EP0220252A1 - REVETEMENT DE PROTECTION EN Cr2O3 ET PROCEDE DE FABRICATION. - Google Patents

REVETEMENT DE PROTECTION EN Cr2O3 ET PROCEDE DE FABRICATION.

Info

Publication number
EP0220252A1
EP0220252A1 EP86902821A EP86902821A EP0220252A1 EP 0220252 A1 EP0220252 A1 EP 0220252A1 EP 86902821 A EP86902821 A EP 86902821A EP 86902821 A EP86902821 A EP 86902821A EP 0220252 A1 EP0220252 A1 EP 0220252A1
Authority
EP
European Patent Office
Prior art keywords
protective layer
layer
carrier
plasma
density
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
EP86902821A
Other languages
German (de)
English (en)
Other versions
EP0220252B1 (fr
Inventor
Heiko Gruner
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.)
Plasmainvent AG
Original Assignee
Plasmainvent AG
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Plasmainvent AG filed Critical Plasmainvent AG
Priority to AT86902821T priority Critical patent/ATE47892T1/de
Publication of EP0220252A1 publication Critical patent/EP0220252A1/fr
Application granted granted Critical
Publication of EP0220252B1 publication Critical patent/EP0220252B1/fr
Expired legal-status Critical Current

Links

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
    • C23C4/10—Oxides, borides, carbides, nitrides or silicides; Mixtures thereof
    • 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
    • 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
    • C23C4/12—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the method of spraying
    • C23C4/137—Spraying in vacuum or in an inert atmosphere

Definitions

  • the invention relates to a Cr_0_ protective layer applied to a carrier in the plasma spraying process and a method for the production thereof.
  • Protective layers of this type can be applied to very different carrier bodies and are applied for various reasons
  • plasma spraying is very suitable for melting oxidic and therefore mostly high-melting powder particles and depositing them as a spray layer on a workpiece surface.
  • the Cr-C protective layer produced in this way is not sufficiently dense, its adhesion to the workpiece surface and the adhesive bond of the individual wettable powder particles to one another is insufficient.
  • the specific physical properties of Cr_0 3 cause additional changes in the chromium oxide plasma spray layer: Da
  • Chromium oxide is a chemically stable compound only significantly below its melting temperature, it partly breaks down when it melts in the plasma flame, and oxygen is released.
  • Vacuum plasma spraying technology with the transfer of the spraying process to vacuum leads to significant improvements in the coating conditions and layer properties in comparison to plasma spraying in the atmosphere (APS).
  • the jet speed is 2 to 3 times higher in a vacuum.
  • the spray powder particles are correspondingly faster, and denser spray layers with reduced residual porosity are formed.
  • the carrier surface can be freed of gas contamination, water vapor and thin oxide skins before coating. This leads to a significant improvement in the adhesion of the spray layer.
  • Additional heating of the carrier before coating also has an effect in the same direction. This can be carried out without risk of oxidation, since the coating process is practically carried out in the absence of reactive gases. At the same time, during coating. With targeted temperature changes, internal stresses in the spray layer can be reduced or even avoided.
  • Atmosphere of the Ar / H_ plasma flame the risk of oxygen loss is greatly increased, ie an even greater reduction in chromium oxide is to be expected.
  • the object of the invention is to create a Cr 2 O. protective layer of the type described at the outset, which does not have the metallic chromium deposits mentioned, is sprayed as tightly as possible or has a specifically set residual porosity for certain applications, in both Cases, however, because of the extensive chemical purity, has a very high layer hardness.
  • the measured hardness according to the Vickers method should be over 2000 kp / mm 2 (HV), in comparison to the layer hardness of
  • APS protective layers which are usually between 750 and 1200 kp / mm 2 (HV), depending on the amount of the incorporated metallic phases. Furthermore, the Cr_0_ protective layer should also far surpass the APS chromium oxide protective layer in its electrical insulation effect.
  • Dielectric strength measured in volts / layer thickness, can be used as an indirect measure of the quantity of the incorporated metallic phases, and thus also of the corrosion stability.
  • the dielectric strength of an APS-applied Cr_0 3 ⁇ protective layer does not exceed 1 V / ⁇ m layer thickness. At least 5 V / ⁇ m layer thickness is required.
  • the Cr 2 0 3 ⁇ oxide protective layer in a vacuum plasma spraying process with a density corresponding to the density of almost Festissonchrom ⁇ is applied to the carrier, • a residual porosity. well below 2%. has ' and ' Vickers hardness of more than 2000 kp / mm 2 (HV) -.
  • the Cr 2 O protective layer sprayed on with the aid of VPS technology has practically no metallic phases, although the pressure within the plasma flame is greatly reduced compared to atmospheric plasma spraying, but the energy content of the plasma flame is increased , there is no oxygen and is injected with reducing plasma gas.
  • the porosity of the Cr 2 0 3 protective layer is advantageously not more than 2%, the specific density of which is not more than
  • the electrical dielectric strength of the Cr-O ⁇ protective layer is advantageously at least 5 V / ⁇ m layer thickness.
  • the surface of the carrier is expediently lightly sandblasted, sputter-cleaned and degassed by the arc by heating before the Cr 2 0 3 protective layer is applied.
  • a Ti0 2 ⁇ protective layer can also be applied instead of a Cr_0 ⁇ protective layer.
  • a method according to the invention for producing a Cr 2 0 3 ⁇ protective layer is characterized in that the Cr 2 0 3 ⁇ protective layer is applied in a vacuum plasma spraying process at an ambient pressure of approximately 140 mbar and a spraying distance of approximately 240 mm, the plasma flow being approximately 720 A, the flame power is about 57 KW and the spray powder delivery is about 30 g / min, while the throughput of plasma gas is about 30 1 / min Ar and about 10 1 / min H 2 .
  • Protective layer is expediently only lightly sandblasted before it is applied directly.
  • the carrier of the Cr-O-j protective layer is sputter-cleaned immediately prior to its application by the transferred arc and degassed with heating.
  • Fig. 1 shows the layer structure of a Cr ⁇ O ⁇ protective layer sprayed according to the APS method in the cutout and
  • Fig. 2 shows the layer structure of an according to the invention
  • VPS process sprayed Cr 2 0 3 ⁇ protective layer in the cutout
  • a carrier 1 is shown schematically, wel ⁇ cher was roughened in the APS coating method by sandblasting on ⁇ .
  • Protective layer 3 is mechanically zahnt with the support surface 2 ver ⁇ - the surface 2 of the support 1 thus has a certain minimum roughness, whereby the Cr O j.. The measured adhesive forces of the APS-up broke ⁇ th Cr 2 0 protective layer.
  • 3 TERIAL the so .behandelten Crowma ⁇ is about 25 MPa .. '.:
  • Cr 2 0 3 ⁇ protective layers 3 are formed with a porosity of over 10%. This can be seen in the structure of the spray layer from microporosities 4, which are evenly distributed over the Cr 2 0 3 protective layer 3. Also depending on the plasma spraying parameters, there is the number of embedded chrome phases 5, which are depicted as thin threads in the sprayed layer structure. They are responsible for the decrease in layer hardness, which fluctuates between approximately 750 and 1200 kp / mm 2 (HV).
  • the diameter of the impression 6 of the layer hardness measurement (in the example shown a rectangle according to the Vickers method) is a direct measure of the layer hardness.
  • the carrier 1 of The Cr 2 0 3 protective layer is, for example, a film drawing roller made of steel. Its surface 2 was coated directly after very light sandblasting, but sputter cleaning and degassing by heating with the aid of the transferred arc took place immediately before coating. In addition to the mechanical interlocking, the layer adhesion is given by the saturation of free surface energy of the cleaned, oxide-free carrier surface due to the sprayed-on first layer layer.
  • the Cr 2 0 3 protective layer 3 sprayed on according to the invention adheres at approximately 65 MPa to the steel roller surface thus prepared.
  • the Cr produced by this invention Figure 2 shows 0, -.
  • Protective layer 3 virtually no lines of different gray tint which the stored be metallized basic chromium phases 5 and the areas of the S 'Stes auerstoffverlu- in the Cr-0 document 3 protective layer. This is also shown by the impression 6 of the layer hardness measurement, which gives 2150 kp / mm 2 (HV) for this layer structure.
  • the required chemical resistance is also present, which is indicated indirectly by the increased dielectric strength, which is at least 5 V / ⁇ m layer thickness.

Landscapes

  • 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)

Abstract

Le revêtement de protection en Cr2O3 (3) est réalisé, au cours de l'application au pistolet sous vide, comme couche étanche sur un support (1), et possède une densité n'excédant pas 5,3 g/cm3, une porosité résiduelle de moins de 2%, une dureté Vickers (HV) de plus de 2000 kp/mm2 et une résistance électrique d'au moins 5 V/mum d'épaisseur protectrice; il convient particulièrement bien comme couche de protection sur des supports (3) exposés à la corrosion et soumis simultanément à des charges mécaniques élevées.
EP86902821A 1985-04-17 1986-04-17 REVETEMENT DE PROTECTION EN Cr2O3 ET PROCEDE DE FABRICATION Expired EP0220252B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT86902821T ATE47892T1 (de) 1985-04-17 1986-04-17 Cr2o3-schutzschicht und verfahren zu deren herstellung.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19853513892 DE3513892A1 (de) 1985-04-17 1985-04-17 Cr(pfeil abwaerts)2(pfeil abwaerts)o(pfeil abwaerts)3(pfeil abwaerts)-schutzschicht und verfahren zu deren herstellung
DE3513892 1985-04-17

Publications (2)

Publication Number Publication Date
EP0220252A1 true EP0220252A1 (fr) 1987-05-06
EP0220252B1 EP0220252B1 (fr) 1989-11-08

Family

ID=6268386

Family Applications (1)

Application Number Title Priority Date Filing Date
EP86902821A Expired EP0220252B1 (fr) 1985-04-17 1986-04-17 REVETEMENT DE PROTECTION EN Cr2O3 ET PROCEDE DE FABRICATION

Country Status (5)

Country Link
US (1) US4898785A (fr)
EP (1) EP0220252B1 (fr)
JP (1) JPS62502975A (fr)
DE (2) DE3513892A1 (fr)
WO (1) WO1986006103A1 (fr)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3821658A1 (de) * 1988-06-27 1989-12-28 Thyssen Guss Ag Verfahren zur herstellung von korrosionsbestaendigen und verschleissfesten schichten auf walzen von druckmaschinen
GB9601236D0 (en) * 1996-01-22 1996-03-20 Atraverda Ltd Conductive coating
EP1507021A1 (fr) * 2003-08-15 2005-02-16 Deutsche Carbone Ag Procédé de dépôt d'une couche métallique sur une disque ou un bloc de graphite et produits correspondants
CA2658210A1 (fr) * 2008-04-04 2009-10-04 Sulzer Metco Ag Methode et dispositif permettant de revetir et de traiter la surface des substrats au moyen d'un faisceau plasma
US20180025794A1 (en) * 2016-07-22 2018-01-25 Westinghouse Electric Company Llc Spray methods for coating nuclear fuel rods to add corrosion resistant barrier
DE102017218580A1 (de) * 2017-10-18 2019-04-18 Christian Maier GmbH & Co. KG Verfahren zum Aufbringen einer Schicht auf ein Bauteil und Bauteil hergestellt nach dem Verfahren

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2964420A (en) * 1955-06-14 1960-12-13 Union Carbide Corp Refractory coated body
FR2117731B2 (fr) * 1967-10-11 1974-08-23 Anvar
US3640757A (en) * 1968-08-09 1972-02-08 Avco Corp Flame deposited oxide coating and method of making same
US3839618A (en) * 1972-01-03 1974-10-01 Geotel Inc Method and apparatus for effecting high-energy dynamic coating of substrates
FR2245779B1 (fr) * 1973-09-28 1978-02-10 Cit Alcatel
CH589149A5 (en) * 1974-05-10 1977-06-30 Oxy Metal Industries Corp Regenerating sulphite electroplating baths for noble metals - by treating bath with anion exchange resin
DE2630507C3 (de) * 1976-07-07 1983-12-15 MTU Motoren- und Turbinen-Union München GmbH, 8000 München Verfahren zur Herstellung von Schutzschichten auf Werkstücken und Vorrichtung zur Durchführung des Verfahrens
US4313975A (en) * 1980-01-17 1982-02-02 Centre De Recherches Metallurgiques-Centrum Voor Research In De Metallurgie Method of improving operation of continuous casting nozzle
JPS6023037B2 (ja) * 1980-03-18 1985-06-05 旭化成株式会社 情報記録部材
US4396661A (en) * 1981-08-20 1983-08-02 Subtex, Inc. Refractory coated and dielectric coated flame resistant insulating fabric composition
US4577431A (en) * 1984-05-02 1986-03-25 General Electric Company Wear resistant gun barrel and method of forming
DE3422718A1 (de) * 1984-06-19 1986-01-09 Plasmainvent AG, Zug Vakuum-plasma-beschichtungsanlage

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO8606103A1 *

Also Published As

Publication number Publication date
EP0220252B1 (fr) 1989-11-08
JPS62502975A (ja) 1987-11-26
US4898785A (en) 1990-02-06
DE3666844D1 (en) 1989-12-14
DE3513892A1 (de) 1986-10-23
WO1986006103A1 (fr) 1986-10-23

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