EP0672197B1 - Procede de fabrication d'une couche de protection sur des parois metalliques soumises a l'influence de gaz chauds, notamment de gaz brules - Google Patents

Procede de fabrication d'une couche de protection sur des parois metalliques soumises a l'influence de gaz chauds, notamment de gaz brules Download PDF

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Publication number
EP0672197B1
EP0672197B1 EP93912953A EP93912953A EP0672197B1 EP 0672197 B1 EP0672197 B1 EP 0672197B1 EP 93912953 A EP93912953 A EP 93912953A EP 93912953 A EP93912953 A EP 93912953A EP 0672197 B1 EP0672197 B1 EP 0672197B1
Authority
EP
European Patent Office
Prior art keywords
powder
protective coating
walls
process according
plasma jet
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
EP93912953A
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German (de)
English (en)
Other versions
EP0672197A1 (fr
Inventor
Bodo Häuser
Wilhelm Heesen
Johannes Hermsen
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.)
HAEUSER & CO. GMBH
Original Assignee
Hauser & Co GmbH
Thyssen Stahl 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 Hauser & Co GmbH, Thyssen Stahl AG filed Critical Hauser & Co GmbH
Publication of EP0672197A1 publication Critical patent/EP0672197A1/fr
Application granted granted Critical
Publication of EP0672197B1 publication Critical patent/EP0672197B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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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
    • C23C4/12—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the method of spraying
    • 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
    • C23C4/134—Plasma spraying
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05B—SPRAYING APPARATUS; ATOMISING APPARATUS; NOZZLES
    • B05B7/00—Spraying apparatus for discharge of liquids or other fluent materials from two or more sources, e.g. of liquid and air, of powder and gas
    • B05B7/16—Spraying apparatus for discharge of liquids or other fluent materials from two or more sources, e.g. of liquid and air, of powder and gas incorporating means for heating or cooling the material to be sprayed
    • B05B7/22—Spraying apparatus for discharge of liquids or other fluent materials from two or more sources, e.g. of liquid and air, of powder and gas incorporating means for heating or cooling the material to be sprayed electrically, magnetically or electromagnetically, e.g. by arc
    • 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
    • C23C4/02—Pretreatment of the material to be coated, e.g. for coating on selected surface areas
    • 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

Definitions

  • the invention relates to a method for producing a protective layer on hot gases, especially flue gases Walls made of metallic base material, preferably from Incinerators or heat exchangers, in which with the help of a Plasma spraying on the previously cleaned, metallic walls to form the protective layer, a powder made of metallic, carbide, oxide ceramic or silicide materials or mixtures of these Materials is applied.
  • Such protective layers should e.g. on cooling walls of waste heat boilers applied to steel converters. These walls are special exposed to high loads. On one side flow approx. 1400 ° - 1800 ° C hot smoke gases loaded with ash and slag particles along, while on the other side saturated steam pressures of approx. 20 - 80 bar rule.
  • the saturated steam-cooled pipe walls are included Internal pressure gradients of up to 2 bar / min.
  • DE 23 55 532 C2 describes a method for powder deposition welding of metals and alloys on a surface prepared by sandblasting, preheated metal pad known, where the metal pad previously is heated to at least 100 to about 650 ° C.
  • Both at Cladding by means of a stick electrode as well as at Powder build-up welding or flame spraying with subsequent melting becomes the base material when the protective layer is applied very strongly heated, which leads to an undesirable structural change.
  • flame spraying in particular, the melting temperature is in Depending on the spray powder used between 980 and 1060 ° C. Due to the high heat input, there is also Warping of the walls to be coated. When installing these walls can then there are problems and additional costs due to the dimensionality come.
  • the protective layer has a thickness of about 8 to 10 mm and with flame spraying from 1 to 2 mm.
  • DE-AS 26 30 507 is also a process for the production of Protective layers on workpieces against hot gas corrosion and / or known mechanical wear, in which by means of plasma spraying Vacuum a made of different alloys Coating powder is applied to the workpiece. With this Vacuum spraying must be done with considerable effort from the outside inaccessible processing chamber creates a vacuum and the Coating can be carried out. With larger, e.g. B. in the waste heat boiler built-in walls this is not possible.
  • the present invention is based on the object propose generic method in which these problems not occur and in particular the distortion of the workpieces and cracking stresses in the base material can be avoided.
  • the composition of the powder is determined as a function of the existing base material and the later operating conditions, in particular the specified temperature ranges.
  • tensile stresses of between 50 and 800 N / mm 2 , preferably between 500 and 800 N / mm 2
  • These stress states are calculated by means of the thermal expansion coefficients of the base material on the one hand and of test workpieces made of different powders on the other hand. The mathematical determination can then be checked in accordance with DIN 50121.
  • heat exchangers especially of waste heat boilers on steel converters
  • Protective layer that is insensitive to thermal shock and easy to repair against hot gas corrosion and / or mechanical wear become.
  • a final layer thickness of 0.1 to 0.5 mm, preferably 0.15 to 0.25 mm is already sufficient to also have a a significantly longer period than previously possible To prevent wear.
  • a protective layer mainly has an 80 KW plasma spray system Inner powder feed proved to be particularly suitable. It will be there Powder with a grain size of less than 75 microns, preferably 20 to 40 ⁇ m used. This powder can be used to make a very thin powder Layer to be applied, which is the condition of insensitivity to thermal shock and meets the resistance to hot gas corrosion, and high residual stress due to the process-related laminar Layer structure, avoids. The entire layer is conveniently in made at least two transitions.
  • the surface of the walls to be treated can be sprayed before plasma spraying with high-grade corundum, preferably with high-purity white high-grade corundum roughened and activated.
  • the inventive Traverse the surface through the plasma jet and the surface inside melted powder particles only to approx. 40 ° C maximum 60 ° C is heated. This can result in warping of the wall surfaces be excluded.
  • a powder containing a Ni alloy is expediently used.
  • the exposure temperature can be covered with a protective layer treated walls in the range between 300 and 1800 ° C, preferably 600 and 1000 ° C.
  • the voltage behavior in the transition zone of the base material and the applied protective layer in the temperature range between 0 and approximately 1200 ° C. is shown as an example in a voltage-temperature diagram.
  • the basis is the measured, average linear thermal expansion coefficient of the two material partners.
  • tensile stresses above 600 N / mm 2 are present in the transition zone between the base material and the coating material.
  • the Spray layer suddenly due to high temperatures from the converter highly sprayed molten steel and the hot slag.
  • the process is due to the voltage curve represented by the neutral voltage range at approx. 700 ° C is passed and is above 700 ° C in the transition zone Build up compressive stresses that cause the layer to flake off or Prevent cracking in the layer.
  • the usual water-cooled pipes of the waste heat boiler walls are built according to the Stress slowly returns to the tensile state, i.e. in the diagram shows the line of the voltage curve in Drive in the opposite direction.
  • the So-called 0 state instead of 700 ° C also at 400 ° or at 800 ° C lie.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Plasma & Fusion (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Electromagnetism (AREA)
  • Coating By Spraying Or Casting (AREA)
  • Laminated Bodies (AREA)
  • Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Chemical Vapour Deposition (AREA)

Claims (8)

  1. Procédé de fabrication d'une couche de protection sur des parois métalliques, de préférence d'installations de combustion ou d'échangeurs de chaleur, soumises à l'influence de gaz chauds, notamment de gaz brûlés, une poudre de matériaux à base de métal, de carbure, de céramique oxydée ou de silicium ou de mélanges de ces métaux étant appliquée par un procédé de projection au plasma de protection sur les parois métalliques nettoyées auparavant pour former une couche
    caractérisé en ce
    a) que la surface des parois est quadrillée et activée au moyen d'un corindon affiné de grande pureté et
    b) qu'immédiatement après, la poudre est appliquée à température ambiante et dans des conditions atmosphériques selon le procédé de projection au plasma,
    c) la composition de la poudre étant choisie au préalable de manière telle que la tension pour la zone de transition entre le matériau de base et la couche appliquée déterminée au moyen des coefficients de dilatation thermique du matériau de base et de pièces d'oeuvre d'essai fabriquées à partir de différentes poudres en tant que fonction de la température à l'état non sollicité (à température ambiante) donne des efforts de traction situés entre 50 et 800 n/mm2, de préférence entre 500 et 800 N/mm2, ladite tension étant pour l'essentiel annulée dans la plage de température sollicitée prévue entre 300 et 1800 °C, de préférence entre 600 et 1000°C, ou ne présentant que de faibles tensions de compression.
  2. Procédé selon la revendication 1 caractérisé en ce que la couche de protection appliquée a une épaisseur finale de 0,1 à 0,5 mm, de préférence de 0,15 à 0,25 mm.
  3. Procédé selon la revendication 1 ou 2 caractérisé en ce que la couche de protection est appliquée au moyen d'un dispositif de projection au plasma 80 KW avec amenée intérieure de la poudre.
  4. Procédé selon au moins l'une des revendications 1 à 3 caractérisé en ce que la poudre utilisée pour l'application de la couche de protection présente une granulométrie inférieure à 75µm, de préférence de 20 à 40 µm.
  5. Procédé selon au moins l'une des revendications 1 à 4 caractérisé en ce que la couche de protection est réalisée en au moins deux phases.
  6. Procédé selon au moins l'une des revendications précédentes caractérisé en ce que la surface des parois n'est échauffée qu'à env. 45 °C, maximum 60 °C, par le jet de plasma et les particules de poudre fondues dans ledit jet.
  7. Procédé selon au moins l'une des revendications précédentes caractérisé en ce qu'une poudre contenant un alliage Ni est utilisée.
  8. Procédé selon la revendication 1 caractérisé en ce que le revêtement atmosphérique au plasma est réalisé 45 minutes au plus tard, de préférence 30 minutes au plus tard, après l'activation de la surface des parois.
EP93912953A 1992-06-19 1993-06-11 Procede de fabrication d'une couche de protection sur des parois metalliques soumises a l'influence de gaz chauds, notamment de gaz brules Expired - Lifetime EP0672197B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE4220063 1992-06-19
DE4220063A DE4220063C1 (de) 1992-06-19 1992-06-19 Verfahren zur Herstellung einer Schutzschicht auf mit heißen Gasen, insbesondere Rauchgasen beaufschlagten metallischen Wänden
PCT/EP1993/001483 WO1994000616A1 (fr) 1992-06-19 1993-06-11 Procede de fabrication d'une couche de protection sur des parois metalliques soumises a l'influence de gaz chauds, notamment de gaz brules

Publications (2)

Publication Number Publication Date
EP0672197A1 EP0672197A1 (fr) 1995-09-20
EP0672197B1 true EP0672197B1 (fr) 1999-03-31

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ID=6461363

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EP93912953A Expired - Lifetime EP0672197B1 (fr) 1992-06-19 1993-06-11 Procede de fabrication d'une couche de protection sur des parois metalliques soumises a l'influence de gaz chauds, notamment de gaz brules

Country Status (14)

Country Link
EP (1) EP0672197B1 (fr)
JP (1) JP3150697B2 (fr)
KR (1) KR950701983A (fr)
AT (1) ATE178364T1 (fr)
AU (1) AU672009B2 (fr)
BR (1) BR9306566A (fr)
CA (1) CA2138255A1 (fr)
CZ (1) CZ313794A3 (fr)
DE (2) DE4220063C1 (fr)
ES (1) ES2132237T3 (fr)
PL (1) PL171965B1 (fr)
RU (1) RU2107744C1 (fr)
SK (1) SK156394A3 (fr)
WO (1) WO1994000616A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AT411625B (de) * 2000-04-28 2004-03-25 Vaillant Gmbh Verfahren zur beschichtung eines wärmetauschers

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0727504A3 (fr) * 1995-02-14 1996-10-23 Gen Electric Procédé de revêtement pour plasma pour améliorer la liaison de revêtements sur des substrats
CZ298780B6 (cs) * 2003-12-23 2008-01-23 Koexpro Ostrava, A. S. Ochranný povlak nářadí a nástrojů pro zamezení vzniku mechanických zápalných jisker
DE102007020420B4 (de) 2007-04-27 2011-02-24 Häuser & Co. GmbH Plasmaspritzverfahren zur Beschichtung von Überhitzerrohren und Verwendung eines Metalllegierungspulvers
DE102013010126B4 (de) 2013-06-18 2015-12-31 Häuser & Co. GmbH Plasmapulverspritzverfahren und Vorrichtung zur Beschichtung von Paneelen für Kesselwände in Verbindung mit einem Laserstrahlgerät
CN108101062A (zh) * 2018-01-17 2018-06-01 江苏中能硅业科技发展有限公司 一种多晶硅还原炉及其炉筒内壁功能层的制备工艺
JP7370793B2 (ja) 2019-09-30 2023-10-30 セコム株式会社 警備装置
JP7370794B2 (ja) 2019-09-30 2023-10-30 セコム株式会社 警備装置

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2630507A1 (de) * 1976-07-07 1978-01-12 Motoren Turbinen Union Verfahren zur herstellung von schutzschichten auf werkstuecken

Family Cites Families (8)

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Publication number Priority date Publication date Assignee Title
FR2213350B1 (fr) * 1972-11-08 1975-04-11 Sfec
US3911891A (en) * 1973-08-13 1975-10-14 Robert D Dowell Coating for metal surfaces and method for application
US4075392A (en) * 1976-09-30 1978-02-21 Eutectic Corporation Alloy-coated ferrous metal substrate
US4588607A (en) * 1984-11-28 1986-05-13 United Technologies Corporation Method of applying continuously graded metallic-ceramic layer on metallic substrates
JP2695835B2 (ja) * 1988-05-06 1998-01-14 株式会社日立製作所 セラミック被覆耐熱部材
DE3815436A1 (de) * 1988-05-06 1989-11-16 Muiden Chemie B V Treibladungen fuer grosskalibrige geschosse
DE3821658A1 (de) * 1988-06-27 1989-12-28 Thyssen Guss Ag Verfahren zur herstellung von korrosionsbestaendigen und verschleissfesten schichten auf walzen von druckmaschinen
CA2053928A1 (fr) * 1990-10-24 1992-04-25 Toshihiko Hashimoto Derives du benzopyrane, antihypertenseurs et vasodilatateurs; preparation et utilisation therapeutique

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2630507A1 (de) * 1976-07-07 1978-01-12 Motoren Turbinen Union Verfahren zur herstellung von schutzschichten auf werkstuecken

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AT411625B (de) * 2000-04-28 2004-03-25 Vaillant Gmbh Verfahren zur beschichtung eines wärmetauschers

Also Published As

Publication number Publication date
EP0672197A1 (fr) 1995-09-20
ATE178364T1 (de) 1999-04-15
CZ313794A3 (en) 1995-08-16
RU94046201A (ru) 1996-10-20
JP3150697B2 (ja) 2001-03-26
DE4220063C1 (de) 1993-11-18
WO1994000616A1 (fr) 1994-01-06
AU4325093A (en) 1994-01-24
RU2107744C1 (ru) 1998-03-27
ES2132237T3 (es) 1999-08-16
KR950701983A (ko) 1995-05-17
DE59309491D1 (de) 1999-05-06
PL171965B1 (pl) 1997-07-31
AU672009B2 (en) 1996-09-19
SK156394A3 (en) 1997-02-05
BR9306566A (pt) 1999-01-12
CA2138255A1 (fr) 1994-01-06
JPH08501350A (ja) 1996-02-13

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