EP0442017B1 - Method of forming abrasion-resistant coating layer - Google Patents

Method of forming abrasion-resistant coating layer Download PDF

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Publication number
EP0442017B1
EP0442017B1 EP19900103062 EP90103062A EP0442017B1 EP 0442017 B1 EP0442017 B1 EP 0442017B1 EP 19900103062 EP19900103062 EP 19900103062 EP 90103062 A EP90103062 A EP 90103062A EP 0442017 B1 EP0442017 B1 EP 0442017B1
Authority
EP
European Patent Office
Prior art keywords
cr2o3
spray coating
weight
coating layer
melting
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
EP19900103062
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German (de)
English (en)
French (fr)
Other versions
EP0442017A1 (en
Inventor
Yoshihisa Kitajima
Masaki Tanaka
Shuzo Hirata
Takashi Nakamura
Masaoki Watanabe
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Mitsui Engineering and Shipbuilding Co Ltd
Original Assignee
Mitsui Engineering and Shipbuilding Co Ltd
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Filing date
Publication date
Application filed by Mitsui Engineering and Shipbuilding Co Ltd filed Critical Mitsui Engineering and Shipbuilding Co Ltd
Priority to DE1990615801 priority Critical patent/DE69015801T2/de
Publication of EP0442017A1 publication Critical patent/EP0442017A1/en
Application granted granted Critical
Publication of EP0442017B1 publication Critical patent/EP0442017B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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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

Definitions

  • the present invention concerns a method of forming an abrasion resistant coating layer and, more in particular, it relates to a method of forming a coating layer having high lubricant retainability and excellent abrasion resistance.
  • spray coating process makes possible to form coating layer of various metals, ceramics or composite materials thereof, because the molten metal, ceramics, and others collide against the surface of substrate at a high speed and a coating layer is formed on the surface of members by the process. Then, by spray coating a metal, for instance, desirable property such as corrosion resistance, heat resistance and electroconductivity can be provided.
  • the surface must not be excessively smooth to keep the scuffing resistance property. If the surfaces is extremely smooth, the lubricant retainability at the sliding surfaces is lowered tending to cause lack of the lubricant and led to scuffing.
  • the abrasion resistance can be improved due to the high hardness of the coating layer.
  • a member is a sliding member
  • the sliding property is inevitably reduced since the roughness at the surface of the coating layer is high.
  • ceramic coating layer of high hardness may possibly injure the mating material.
  • the fracture toughness of the ceramics is low, the brittle fracture occurs on the friction surface, follows a problem that abrasion can not be reduced sufficiently.
  • a spray coating gun 1 as shown in Fig. 3 is usually employed and spray coating material is supplied from a spray coating material supply port 2 and jetted in a flame or plasma 4 onto the surface of a substrate 3 to form the coating layer.
  • the spray coating gun 1 is moved relative to the plate surface of the substrate 3 as shown in Fig. 4.
  • Fig. 4 shows a trace of a center of the working spray coating gun (center of the plasma) projected on the plate surface of the substrate 3.
  • the spray coating gun is reciprocated leftward and lightward from a starting point A for spray coating and, simultaneously, displaced little by little downwardly at each of the turning points on both ends. Then, after reaching the lowermost end of the substrate 3, the gun is returned to the starting point A for spray coating.
  • Such procedures of the spray coating gun are usually repeated by an appropriate number of cycles to form required coating thickness.
  • an abrasion resistant coating layer excellent both in the lubricant retainability and the sliding property can be formed.
  • a spray coating layer using a powder mixture of a Mo or Mo alloy powder and a Cr2O3 powder as the spray coating material there is the following problem.
  • the spray coating layer 5 thus formed comprises the Cr2O3-enriched layer 5a and the Mo-enriched layer 5b stacked one above the other and it is impossible to form a Cr2O3-Mo composite material coating layer in which Mo and Cr2O3 are finely dispersed.
  • Mo and Cr2O3 can be dispersed extremely finely. Accordingly, a powder obtained by cooling to solidify the molten mixture and then pulverizing them can provide Cr2O3-Mo composite material particles in which respective particles are finely dispersed therein.
  • the spray coating layer formed by the method according to the present invention is a coating layer of composite material comprising Mo as high melting point metal and Cr2O3 as ceramics of high hardness. Accordingly, the coating layer is excellent having both of the high toughness of Mo and heat resistance, high hardness and chemical stability of Cr2O3. Great toughness and high hardness thus combined can remarkably improve the abrasion resistance of the coating layers.
  • the coating layer formed in accordance with the present invention has a structure in which a Mo phase is dispersed into a Cr2O3 matrix phase.
  • the Mo phase hardness lower than Cr2O3 is abraded to form a plurality of fine pits at the surface of the coating layer.
  • the pits function as a retainer of the lubricant, remarkably improve the lubricant supply and improve the abrasion resistance at the surface of the member.
  • An object of the present invention is to provide a method capable of preventing separate flying of Mo or Mo alloy particles and Cr2O3 particles during spray coating and forming a coating layer of Cr2O3-Mo composite material coating layer having satisfactory abrasion resistance and sliding property together.
  • Another object of the present invention is to provide a method of forming a coating layer of Cr2O3-Mo composite material capable of greatly improving the endurance of sliding members, etc. using a lubricant.
  • Fig. 1 is a systematic diagram illustrating a method of practicing the present invention.
  • a Mo or Mo alloy powder, a Cr2O3 powder and, optionally, other powder are at first mixed at a predetermined ratio and the resultant powder mixture is melted.
  • arc melting is suitable.
  • Upon melting it is preferred to apply heating under an inert gas atmosphere such as of Ar gas for preventing degeneration of the starting material such as oxidation of Mo upon melting under heating.
  • an inert gas atmosphere such as of Ar gas
  • Melting may be conducted at any temperature so long as the powder mixture can be melted and, usually, it is conducted at a temperature higher than the melting point of Mo or Mo alloy. By the melting, the powder mixture is formed into a state where Mo, Cr2O3, etc. are finely dispersed and mixed to each other.
  • solidified products obtained by cooling after melting the powder mixture constitute an ingot of Cr2O3-Mo series composite material in which Mo, Cr2O3, etc. are finely dispersed.
  • the resultant ingot of Cr2O3-Mo system composite material is then pulverized and sieved using appropriate means.
  • the ingot is coarsely pulverized by using a hammer mill, etc. and then finely pulverized by a ball mill, etc. and then sieved.
  • the grain size is adjusted such that it is suitable to spray coating, that is, about from 1 to 100 ⁇ m, preferably, from 10 to 44 ⁇ m.
  • the Cr2O3-Mo system composite material powder as the starting material, may be spray coated to the surface of a member and, subsequently, laser beams may be irradiated further to the surface of the spray-coated layer thus formed for promoting melting of the coating layer.
  • Irradiation of laser beams is suitable to a case where the melting of starting material is insufficient but it also has an effect of increasing the density of the spray coating layer even in a case where sufficiently melted powder is spray coated. Further, it has an effect of melting also the mating interface between the coating layer and the substrate thereby increasing the bonding strength and enabling to form the coating layer to all kinds of substrates.
  • coating layer can be formed to the surface of members of any kind of materials with no particular restriction. Further, the thickness of the coating layer formed can be varied optionally by changing conditions for spray coating such as a spray coating time.
  • content of other ingredients than Cr2O3 and Mo is defined as below 34% in view of the preferred range described above (60% of Cr2O3 and 6% (60 x 0.10) of Mo).
  • ingredients other than Cr2O3 and Mo there can be mentioned, for example, the following ingredients (1) - (4).
  • R2O3 type oxides R represents rare earth element
  • R represents rare earth element
  • La Nd, Sm, Eu, Gd, Dy, Ho, Er, Tm, Yb and Lu.
  • the Mo alloy when a Mo alloy is used as the starting material, it is preferred that the Mo alloy contains not greater than 30% of Fe, not greater than 10% of Al, not greater than 10% of Ni, not greater than 15% of Cr, not greater than 10% of Co, not greater than 3% of C.
  • Fe is inexpensive and capable of reducing the cost of the Mo alloy but, since excess Fe will deteriorate the abrasion resistance and the melting point of the coating layer, it is preferred that Fe is not greater than 30%, particularly, not greater than 20%.
  • Al can refine the metal texture and improve the corrosion resistance thereof but, since excess amount of Al will reduce the corrosion resistance and lower the melting point of the coating layer, it is preferably not greater than 10%, more preferably, not greater than 7%.
  • Ni is effective for reinforcing the substrate but excess amount of Ni tends to cause different textures. Accordingly, Ni is preferably not greater than 10% and, particularly, not greater than 7%.
  • Cr improves the corrosion resistance of the substrate but it easily tends to form carbides and excess content thereof tends to deteriorate the toughness of the metal texture. Accordingly, Cr is preferably not greater than 15%, particularly preferably, not greater than 10%.
  • Co has an effect of reinforcing the substrate but, since excess Co will lower the melting point of the substrate, it is preferably not greater than 10% and, particularly preferably, not greater than 7%.
  • C has a function of improving the scuffing resistance and the abrasion resistance of the substrate but, since excess amount of C increases the deposition amount of the carbide and deteriorating the strength of the substrate itself, it is preferably not greater than 3%.
  • the method of forming the abrasion resistance coating layer according to the present invention it is possible to easily form a coating layer of high performance comprising Cr2O3 and Mo finely dispersed therein having satisfactory lubricant-retainability, excellent both in abrasion resistance and scuffing resistance and also excellent in mechanical property onto the surface of substrates made of any kind of materials.
  • a Cr2O3 powder and a Mo powder were mixed to obtain a powder mixture of a composition comprising 76%Cr2O3 - 24%Mo and a powder mixture 10 was melted in an arc melting furnace 11 shown in Fig. 6.
  • a valve V1 was at first opened to evacuate the inside to 1.33 x 10 ⁇ 4 mbar (1 x 10 ⁇ 4 Torr) by means of a vacuum pump 13. Then, the valve V1 is closed and another valve V2 was opened to introduce an Ar gas at 99.99% purity to increase the pressure in a melting chamber 15,96 to 1010,8 mbar (12 to 760 Torr).
  • a voltage was applied between a tungsten electrode (negative electrode) 14 and a water-cooled copper crucible (positive electrode) 15 in a melting chamber 12 (16 represents an inlet and 17 represents an exit of coolants) and arc discharge was conducted to melt the powder mixture 10 by the heat of the arc.
  • the obtained solidified product was coarsely pulverized by using a hammer mill, finely pulverized in a ball mill using an alumina pot and alumina balls and then sieved to obtain a powder of a grain size of 10 to 44 ⁇ m.
  • the cross section of the resultant particulate grains was observed by way of an optical microscope. It was confirmed that the respective grains were Cr2O3 - Mo composite material particles in which Mo was finely dispersed in the Cr2O3 matrix.
  • the resultant Cr2O3-Mo composite material powder was plasma spray coated to the surface of a substrate made of SUS 430 to form a coating layer of 300 ⁇ m thickness.
  • Spray coating device Low pressure plasma spray coating device Pressure of atmosphere (100 ⁇ 120 Torr) 133 ⁇ 159.6 mbar Amount of power supplied 1.5 kg/hr
  • a coating layer was formed in the same procedures as those in Example 1 except for using a powder mixture of Cr2O3 - 24%Mo prepared by merely mixing a Cr2O3 powder and a Mo powder as the spray coating material.
  • the coating layer had a laminated structure in which white Mo layers and gray Cr2O3 layers were alternately laminated with respect to the direction along the thickness of the coating layer.
  • Fig. 10 After grinding the surface of the resultant pin-type specimen (rotation side) 21 and the disc-type specimen (fixing side) 22 on the side of sliding movement, they were set so as to be applied with the rotational force R and vertical load W as shown in Fig. 9 and the abrasion amount was measured by using a device as shown in Fig. 10.
  • Fig. 10 In Fig. 10, are shown a belt 23, a shaft 24, a motor 25, a coolant oil circulating pipe 26, a lubricant 27 and air cylinder 28.
  • the experiment conditions in this case are as shown in Table-2. Results are shown in Fig. 11.
  • Test specimen was prepared in the same procedures as those in Example 2 except for using a powder mixture of Cr2O3 + 24%Mo only by mixing a Cr2O3 powder and a Mo powder.
  • the resultant test specimen was measured for the abrasion amount in the same way as in Example 2. The results are shown in Fig. 11(a) and (b).

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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)
  • Manufacture Of Metal Powder And Suspensions Thereof (AREA)
EP19900103062 1988-08-24 1990-02-16 Method of forming abrasion-resistant coating layer Expired - Lifetime EP0442017B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
DE1990615801 DE69015801T2 (de) 1990-02-16 1990-02-16 Verfahren zur Herstellung einer verschleissfesten Oberflächenschicht.

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP63210095A JPH0261050A (ja) 1988-08-24 1988-08-24 耐摩耗性被膜の形成方法

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EP0442017A1 EP0442017A1 (en) 1991-08-21
EP0442017B1 true EP0442017B1 (en) 1995-01-04

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JP (1) JPH0261050A (enExample)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5549834B2 (ja) * 2009-04-30 2014-07-16 住友大阪セメント株式会社 溶射膜及びその製造方法
DE102010038947A1 (de) * 2010-08-05 2012-02-09 Aktiebolaget Skf Verbindungsanordnung und Verfahren zur Herstellung eines hülsenförmig ausgebildeten Verbindungselements

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* Cited by examiner, † Cited by third party
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JPS6299449A (ja) * 1985-10-25 1987-05-08 Showa Denko Kk クロムカ−バイト系溶射用粉末
JPS6314851A (ja) * 1986-07-03 1988-01-22 Tech Res Assoc Highly Reliab Marine Propul Plant 耐摩耗性被膜及びその形成方法

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Publication number Publication date
JPH0261050A (ja) 1990-03-01
EP0442017A1 (en) 1991-08-21
JPH0327627B2 (enExample) 1991-04-16

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