EP0143343A1 - Revêtements résistant à l'usure et à la corrosion et procédé pour leur fabrication - Google Patents

Revêtements résistant à l'usure et à la corrosion et procédé pour leur fabrication Download PDF

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Publication number
EP0143343A1
EP0143343A1 EP84112938A EP84112938A EP0143343A1 EP 0143343 A1 EP0143343 A1 EP 0143343A1 EP 84112938 A EP84112938 A EP 84112938A EP 84112938 A EP84112938 A EP 84112938A EP 0143343 A1 EP0143343 A1 EP 0143343A1
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EP
European Patent Office
Prior art keywords
weight percent
coating
composition
substrate
cobalt
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP84112938A
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German (de)
English (en)
Other versions
EP0143343B1 (fr
Inventor
John Eric Jackson
Thomas Allen Adler
Jean Marie Quets
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.)
Union Carbide Corp
Original Assignee
Union Carbide Corp
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Filing date
Publication date
Application filed by Union Carbide Corp filed Critical Union Carbide Corp
Publication of EP0143343A1 publication Critical patent/EP0143343A1/fr
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Publication of EP0143343B1 publication Critical patent/EP0143343B1/fr
Expired legal-status Critical Current

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Classifications

    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C4/00Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/04Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C29/00Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
    • C22C29/02Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides
    • C22C29/06Alloys 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
    • C22C29/08Alloys 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
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C4/00Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/04Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
    • C23C4/06Metallic material
    • C23C4/067Metallic material containing free particles of non-metal elements, e.g. carbon, silicon, boron, phosphorus or arsenic

Definitions

  • the present invention relates to wear and corrosion resistant coatings and to a method for producing such coatings. More particularly, the invention relates to a new family of W-Co-Cr-C coatings having improved strength and wear resistance.
  • Coatings of W-Co-Cr-C are used in those applications where both superior wear and corrosion resistance are required.
  • a typical composition for these coatings comprises about 8 to 10 weight percent cobalt, about 3 to 4 weight percent chromium, about 4.5 to 5.5 weight percent carbon and the balance tungsten.
  • These coatings can be successfully applied to various substrates, e.g., iron base alloy substrates, using known thermal spray techniques. Such techniques include, for example, detonation gun (D-Gun) deposition as disclosed in U.S. Patent Nos. 2,714,563 and 2,950,867, plasma arc spray as disclosed in U.S. Patent Nos. 2,858,411 and 3,016,447 and other so-called "high velocity" plasma or "hypersonic" combustion spray processes.
  • D-Gun detonation gun
  • a coating composition in accordance with the present invention consists essentially of from about 6.5 to about 9.0 weight percent cobalt, from about 2.0 to about 4.0 weight percent chromium, from about 3.0 to about 4.0 weight percent carbon and the balance tungsten.
  • the coatings of the present invention can be applied to a substrate using any conventional thermal spray technique.
  • the preferred method of applying the coating is by detonation gun (D-Gun) deposition.
  • D-Gun detonation gun
  • a typical D-Gun consists essentially of a water-cooled barrel which is several feet long with an inside diameter of about 1 inch.
  • a mixture of oxygen and a fuel gas, e.g., acetylene, in a specified ratio (usually about 1:1) is fed into the barrel along with a charge of powder to be coated.
  • the gas is then ignited and the detonation wave accelerates the powder to about 2400 ft./ sec. (730 m/sec.) while heating the powder close to or above its melting point.
  • a pulse of nitrogen purges the barrel and readies the system for the next detonation. The cycle is then repeated many times a second.
  • the D-Gun deposits a circle of coating on the substrata with each detonation.
  • the circles of coating are about 1 inch (25 mm) in diameter and a few ten thousandths of an inch (microns) thick.
  • Each circle of coating is composed of many overlapping microscopic .plats corresponding to the individual powder particles. The overlapping splats interlock and mechanically bond to each other and to the substrate without substantially alloying at the interface thereof.
  • the placement of the circles and the coating deposition are closely controlled to build up a smooth coating of uniform thickness and to minimize substrate heating and establishment of residual stresses in the applied coating.
  • the powder used in producing the coating of the present invention may be essentially the same powder composition as heretofore employed in depositing W-Co-Cr-C coatings of the prior art.
  • the oxy-fuel gas ratio employed in the D-Gun process is increased from a value of about 1.0 to a value of between about 1.1 and 1.2. Under these conditions, changes during the coating process result in the desired coating composition. It is also possible to use other operating conditions with a D-Gun and still obtain the desired coating composition if,the powder composition is adjusted accordingly.
  • other powder compositions may be used with other thermal spray coating devices to compensate for changes in composition during deposition and obtain the desired coating composition of this invention.
  • the powders used in the D-Gun for applying a coating according to the present invention are preferably sintered powders. However, other forms of powder such as cast and crushed powder can also be used. Generally, the size of the powder should be about -325 mesh. Powders produced by other methods of manufacture and with other size distributions may be used according to the present invention with other thermal spray deposition techniques if they are more suited to a particular spray device and/or size.
  • This powder composition consists essentially of about 10 weight percent cobalt, about 4 weight percent chromium, about 5 weight percent carbon and the balance tungsten.
  • the feed rate of both oxygen and fuel gas e.g,, acetylene
  • the feed rate of both oxygen and fuel gas should be adjusted to provide an oxy-fuel gas ratio of between about 1.1 and 1.2 This ratio is higher than that usually used heretofore with the same powder composition and provides an oxidizing mixture which reduces the carbon content of the applied coating.
  • the coating of the present invention can be applied to a substrate by plasma arc spray or other thermal spray techniques.
  • plasma arc spray process an electric arc is established between a non-consumable electrode and a second non-consumable electrode spaced therefrom.
  • a gas is passed in contact with the non-consumable electrode such that it contains the arc.
  • the arc-containing gas is constricted by a nozzle and results in a high thermal content effluent.
  • Powdered coating material is injected into the high thermal content effluent from the nozzle and is deposited onto the surface to be coated.
  • This process which is described in U.S. Patent No. 2,858,411, supra, produces a deposited coating which is sound, dense and adherent to the substrate.
  • the applied coating also consists of irregularly shaped microscopic splats or leaves which are interlocked and mechanically bonded to one another and also to the substrate.
  • powders fed to the arc torch may have essentially the same composition as the applied coating itself.
  • some change in composition is to be expected and, in such cases, the powder composition may be adjusted accordingly to achieve the coating composition of the present invention.
  • the coatings of the present invention may be applied to almost any type of substrate, e.g., metallic substrates such as iron or steel or non-metallic substrates such as carbon, graphite and polymers, for instance.
  • substrate material used in various environments and admirably suited as substrates for the coatings of the present invention include, for example, steel, stainless steel, iron base alloys, nickel, nickel base alloys, cobalt, cobalt base alloys, chromium, chromium base alloys, titanium, titanium base alloys, aluminum, aluminum base alloys, copper, copper base alloys, refractory metals, and refractory-metal base alloys.
  • the composition of the coatings of the present invention may vary within the ranges indicated above, the preferred coating composition consists essentially of from about 7.0 to 8.5 weight percent cobalt, from about 2.5 to 3.5 weight percent chromium, from about 3.0 to 4.0 weight percent carbon and the balance tungsten.
  • Such coatings are ideally edited for industrial valves, mechanical seals, bushings and the like. They are also ideally suited for use in the textile industry as crimper rolls, for example.
  • the microstructure of the coatings of the present invention are very complex and not completely understood. However, it is believed that the major portion of the coatings consist essentially of a mixture of WC and (W,Cr,Co) 2 C with other metal carbides and possibly metallic phases. Despite the lower volume fraction of carbides present as compared to similar coatings of the prior art, the coatings of the present invention surprisingly exhibit improved wear resistance without sacrificing other desirable characteristics such as hardness, toughness, etc. Typical hardness values for coatings of the present invention exceed about 900 DP H 3 00'
  • Specimens of AISI 1018 steel were cleaned and prepared for coating as follows. The surface on one side of each specimen was ground smooth and parallel to the opposite side. The surface was then grit blasted with 60 mesh Al 2 O 3 to a surrace roughness of about 120 micro-inch RMS. All the specimens were then coated according to the prior art using a detonation gun (D-Gun) and a sintered powder of the following composition: 10 weight percent Co, 4 weight percent Cr, 5.2 weight percent C and the balance W. The size of the powders was about -325 mesh. Acetylene was used as the fuel gas. The oxy-fuel gas ratio was 0.98.
  • a chemical analysis of the coating showed the following composition: 8 weight percent Co, 3.2 weight percent Cr, 4.7 weight percent C and the balance W.
  • the chemical analysis was carried out principally by two methods. Carbon was analyzed by a combustion analysis technique using a Loco Carbon Analyzer and volumetric determination of gaseous output. Cobalt and chromium were analyzed by first fusing the sample in Na 2 0 2 and separating the cobalt and chromium, then determining the amount of each potentiometrically.
  • Abrasive wear properties of the applied coating were determined using the standard dry sand/rubber wheel abrasion test described in ASTM Standard G65-80, Procedure A.
  • ASTM Standard G65-80, Procedure A the specimen was loaded by means of a lever arm against a rotating wheel with a chlorobutyl rubber rim around the wheel.
  • An abrasive i.e., 50-70 mesh Ottawa Silica Sand
  • the wheel was rotated in the direction of abrasive flow.
  • the test specimen was weighed before, after and periodically during the test, and its weight loss was recorded. Because of the wide differences in the densities of different materials tested, the mass loss is normally converted to volume loss to evaluate the relative ranking of materials.
  • the average volume loss for these specimens (conventional W-Co-Cr-C coating) was 1.7 mm 3 per 1000 revolutions.
  • the hardness of these specimens was also measured by standard methods. The average hardness was found to be 1100 DPH 300' The specimens were also easily ground to a smooth finish using the normal method of finishing wear resistant coating with a diamond grinding wheel and an infeed of 0.0005 inch per pass.
  • Specimens of AISI 1018 steel were prepared in the same manner as described in Example I. The specimen surfaces were then coated using a D-Gun and the same sintered powder, i.e., 10 weight percent Co, 4 weight percent Cr, 5.2 weight percent C and the balance W. The powder size was also identical, i.e., -325 mesh. Acetylene was also used as the fuel gas. In this instance, however, the oxy-fuel gas ratio in the D-Gun was 1.1 according to the present invention.
  • a chemical analysis of the coating showed the following composition: 7.6 weight percent Co, 2.9 weight percent Cr, 3.5 weight percent C and the balance W.
  • the hardness of the specimens was also measured and found to be 1150 DPH 300 .
  • the specimens were also easily ground to a smooth finish using the normal method as in Example I.
  • Specimens of AISI 1018 steel were prepared in the same manner as described in Example I. The specimen surfaces were then coated with a D-Gun and the same sintered powder, i.e., 10 weight percent Co, 4 weight percent Cr, 5.2 weight percent C and the balance W. The powder size was also identical, i.e., -325 mesh. Acetylene was also used as the fuel gas. However, the oxy-fuel gas ratio used in this instance was 1.2 according to the present invention.
  • a chemical analysis of the coating showed the following composition: 7.8 weight percent Co, 2.9 weight percent Cr, 3.1 weight percent C and the balance W.
  • the hardness of the specimen was also measured and found to be 1080 DPH300.
  • the specimen was ground to a smooth but somewhat rougher finish using the normal method as in Example I.
  • Specimens. of AISI 1018 steel were prepared in the same manner as described in Example I. The specimen surfaces were then coated with a D-Gun and the same sintered powder; i.e., 10 weight percent Co, 4 weight percent Cr, 5.2 weight percent C and the balance W. The powder size was also identical, i.e., -325 mesh. Acetylene was also used as the fuel gas. However, the oxy-fuel gas mixture used in this instance was 1.3.
  • a chemical analysis of the coating showed the following composition: 7.6 weight percent Co, 2.7 weight percent Cr, 2.6 weight percent C and the balance W.
  • the hardness of this type of coating is about 1125 DPH 300 .
  • Abrasive wear tests were carried out on this coating as in Example I, II, and III with a volume loss of 1.5 mm3 per revolution. However, attempts to grind the coating to a smooth finish were unsuccessful using the normal method as described in Example 1.
  • Specimens of AISI 1018 steel were prepared in the same manner as described in Example I. The specimen surfaces were then coated using a plasma spray torch and the same sintered powder; i.e., 10 weight percent Co, 4 weight percent Cr, 5.2 weight percent C and the balance W. The powder size was also -325 mesh.
  • a chemical analysis of the coating showed the following composition: 9.2 weight percent Co, 3.5 weight percent Cr, 5.0 weight percent C and the balance W.
  • the cobalt and carbon content of this coating was higher than that of the coatings of the present invention.
  • the hardness of the specimen was also measured and found to be 687 DPH300.
  • Specimens of AISI 1018 steel were prepared in the same manner as described in Example I. The specimen surfaces were then coated using a plasma spray torch and a sintered powder of the following composition: 10.9 weight percent Co, 4.3 weight percent Cr, 3.8 weight percent C and the balance W. The powder size was -325 mesh.
  • a chemical analysis of the coating showed the following composition: 8.6 weight percent Co, 3.6 weight percent Cr, 3.4 weight percent C and the balance W. This coating composition was within the scope of the present invention.
  • the hardness of the coated specimen was also measured and found to be 8 3 0 DPH 300'
  • iron is usually the principal impurity in the coating resulting from grinding operations and may be present in amounts up to about 1.5 and in some cases 2.0 weight percent of the composition.

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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)
  • Coating By Spraying Or Casting (AREA)
EP84112938A 1983-10-28 1984-10-26 Revêtements résistant à l'usure et à la corrosion et procédé pour leur fabrication Expired EP0143343B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US54654283A 1983-10-28 1983-10-28
US546542 1983-10-28

Publications (2)

Publication Number Publication Date
EP0143343A1 true EP0143343A1 (fr) 1985-06-05
EP0143343B1 EP0143343B1 (fr) 1987-09-16

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ID=24180888

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EP84112938A Expired EP0143343B1 (fr) 1983-10-28 1984-10-26 Revêtements résistant à l'usure et à la corrosion et procédé pour leur fabrication

Country Status (9)

Country Link
EP (1) EP0143343B1 (fr)
JP (1) JPS60128257A (fr)
KR (1) KR890005129B1 (fr)
AU (1) AU564804B2 (fr)
CA (1) CA1229204A (fr)
DE (1) DE3466251D1 (fr)
HK (1) HK35888A (fr)
IN (1) IN167503B (fr)
SG (1) SG5188G (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0399375A1 (fr) * 1989-05-24 1990-11-28 Outokumpu Oy Procédé pour le traitement et la préparation de matériau
EP0687746A1 (fr) 1994-06-13 1995-12-20 VOEST-ALPINE STAHL LINZ Gesellschaft m.b.H. Elément de construction destiné à l'utilisation dans un bain métallique
CN116714317A (zh) * 2023-04-27 2023-09-08 德州春祥包装制品有限公司 一种高强度纳米碳化钨瓦楞辊

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100467218B1 (ko) * 1997-03-15 2005-09-02 삼성중공업 주식회사 캐비테이션현상으로인한침식을방지하기위한내침식성코팅방법

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2950867A (en) * 1954-10-21 1960-08-30 Union Carbide Corp Pulse powder feed for detonation waves
DE1185034B (de) * 1958-04-24 1965-01-07 Metco Inc Metallcarbid enthaltende Metallpulvermischung zur Herstellung von UEberzuegen auf Metallkoerpern durch Spritzschweissen
US4173685A (en) * 1978-05-23 1979-11-06 Union Carbide Corporation Coating material and method of applying same for producing wear and corrosion resistant coated articles
DE2829369B2 (de) * 1977-07-05 1981-06-04 Union Carbide Corp., 10017 New York, N.Y. Verfahren zum Ausbilden von harten, verschleißfestenMetallkarbide enthaltenden Überzügen

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2950867A (en) * 1954-10-21 1960-08-30 Union Carbide Corp Pulse powder feed for detonation waves
DE1185034B (de) * 1958-04-24 1965-01-07 Metco Inc Metallcarbid enthaltende Metallpulvermischung zur Herstellung von UEberzuegen auf Metallkoerpern durch Spritzschweissen
DE2829369B2 (de) * 1977-07-05 1981-06-04 Union Carbide Corp., 10017 New York, N.Y. Verfahren zum Ausbilden von harten, verschleißfestenMetallkarbide enthaltenden Überzügen
US4173685A (en) * 1978-05-23 1979-11-06 Union Carbide Corporation Coating material and method of applying same for producing wear and corrosion resistant coated articles

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0399375A1 (fr) * 1989-05-24 1990-11-28 Outokumpu Oy Procédé pour le traitement et la préparation de matériau
EP0687746A1 (fr) 1994-06-13 1995-12-20 VOEST-ALPINE STAHL LINZ Gesellschaft m.b.H. Elément de construction destiné à l'utilisation dans un bain métallique
AT400726B (de) * 1994-06-13 1996-03-25 Voest Alpine Stahl Metallischer bauteil zur verwendung in einem metallbad
CN116714317A (zh) * 2023-04-27 2023-09-08 德州春祥包装制品有限公司 一种高强度纳米碳化钨瓦楞辊

Also Published As

Publication number Publication date
SG5188G (en) 1988-06-17
HK35888A (en) 1988-05-20
CA1229204A (fr) 1987-11-17
IN167503B (fr) 1990-11-10
EP0143343B1 (fr) 1987-09-16
KR850003905A (ko) 1985-06-29
JPS6331547B2 (fr) 1988-06-24
KR890005129B1 (ko) 1989-12-11
DE3466251D1 (en) 1987-10-22
AU3473184A (en) 1985-05-02
AU564804B2 (en) 1987-08-27
JPS60128257A (ja) 1985-07-09

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