche de projection thermique selon la revendication 13.
EP10189151.3A 2009-12-03 2010-10-28 Composition pour revêtement par projection à chaud, ainsi que cylindre doté d'une couche deposée par projection à chaud Not-in-force EP2330228B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP10189151.3A EP2330228B1 (fr) 2009-12-03 2010-10-28 Composition pour revêtement par projection à chaud, ainsi que cylindre doté d'une couche deposée par projection à chaud

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP09177917 2009-12-03
EP10189151.3A EP2330228B1 (fr) 2009-12-03 2010-10-28 Composition pour revêtement par projection à chaud, ainsi que cylindre doté d'une couche deposée par projection à chaud

Publications (2)

Publication Number Publication Date
EP2330228A1 EP2330228A1 (fr) 2011-06-08
EP2330228B1 true EP2330228B1 (fr) 2017-09-27

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EP10189151.3A Not-in-force EP2330228B1 (fr) 2009-12-03 2010-10-28 Composition pour revêtement par projection à chaud, ainsi que cylindre doté d'une couche deposée par projection à chaud

Country Status (7)

Country Link
US (1) US8492318B2 (fr)
EP (1) EP2330228B1 (fr)
JP (1) JP5595229B2 (fr)
CN (1) CN102086499B (fr)
AU (1) AU2010246513B2 (fr)
CA (1) CA2722865C (fr)
ES (1) ES2654311T3 (fr)

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ES2654311T3 (es) 2018-02-13
JP2011117079A (ja) 2011-06-16
US20110155090A1 (en) 2011-06-30
CN102086499B (zh) 2015-07-29
CA2722865C (fr) 2018-07-10
US8492318B2 (en) 2013-07-23
AU2010246513A1 (en) 2011-06-23
CN102086499A (zh) 2011-06-08
CA2722865A1 (fr) 2011-06-03
AU2010246513B2 (en) 2014-07-24
JP5595229B2 (ja) 2014-09-24
EP2330228A1 (fr) 2011-06-08

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