EP1236813B1 - Eléments revêtus de couches d'oxydes composites imperméables à l'hydrogène et procédé de fabrication de ces éléments - Google Patents

Eléments revêtus de couches d'oxydes composites imperméables à l'hydrogène et procédé de fabrication de ces éléments Download PDF

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Publication number
EP1236813B1
EP1236813B1 EP20020090080 EP02090080A EP1236813B1 EP 1236813 B1 EP1236813 B1 EP 1236813B1 EP 20020090080 EP20020090080 EP 20020090080 EP 02090080 A EP02090080 A EP 02090080A EP 1236813 B1 EP1236813 B1 EP 1236813B1
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EP
European Patent Office
Prior art keywords
coating
chemical
chemical densified
composite
amorphous inorganic
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 - Fee Related
Application number
EP20020090080
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German (de)
English (en)
Other versions
EP1236813A2 (fr
EP1236813A3 (fr
Inventor
Hiroshi c/o Japan Atomic Energy Rch Ins Kawamura
Masaru c/o Japan Atomic Energy Rch Ins Nakamichi
Kazumi c/o Tocalo Co. Ltd. Tani
Kiyoshi c/o Tocalo Co. Ltd. Miyajima
Takema c/o Tocalo Co. Ltd. Teratani
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Japan Atomic Energy Agency
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Japan Atomic Energy Agency
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Publication date
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Publication of EP1236813A3 publication Critical patent/EP1236813A3/fr
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Publication of EP1236813B1 publication Critical patent/EP1236813B1/fr
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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
    • C23C30/00—Coating with metallic material characterised only by the composition of the metallic material, i.e. not characterised by the coating process
    • 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
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/1204—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
    • C23C18/1208—Oxides, e.g. ceramics
    • C23C18/1216—Metal 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
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/1229—Composition of the substrate
    • C23C18/1241—Metallic substrates
    • 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
    • C23C26/00—Coating not provided for in groups C23C2/00 - C23C24/00

Definitions

  • This invention relates to members coated with composite oxide coatings having high ability to prevent the permation of hydrogen isotopes and a process for producing such members.
  • Continuous coatings of a SiO 2 -Cr 2 O 3 system that are chemically densified by chromium oxide have very high hardness, so they have been and are still used as wear-resistant coatings on various mechanical structural members.
  • US-A-5 820 976 discloses a thin insulative ceramic coating for a substrate comprising an insulative coating comprised of refractory oxide bubbles with a melting point above that of glass bubbles, a refractory oxide and a solution of a binder capable of being converted to an oxide upon being heated, thereby effecting a bond between refractory oxide and the substrate, the coating provides increased thermal barrier characteristics.
  • An object, therefore, of the invention is to establish a technology that can eliminate the aforementioned defect of the prior art SiO 2 -Cr 2 O 3 chemical densified coatings by transforming them to composite oxide coatings having high ability to prevent the permeation of hydrogen isotopes.
  • the present inventors treated the tiny pores and cracks in the coatings by one of the following methods.
  • a SiO 2 -Cr 2 O 3 chemical densified coating that covers the surface of a stainless steel substrate is formed by the process flow shown in Fig. 1 .
  • the chemical densified coating formed by this process is very hard and highly wear-resistant; on the other hand, the coating contains tiny pores and cracks, some of which are deep enough to reach the substrate.
  • the surface of the chemical densified coating is directly coated or sprayed with a mixture of chromic acid in aqueous solution and an aqueous solution containing a material capable of forming an amorphous inorganic substance upon sintering, or alternatively, the chemical densified coating is dipped in the mixture of such aqueous solutions; the coating is then heated and sintered so that the amorphous inorganic substance gets into the pores and cracks in the coating to fill them up.
  • the aqueous solution containing a material capable of forming the amorphous inorganic substance upon sintering is one that contains a borate compound or a silicate compound.
  • the temperature of heating the chemical densified coating depends on what mixture of aqueous solutions it is treated with. If it is treated by coating with a mixture of chromic acid in aqueous solution and an aqueous solution containing chromic acid and a borate compound, the chemical densified coating is heated at 550 - 720°C for 0.5 - 2 hours. If the treatment is by coating with a mixture of chromic acid in aqueous solution and an aqueous solution of a phosphate compound, the heating temperature is at 250 - 750°C. In either case, the water in the aqueous solutions evaporates whereas the fine particles of chromium oxide which remain as heating residue not only fill up the pores and cracks in the chemical densified coating but they are also deposited on the surface of the coating.
  • chromic acid turns into Cr 2 O 3 (chromium oxide) via an intermediate and the concomitant aqueous solution of a borate compound, a silicate compound or a phosphate compound releases water to become an amorphous inorganic substance.
  • the Cr 2 O 3 precipitated from this aqueous solution comprises very small particles that are hard and have high resistance to wear and corrosion.
  • Each of the phosphate, borate and silicate compounds is amorphous and partly glassy; they are precipitated in the pores and cracks in the chemical densified coating to seal them up. They are also effective in enhancing the adhesion between the constituent particles in the coating.
  • the pathways for the encroaching hydrogen isotopes are effectively blocked by the precipitation of fine Cr 2 O 3 particles and enhancement of the strength of their binding by the amorphous inorganic substance resulting from the borate, silicate or phosphate compound.
  • the chemical densified coating is coated or sprayed with a processing fluid based on chromic acid and an aqueous solution of the borate, silicate or phosphate compound or, alternatively, the coating is dipped in the processing fluid and the thus treated coating is then heated. If this process is repeated several times, the pores and cracks in the coating are not only filled with Cr 2 O 3 and the amorphous inorganic substance, it is also covered with a layer of excess composite of chromium oxide and the amorphous inorganic compound.
  • the coating effectively maintains the ability to prevent permeation of hydrogen isotopes.
  • Table 1 shows the conditions for applying the composite oxide coating capable of preventing the permeation of hydrogen isotopes. Table 1.
  • Composite oxide coating for preventing the permeation of hydrogen isotopes Major ingredients Sinter Slurry slurry of SiO 2 particles plus CrO 3 in aqueous solution yes Impregnant CrO 3 in aqueous solution CrO 3 in aqueous solution plus aqueous solution of borate or silicate compound yes
  • Fig. 2 is a partial section of a member coated with a composite oxide coating to prevent the permeation of hydrogen isotopes in accordance with the invention.
  • the numeral 1 designates a stainless steel substrate
  • 2 is a chemical densified coating
  • 3 is a pore (or crack) that is open through the chemical densified coating
  • 4 refers to fine particles of chromium oxide and amorphous inorganic substance in composite form that fill up the pore or crack
  • 5 is a layer of such fine particles of chromium oxide and amorphous inorganic substance in composite form that covers the surface of the coating 2.
  • the fine particles which comprise the layer 5 of chromium oxide and amorphous inorganic substance in composite form completely fill up the pores and cracks in the chemical densified coating 2, so the layer 5 exhibits very strong adhesion.
  • Example 1 a chemical densified coating was applied to the surface of an SS 400 steel substrate; the pores and cracks in the coating were filled and covered with a layer of the fine particles of chromium oxide and amorphous inorganic substance in composite form to produce a composite oxide coating capable of preventing the permeation of hydrogen isotopes.
  • the corrosion resistance of the resulting coating coated member was evaluated by the CASS test according to JIS H8502.
  • the composite oxide coating capable of preventing the permeation of hydrogen isotopes which was produced by the treatment of the invention was evaluated for permeability of deuterium.
  • Invention composite oxide coating capable of preventing the permeation of hydrogen isotopes The inner surface of a substrate (SS 316L steel) in tubular form (30.0 mm in outside diameter by 0.9 mm in thickness) was coated with a chemical densified coating, dipped in an aqueous solution based on CrO 3 and phosphoric acid, recovered and heated at 450°C for 1 hour. This process was conducted six times to prepare a test tube having a composite oxide coating formed in a thickness of 50 ⁇ m on the inner surface.
  • the test apparatus comprised the sample tube 1, a measuring Hastelloy X tube 2 (50.0 mm in inside diameter by 3.0 mm in thickness), a mass spectrometer 3 for measuring the permeation of deuterium through the test tube wall, a line 6 for supplying deuterium-containing argon gas into the test tube, a line 7 for discharging the deuterium-containing argon gas out of the test tube, a line 8 for supplying pure argon gas into the measuring tube so that the deuterium permeating the test tube wall can be directed to the mass spectrometer, and a line 9 for discharging the pure argon out of the measuring tube.
  • members having a chemical densified coating involving pores and cracks are coated or otherwise treated with chromic acid in aqueous solution and an aqueous solution containing a material capable of forming an amorphous inorganic substance and subsequently heated to generate the fine particles of chromium oxide and amorphous inorganic substance in composite form, which are filled into the pores and cracks in the chemical densified coating and optionaly applied to cover its surface in a specified thickness.
  • the chemical densified coating has heretofore been found unsatisfactory in its ability to prevent the permeation of hydrogen isotopes but this problem is solved by the invention and the composite oxide coating of the invention finds a wider scope of applications in mechanical structures and members that need to be protected against gas permeation.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Ceramic Engineering (AREA)
  • Chemical Treatment Of Metals (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)

Claims (5)

  1. Pièce revêtue d'un revêtement en oxyde composite capable de prévenir la perméation des isotopes de l'hydrogène, qui comprend un substrat en acier inoxydable dont la surface est recouverte d'un revêtement continu de SiO2-Cr2O3 qui est épaissi chimiquement par de l'oxyde de chrome qui à son tour est recouvert d'un revêtement formé en remplissant les pores et les fissures du revêtement épaissi chimiquement avec les particules fines d'un composite d'oxyde de chrome et d'une matière inorganique amorphe à base de verre de silicate ou de verre de borosilicate.
  2. Pièce selon la revendication 1, dans laquelle la surface dudit revêtement épaissi chimiquement est recouverte d'une couche d'un composite d'oxyde de chrome et d'une matière inorganique amorphe à base de verre de silicate ou de verre de borosilicate.
  3. Procédé de production d'une pièce revêtue d'un revêtement en oxyde composite capable de prévenir la perméation des isotopes de l'hydrogène, qui comprend les étapes consistant à :
    appliquer un revêtement épaissi chimiquement sur la surface d'un substrat en acier inoxydable ;
    revêtir ou pulvériser la surface du revêtement épaissi chimiquement avec une solution aqueuse contenant de l'acide chromique et un matériau capable de former une substance inorganique amorphe en frittant ou en plongeant le revêtements chimiquement densifié dans ladite solution aqueuse; et maintenir le revêtement épaissi chimiquement à 250 - 750 °C de manière à ce que les pores et les fissures du revêtement épaissi chimiquement se remplissent avec les particules fines d'un composite d'oxyde de chrome et d'une une matière inorganique amorphe, à base de verre de silicate ou de verre de borosilicate, pour former un revêtement en oxyde composite.
  4. Procédé selon la revendication 3, dans lequel ladite étape de maintien est réalisée de sorte à fritter le revêtement épaissi chimiquement par chauffage à 250 - 750 °C de manière à ce que, en même temps, la surface du revêtement épaissi chimiquement soit revêtue d'une couche dudit composite d'oxyde de chrome et d'une matière inorganique amorphe à base de verre de silicate ou de verre de borosilicate.
  5. Procédé selon la revendication 3 ou 4, dans lequel le procédé comprenant les étapes consistant à revêtir ou à pulvériser le revêtement épaissi chimiquement avec ladite solution aqueuse ou à plonger le revêtement épaissi chimiquement dans ladite solution aqueuse et à chauffer le revêtement épaissi chimiquement ainsi traité est réalisé plus d'une fois de manière à ce que les pores et les fissures du revêtement épaissi chimiquement se remplissent avec les particules fines d'un composite d'oxyde de chrome et d'une matière inorganique amorphe ou à ce que la surface du revêtement épaissi chimiquement soit revêtue d'une couche dudit composite d'oxyde de chrome et d'une matière inorganique amorphe.
EP20020090080 2001-03-02 2002-02-28 Eléments revêtus de couches d'oxydes composites imperméables à l'hydrogène et procédé de fabrication de ces éléments Expired - Fee Related EP1236813B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2001058253A JP4863181B2 (ja) 2001-03-02 2001-03-02 水素同位体透過防止用複合酸化物皮膜被覆部材及びその製造方法
JP2001058253 2001-03-02

Publications (3)

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EP1236813A2 EP1236813A2 (fr) 2002-09-04
EP1236813A3 EP1236813A3 (fr) 2003-08-13
EP1236813B1 true EP1236813B1 (fr) 2011-05-25

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EP (1) EP1236813B1 (fr)
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107217281A (zh) * 2017-05-26 2017-09-29 华中科技大学 一种新型复合阻氚涂层及其制备方法
US11111108B2 (en) 2018-05-04 2021-09-07 Otis Elevator Company Coated sheave

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101518618B1 (ko) * 2013-11-27 2015-05-13 주식회사 포스코 밀착력이 향상된 강판의 표면 코팅 방법 및 이를 이용하여 처리된 강판

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3956531A (en) * 1967-06-01 1976-05-11 Kaman Sciences Corporation Chromium oxide densification, bonding, hardening and strengthening of bodies having interconnected porosity
US5360634A (en) * 1988-12-05 1994-11-01 Adiabatics, Inc. Composition and methods for densifying refractory oxide coatings
US5820976A (en) * 1988-12-05 1998-10-13 Adiabatics, Inc. Thin insulative ceramic coating and process
JPH02194183A (ja) * 1989-01-20 1990-07-31 Japan Atom Energy Res Inst セラミックス被覆ジルコニウム合金製物品およびその製造方法
JP3220012B2 (ja) * 1996-06-27 2001-10-22 トーカロ株式会社 硬質めっき皮膜被覆部材とその製造方法

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107217281A (zh) * 2017-05-26 2017-09-29 华中科技大学 一种新型复合阻氚涂层及其制备方法
US11111108B2 (en) 2018-05-04 2021-09-07 Otis Elevator Company Coated sheave

Also Published As

Publication number Publication date
EP1236813A2 (fr) 2002-09-04
JP4863181B2 (ja) 2012-01-25
EP1236813A3 (fr) 2003-08-13
JP2002256450A (ja) 2002-09-11

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