EP2636763A1 - Procédé pour appliquer une couche de revêtement stable à haute température sur la surface d'un composant et composant avec une telle couche de revêtement - Google Patents

Procédé pour appliquer une couche de revêtement stable à haute température sur la surface d'un composant et composant avec une telle couche de revêtement Download PDF

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Publication number
EP2636763A1
EP2636763A1 EP12158129.2A EP12158129A EP2636763A1 EP 2636763 A1 EP2636763 A1 EP 2636763A1 EP 12158129 A EP12158129 A EP 12158129A EP 2636763 A1 EP2636763 A1 EP 2636763A1
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EP
European Patent Office
Prior art keywords
coating layer
micron
component
powder
sub
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
EP12158129.2A
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German (de)
English (en)
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EP2636763B1 (fr
Inventor
Sophie Duval
Piero-Daniele Grasso
Sven Olliges
Alexander Stankowski
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.)
Ansaldo Energia Switzerland AG
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Alstom Technology AG
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Filing date
Publication date
Application filed by Alstom Technology AG filed Critical Alstom Technology AG
Priority to EP12158129.2A priority Critical patent/EP2636763B1/fr
Priority to PCT/EP2013/054337 priority patent/WO2013131874A1/fr
Priority to CA2864618A priority patent/CA2864618A1/fr
Priority to CN201380012678.5A priority patent/CN104160059B/zh
Publication of EP2636763A1 publication Critical patent/EP2636763A1/fr
Priority to US14/474,564 priority patent/US20150284834A1/en
Application granted granted Critical
Publication of EP2636763B1 publication Critical patent/EP2636763B1/fr
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    • 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
    • C23C4/12Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the method of spraying
    • 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
    • C23C4/02Pretreatment of the material to be coated, e.g. for coating on selected surface areas
    • 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
    • C23C4/073Metallic material containing MCrAl or MCrAlY alloys, where M is nickel, cobalt or iron, with or without non-metal elements
    • 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
    • C23C4/08Metallic material containing only metal elements
    • 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
    • C23C4/10Oxides, borides, carbides, nitrides or silicides; Mixtures thereof
    • 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
    • C23C4/10Oxides, borides, carbides, nitrides or silicides; Mixtures thereof
    • C23C4/11Oxides
    • 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
    • C23C4/12Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the method of spraying
    • C23C4/134Plasma spraying
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/25Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
    • Y10T428/256Heavy metal or aluminum or compound thereof

Definitions

  • the present invention relates to thermally loaded components of thermal machines, especially gas turbines. It refers to a method for applying a high-temperature stable coating layer on the surface of a component. It further refers to a component with such a coating layer.
  • a thermal barrier coating TBC
  • a bond coat may be provided between the base material of the component and the TBC.
  • the hot-section stationary components mainly combustors, transition pieces, and vanes
  • TBCs thermal barrier coatings
  • M metallic MCrAIY
  • YPSZ Yttria partially stabilized zirconia
  • the document further asserts that the full potential of the YPSZ TBCs is yet to be realized due mainly to the cracking problem that occurs along or near the bond coat/top coat interface after a limited number of cycles of engine operation.
  • This interfacial cracking often leading to premature coating failure by debonding (spallation) of the top coat from the bond coat, has been amply demonstrated from microstructural evidence that was obtained from in-service degradation of deposited coatings as well as from laboratory experiments that have been conducted.
  • the thin oxide layer that grows on top of the bond coat, at the bond coat/top coat interface plays a critical role in the interface cracking. It is quite evident that this cracking problem negatively impacts the coating performance by reducing both the engine efficiency (because the engine operating temperature is kept below its optimum temperature) and the lifetime of the engine components. In turn, this greatly affects the reliability and the efficiency of the entire engine system.
  • the bond coat surface, onto which the YPSZ top coat is disposed has a thin oxide layer that consists mostly of various oxides (NiO, Ni(Cr,Al) 2 O 4 , Cr 2 O 3 , Y 2 O 3 , Al 2 O 3 ).
  • This thin oxide layer plays an important role in the adhesion (bonding) between the metallic bond coat and the ceramic top coat.
  • another oxide layer forms in addition to the native oxide.
  • This second layer also mostly alumina, is commonly referred to as the thermally grown oxide (TGO) and slowly grows during exposure to elevated temperatures.
  • TGO thermally grown oxide
  • Interfacial oxides, in particular the TGO layer play a pivotal role in the cracking process. It is believed that the growth of the TGO layer leads to the build up of stresses at the interface region between the TGO layer and top coat.
  • document US 7,361,386 B2 proposes to modify the microstructure of the MCrAIY bond coat (in a thermal barrier coating) in a controlled way prior to exposure to high temperatures, in order to control the subsequent changes during high temperature exposure. More specifically, the structure, composition, and growth rate of the thermally grown oxide (TGO) is controlled to ultimately improve the performance of TBCs.
  • a nanostructure is provided in the bond coat and, consequently, nanocrystalline dispersoids are introduced into the structure. The purpose of the dispersoids is to stabilize the nanocrystalline structure and to nucleate the desirable [alpha]-Al 2 O 3 in the TGO.
  • the method according to the invention for applying a high-temperature stable coating layer on the surface of a component comprises the steps of:
  • said powder material is applied to the surface of the component by means of a thermal spraying technique.
  • the thermal spraying technique used is one of High Velocity Oxygen Fuel Spraying (HVOF), Low Pressure Plasma Spraying (LPPS), Air Plasma Spraying (APS) or Suspension Plasma Spraying (SPS).
  • HVOF High Velocity Oxygen Fuel Spraying
  • LPPS Low Pressure Plasma Spraying
  • APS Air Plasma Spraying
  • SPS Suspension Plasma Spraying
  • said powder material has the form of agglomerates.
  • said powder material has the form of a suspension.
  • the powder material contains powder particles of micron size and/or larger agglomerates, and that the sub-micron powder particles are in said coating layer distributed around the surface of said powder particles of micron size and/or said larger agglomerates.
  • the sub-micron powder particles are pre-oxidized before being incorporated into said coating layer.
  • the pre-oxidation takes place in-flight during spraying.
  • the pre-oxidation is done by an oxidative pre heat treatment of the powder material.
  • the powder material is a metallic powder.
  • the coating layer is a bond coat or an overlay coating.
  • said component having a surface, which is coated with a coating layer is characterized in that said coating layer comprises sub-micron powder particles, which are each at least partially surrounded by an oxide shell and establish with their oxide shells an at least partially interconnected sub-micron oxide network within said coating layer.
  • said coating layer further comprises powder particles of micron size and/or larger agglomerates.
  • said sub-micron powder particles are in said coating layer distributed around the surface of said powder particles of micron size and/or said larger agglomerates.
  • the present invention discloses a specific type of sub-micron structured coating. Due to a sub-micron scale oxide network and fine grain microstructure, the invention aims to reduce the LCF/TMF cracking.
  • Another aspect of the invention is the retardant effect for the oxidation and the corrosion. Due to the nano-scale oxide network of the bond coat/overlay coating, the impact by oxidation and corrosion is slowed down.
  • the invention should enable a longer service life and/or assure reconditionability with less scrap parts and/or decreased operation risks, such as crack formation in critical area of the component due to mechanical/thermal load, and/or oxidation/corrosion and/or FOD (Foreign Objects Damage) events.
  • the invention enables:
  • the novelty of the invention is the use of a sub-micron powder (at least to a certain percentage of the total powder mixture) and the way to process it (preparation and thermal spray application) to reach the mentioned improved coating properties.
  • the improved coating behavior is particularly based on a reduced TMF/LCF effect of the coating with (at least partial) sub-micron structure.
  • the invention is based on:
  • In-flight oxidation during spraying has the effect of pre-oxidizing the sub-micron powder of the agglomerate or suspension. Pre-oxidation can also be achieved by oxidative pre heat treatment of the powder mixture. When only a portion of the powder exhibits a sub-micron scale, it is preferable to have the sub-micron particles distributed around the surface of the micron and/or agglomerated spray powder particles.
  • Fig. 1 shows a typical thermal spray configuration 10, which can be used to apply the sub-micron powder coating layer according to the invention.
  • the thermal spray configuration 10 comprises a spray gun 13, which is supplied with the sub-micron powder 15, a fuel 16 and an oxidant 17. By burning the fuel 16, a flame 14 is generated, which transports the powder particles to the surface of a component 11, thereby building the coating layer 12.
  • the sub-micron powder particles 18 undergo a reaction, as can be seen in Fig. 2 , such that they are transformed into particles having a (metallic) core 19 surrounded by an oxide shell 20.
  • those oxidized sub-micron particles build up an interconnected structure with a sub-micron oxide network 22.
  • the resulting coating layer 12a comprises those agglomerates or micron powder particles 21 being surrounded by oxidized sub-micron powder particles 18.
  • the initiation and propagation of damages within coatings exhibiting an at least partial sub-micron scale structure is retarded compared to conventional coating microstructures.
  • the "sub-micron effect" is retained over extended lifetime periods, also due to the (at least partial) oxide network.
  • Such aspects of the invention give to the coating a so-called self healing characteristic.
  • the fine grain sized coating allows a diffusion heat treatment with a reduced number of heat treatment cycles.
  • a nano coating as top layer improves the TMF and oxidation resistance, which results in an improved overall coating lifetime.

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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)
  • Other Surface Treatments For Metallic Materials (AREA)
EP12158129.2A 2012-03-05 2012-03-05 Procédé pour appliquer une couche de revêtement stable à haute température sur la surface d'un composant et composant avec une telle couche de revêtement Active EP2636763B1 (fr)

Priority Applications (5)

Application Number Priority Date Filing Date Title
EP12158129.2A EP2636763B1 (fr) 2012-03-05 2012-03-05 Procédé pour appliquer une couche de revêtement stable à haute température sur la surface d'un composant et composant avec une telle couche de revêtement
PCT/EP2013/054337 WO2013131874A1 (fr) 2012-03-05 2013-03-05 Procédé pour l'application d'une couche de revêtement stable à haute température sur la surface d'un composant et composant pourvu d'une telle couche de revêtement
CA2864618A CA2864618A1 (fr) 2012-03-05 2013-03-05 Procede pour l'application d'une couche de revetement stable a haute temperature sur la surface d'un composant et composant pourvu d'une telle couche de revetement
CN201380012678.5A CN104160059B (zh) 2012-03-05 2013-03-05 在组件的表面上涂敷高温稳定涂层的方法和具有这种涂层的组件
US14/474,564 US20150284834A1 (en) 2012-03-05 2014-09-02 Method for applying a high-temperature stable coating layer on the surface of a component and component with such a coating layer

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP12158129.2A EP2636763B1 (fr) 2012-03-05 2012-03-05 Procédé pour appliquer une couche de revêtement stable à haute température sur la surface d'un composant et composant avec une telle couche de revêtement

Publications (2)

Publication Number Publication Date
EP2636763A1 true EP2636763A1 (fr) 2013-09-11
EP2636763B1 EP2636763B1 (fr) 2020-09-02

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EP12158129.2A Active EP2636763B1 (fr) 2012-03-05 2012-03-05 Procédé pour appliquer une couche de revêtement stable à haute température sur la surface d'un composant et composant avec une telle couche de revêtement

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US (1) US20150284834A1 (fr)
EP (1) EP2636763B1 (fr)
CN (1) CN104160059B (fr)
CA (1) CA2864618A1 (fr)
WO (1) WO2013131874A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104451520A (zh) * 2014-12-04 2015-03-25 中国船舶重工集团公司第十二研究所 一种氧化锆多晶团陶瓷涂层的制备方法

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3168204B1 (fr) * 2015-11-12 2019-02-27 Ansaldo Energia IP UK Limited Procédé de fabrication d'une pièce de turbine à gaz
US10752999B2 (en) 2016-04-18 2020-08-25 Rolls-Royce Corporation High strength aerospace components
US10763715B2 (en) 2017-12-27 2020-09-01 Rolls Royce North American Technologies, Inc. Nano-crystalline coating for magnet retention in a rotor assembly
CN108004498A (zh) * 2017-12-29 2018-05-08 上海英佛曼纳米科技股份有限公司 一种具有抗高温结瘤抗氧化耐腐蚀耐磨损涂层的高温热轧钢炉辊
US11317540B2 (en) 2019-09-20 2022-04-26 Samsung Electronics Co., Ltd. Solid state drive apparatus and data storage apparatus including the same
CN113881912B (zh) * 2021-10-09 2023-01-31 矿冶科技集团有限公司 一种纳米氧化物弥散型MCrAlY抗氧化涂层及其制备方法

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EP0368082A2 (fr) * 1988-11-08 1990-05-16 H.C. Starck GmbH & Co. KG Poudre métallique de molybdène et son procédé de préparation
US20060165910A1 (en) * 2005-01-21 2006-07-27 Cabot Corporation Processes for forming nanoparticles
GB2426010A (en) * 2005-05-14 2006-11-15 Jeffrey Boardman Production of oxide coated metallic particles for use in semiconductor devices.
US20080090071A1 (en) * 2004-10-21 2008-04-17 Commissariat A L'energie Atomique Nanosturctured Coating and Coating Method
US7361386B2 (en) 2002-07-22 2008-04-22 The Regents Of The University Of California Functional coatings for the reduction of oxygen permeation and stress and method of forming the same
US20100032619A1 (en) * 2006-09-14 2010-02-11 Rene Jabado Method for producing a particle-containing functional layer and functional element comprising such a layer
US20100080921A1 (en) * 2008-09-30 2010-04-01 Beardsley M Brad Thermal spray coatings for reduced hexavalent and leachable chromuim byproducts

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US7361386B2 (en) 2002-07-22 2008-04-22 The Regents Of The University Of California Functional coatings for the reduction of oxygen permeation and stress and method of forming the same
US20080090071A1 (en) * 2004-10-21 2008-04-17 Commissariat A L'energie Atomique Nanosturctured Coating and Coating Method
US20060165910A1 (en) * 2005-01-21 2006-07-27 Cabot Corporation Processes for forming nanoparticles
GB2426010A (en) * 2005-05-14 2006-11-15 Jeffrey Boardman Production of oxide coated metallic particles for use in semiconductor devices.
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US20100080921A1 (en) * 2008-09-30 2010-04-01 Beardsley M Brad Thermal spray coatings for reduced hexavalent and leachable chromuim byproducts

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Cited By (2)

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Publication number Priority date Publication date Assignee Title
CN104451520A (zh) * 2014-12-04 2015-03-25 中国船舶重工集团公司第十二研究所 一种氧化锆多晶团陶瓷涂层的制备方法
CN104451520B (zh) * 2014-12-04 2017-08-01 中国船舶重工集团公司第十二研究所 一种氧化锆多晶团陶瓷涂层的制备方法

Also Published As

Publication number Publication date
CN104160059A (zh) 2014-11-19
EP2636763B1 (fr) 2020-09-02
CA2864618A1 (fr) 2013-09-12
CN104160059B (zh) 2019-01-08
WO2013131874A1 (fr) 2013-09-12
US20150284834A1 (en) 2015-10-08

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