EP0302465A2 - Verfahren zur keramischen Beschichtung von Metallen - Google Patents
Verfahren zur keramischen Beschichtung von Metallen Download PDFInfo
- Publication number
- EP0302465A2 EP0302465A2 EP88112601A EP88112601A EP0302465A2 EP 0302465 A2 EP0302465 A2 EP 0302465A2 EP 88112601 A EP88112601 A EP 88112601A EP 88112601 A EP88112601 A EP 88112601A EP 0302465 A2 EP0302465 A2 EP 0302465A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- coating
- ion
- ceramic
- grams
- ceramic coating
- 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.)
- Withdrawn
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
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/04—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material
-
- 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
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/07—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing phosphates
- C23C22/08—Orthophosphates
- C23C22/20—Orthophosphates containing aluminium cations
-
- 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
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/04—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material
- C23C28/042—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material including a refractory ceramic layer, e.g. refractory metal oxides, ZrO2, rare earth oxides
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/36—Phosphatising
Definitions
- the present invention is a method for ceramic coating of metals.
- ceramic coatings with carbides such as TiC, SiC, nitrides such as TiN, Si3N4, borides such as TiB2, oxides such as Al203 or silicides such as MoSi2 can provide metals with improved heat and oxidation resistance.
- the ceramic coatings can be applied to metals by flame spray methods, ion sputtering methods, chemical vapour deposition methods (CVD), dry-in-place (coating-drying) methods, baking-in-place (coating-baking) methods and the like.
- flame spray methods ion sputtering methods, chemical vapour deposition methods (CVD), dry-in-place (coating-drying) methods, baking-in-place (coating-baking) methods and the like.
- one method is to treat a metal coated with frit at a temperature as high as 677-871°C (Jap.Pat.Publ SHO 55-26714/1980). Generally the method is carried out at a temperature used for inorganic coating materials. In the known processes the ceramic coating is applied directly on the surface of the metal which has been cleaned mechanically or chemically.
- This material comprises a denatured silicone varnish binder and alumina-silica short fibers as the ceramic material (Nikkei New Material, p.101, 5-19, 1986). According to this article, one of the advantages of the material is the capability of the film to follow the expansion of the substrate metal.
- the adhesion between the coating film and substrate metal is poor and the ceramic coatings delaminate because of the difference between the coefficient of thermal expansion of the substrate metal and the ceramic. Delamination can also be caused by oxidation of the substrate metal when exposed to high temperature.
- An object of the present invention is to provide a method for ceramic coating of metals; which coated metals can be used at high temperature without delamination.
- a further object of the invention is to provide a coating which protects the metal substrate from oxidation.
- the metal article comprising the aluminum phosphate coated metal substrate with the ceramic coating overlay also comprises the invention.
- aluminum phosphate coating refers to a film obtained by the method described in Jap.Pat.Pub.SHO 53-6945/1978 by the present applicants, wherein a coating is formed by a chemical conversion treatment or electrolytic treatment with an acidic liquid at a pH from 1.5 to 5 containing aluminum ion in a concentration of from about 0.01 to about 10 g/l and phosphate ion in about 1.0 to about 100 g/l, the principal component of such a film being aluminum phosphate (AlPO4-xH2O).
- Jap.Pat.Pub. SHO 53-6945/1978 is incorporated herein be reference.
- Publication SHO 53-6945/1978 is directed to preventing ferrous materials from corrosion by providing an alternative coating as a substitute for coatings of zinc, manganese, and calcium phosphate or the like and chromate coating for painting, and particularly for painting with acrylic-based paint.
- an aluminum phosphate coating is an excellent base coat for a ceramic coating.
- the characteristics of an aluminum phosphate coating have been investigated in more detail.
- Figure 1 shows thermal weight change and differential thermal analysis up to 500°C of an aluminum phosphate coating obtained according to the method described in the above-cited patent published herein.
- the coating of aluminum phosphate is amorphous AlPO4-xH2O, undergoes loss of x ⁇ H2O at about 150°C to 200°C (weight loss of about 12%), then up to about 500°C it is the stable form of AlPO4.
- the thermal analysis shows that the loss of adsorbed water and crystal water takes place respectively at 50-100°C and at about 150°C but at over 200°C no weight change occurs. This is an indication of the thermal stability of AlPO4.
- the drying of the aluminum phosphate coating is not critical. With air-drying of the film, residual moisture and water of crystallization are removed during baking without affecting the adhesion of the ceramic coating.
- the AlPO4 provides a base for high adhesion with the ceramic coating.
- the AlPO4 undergoes no further decomposition than the above-mentioned dehydration.
- a ceramic coating is deposited on cleaned metal surfaces according to known methods, the metal surface is oxidized when subjected to the heat resistance test and is accompanied by delamination of the ceramic coating.
- the composition containing aluminum ion for use in forming the AlPO4 coating is a liquid prepared by adding an aluminum compound such as nitrate, hydroxide or sulphate in the form of a solid or liquid to an acidic phosphate solution. The pH is adjusted so that the mixture is acidic.
- the content of aluminum ion in the mixture is from about 0.01 to 10 g/l, preferably 0.2 to 3 g/l. When less than about 0.01 g/l of Al ion is present, the deposit of aluminum phosphate is not sufficient. When the aluminum ion content exceeds about 3 g/l, economical disadvantages result.
- the acidic phosphate liquid mixture is prepared by diluting phosphoric acid, sodium dihydrogen phosphate or disodium hydrogen phosphate and the like with water so as to contain 1 to 100 g/l, preferably 5 to 50 g/l, of the phosphate ion.
- the pH is less than about 1.5, the metal being treated receives a large amount of etching.
- the pH is above about 5.0, precipitation of aluminum phosphate and aluminum hydroxide take place in the treating bath.
- nitrate ion in an amount of from 0 to about 20 g/l preferably 1 to 5 g/l, chlorate ion in an amount of from 0 to about 20 g/l preferably 1 to 5 g/l, or nickel ion in an amount of from 0 to about 5 g/l preferably 0.01 to 2 g/l. It is also useful, for the purpose of increasing coating weight, to add sulphate ion in an amount of from 0 to about 10 g/l.
- the metals to which the method of the present invention is applicable are those metallic materials which require improved heat resistance and which can be etched by phosphoric acid. Metals such as iron, steel, stainless steel, heat-resistant steel, aluminum, aluminum alloy, etc., can be treated by the method of the present invention.
- the metal substrate can be coated with the AlPO4 coating by:
- the coating formed is dried and preferably baked at a temperature above about 150°C.
- Ceramics such as carbides, nitrides, borides, oxides, silicides, mixtures or compositions containing these and the like are useful.
- Alkali metal silicate type coating compositions, metal alcoholate type coating compositions, silica sol type compositions and silicone compositions and the like can be used in the process.
- the baking-in-place (coating/baking) process of the present invention for ceramic coating can provide a coating film with adhesion to the substrate comparable to that provided by conventional CVD processes.
- the substrate becomes hot so that the heat resistance of aluminum phosphate can be utilized in the ceramic coating. Heating the substrate, during the ceramic coating, up to about 200 to about 400°C is also useful. A similar effect occurs in the ion sputtering process or flame spray process.
- Test piece SPCC steel sheet (70 x 150 x 0.8 mm) was used.
- the composition of the treating liquid was as follows: PO43 ⁇ 22.8 g/l A13+ 0.9 g/l NO3 3.1 g/l This liquid was neutralized with sodium hydroxide to adjust the pH to about 2.5.
- the metal test piece was surface cleaned and immersed in the treating liquid for 3 minutes.
- the treating liquid was maintained at a temperature of 60°C.
- the test piece was removed from the treating liquid, rinsed with water and dried. A coating weighing 1 g/m2 was formed on the test piece.
- test piece was dip-coated with GLASCA 90 (a product of Nichiban R&D Ltd., metal alcoholate type: colorless transparent, ceramic component: alkoxysilane 19-23%), then baked at 150°C for 30 minutes to form a colorless, transparent ceramic coating.
- the film thickness was 5 ⁇ m.
- An SPCC steel sheet (70 x 150 x 0.8 mm) test piece which was previously surface cleaned was subject to an electrolytic treatment in a liquid of the composition PO43 ⁇ 25.0 g/l A13+ 1.2 g/l NO3 9.0 g/l
- the liquid was neutralized with sodium hydroxide to adjust the pH to 2.5.
- the test piece was immersed in the liquid and was electrolytically treated with direct current at a temperature of 65°C, a current density of 5A/dm2 for 30 seconds.
- the opposite electrode was a graphite plate at an electrode distance of 40 mm and electrode ratio of 1:1. After the electrolytic coating, the test piece was rinsed with water and dried.
- a ceramic coating as in Example 1 was applied to the coated test piece.
- Example 1 For comparison, a ceramic coating as in Example 1 was applied to a test piece without precoating (the steel sheet was surface-cleaned with a cleaner).
- Example 1 and Example 2 were heated in an over at 250°C, 400°C or 500°C for 2 hours, then cooled in air.
- the result of an appearance inspection is shown in Table 1.
- the discoloring of the metal surface by oxidation was visually observed either through the transparent ceramic coating or, in the case the ceramic coating was delaminated, directly on such portions of the metal.
- Test pieces were coated by the conversion treatment of Example 1 or 2. The coated test pieces were then coated with various kinds of ceramic coating compositions and subjected to the following tests which results are shown in Table 3.
- test pieces After receiving the base coat and ceramic coating, test pieces were heated to various temperatures and cooled to room temperature.
- ceramic coating without precoating permits oxidation of the metal surface, often resulting in delamination.
- delamination does not take place below about 500°C and oxidation of the metal surface is suppressed.
- the heat resistance attained by means of the baking-in-place process of the invention is comparable to that obtained by a conventioned CVD process.
- the method of the present invention is free of the disadvantages of the CVD process such as long treatment time (as much as 2 to 8 hrs), poor productivity and high apparatus cost.
- the process of the invention when used with a baking-in-place process provides a simple treatment process with high productivity.
- the method of the present invention is also applicable to a CVD process and the like, and provides for excellent adhesion and oxidation resistance.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Inorganic Chemistry (AREA)
- Ceramic Engineering (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
- Chemical Treatment Of Metals (AREA)
- Laminated Bodies (AREA)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP192591/87 | 1987-08-03 | ||
JP62192591A JPH0730459B2 (ja) | 1987-08-03 | 1987-08-03 | 金属へのセラミックコ−ティング法 |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0302465A2 true EP0302465A2 (de) | 1989-02-08 |
EP0302465A3 EP0302465A3 (de) | 1990-01-31 |
Family
ID=16293823
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP88112601A Withdrawn EP0302465A3 (de) | 1987-08-03 | 1988-08-03 | Verfahren zur keramischen Beschichtung von Metallen |
Country Status (5)
Country | Link |
---|---|
EP (1) | EP0302465A3 (de) |
JP (1) | JPH0730459B2 (de) |
AU (1) | AU606726B2 (de) |
BR (1) | BR8803842A (de) |
MX (1) | MX170165B (de) |
Cited By (18)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0991365A1 (de) * | 1997-04-30 | 2000-04-12 | Medquest Products, Inc. | Elektrochirurgische klinge mit einem leitenden nicht klebendem überzug |
WO2005061218A1 (en) * | 2003-11-19 | 2005-07-07 | Applied Thin Films, Inc. | Aluminum phosphate compounds, compositions, materials and related metal coatings |
DE10014035B4 (de) * | 2000-03-22 | 2006-07-13 | Electro Chemical Engineering Gmbh | Gefärbte Konversionsschicht, eine Lösung zu ihrer Herstellung sowie ihre Verwendung |
EP1743955A2 (de) | 2005-07-15 | 2007-01-17 | NHK Spring Co., Ltd. | Stahlteil mit hervorragendem Korrosionswiderstand und Korrosionsermüdungswiderstand, sowie Oberflächendbehandlung zur Herstellung |
US7311944B2 (en) | 2002-12-23 | 2007-12-25 | Applied Thin Films, Inc. | Aluminum phosphate coatings |
US7678465B2 (en) | 2002-07-24 | 2010-03-16 | Applied Thin Films, Inc. | Aluminum phosphate compounds, compositions, materials and related metal coatings |
US7682700B2 (en) | 2002-08-14 | 2010-03-23 | Applied Thin Films, Inc. | Aluminum phosphate compounds, compositions, materials and related composites |
US7887917B2 (en) | 2005-06-30 | 2011-02-15 | Unifrax I Llc | Inorganic fiber |
CN103044995A (zh) * | 2013-01-28 | 2013-04-17 | 陈立晓 | 一种柴油机排气管道高温涂料 |
US8497018B2 (en) | 2010-01-27 | 2013-07-30 | Applied Thin Films, Inc. | High temperature stable amorphous silica-rich aluminosilicates |
CN103741195A (zh) * | 2013-12-23 | 2014-04-23 | 南通恒新金属工艺科技有限公司 | 钢丝电解磷化处理装置 |
US9556063B2 (en) | 2014-07-17 | 2017-01-31 | Unifrax I Llc | Inorganic fiber with improved shrinkage and strength |
US9567256B2 (en) | 2013-03-15 | 2017-02-14 | Unifrax I Llc | Inorganic fiber |
US9708214B2 (en) | 2014-07-16 | 2017-07-18 | Unifrax I Llc | Inorganic fiber with improved shrinkage and strength |
US9919957B2 (en) | 2016-01-19 | 2018-03-20 | Unifrax I Llc | Inorganic fiber |
US10023491B2 (en) | 2014-07-16 | 2018-07-17 | Unifrax I Llc | Inorganic fiber |
US10882779B2 (en) | 2018-05-25 | 2021-01-05 | Unifrax I Llc | Inorganic fiber |
US11203551B2 (en) | 2017-10-10 | 2021-12-21 | Unifrax I Llc | Low biopersistence inorganic fiber free of crystalline silica |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2008106340A (ja) * | 2006-10-27 | 2008-05-08 | Nhk Spring Co Ltd | 鉄鋼用りん酸アルミニウム系化成処理液及びその作製方法 |
CN110438485A (zh) * | 2019-07-29 | 2019-11-12 | 吴俊杰 | 一种pvc喷胶工艺的磷化处理系统 |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR884852A (fr) * | 1940-05-10 | 1943-08-30 | Opel Adam Ag | Procédé pour protéger contre la rouille la surface intérieure des réservoirs àessence et des canalisations pour combustibles liquides |
FR2219245A1 (de) * | 1973-02-27 | 1974-09-20 | Parker Ste Continentale | |
JPS51136539A (en) * | 1975-05-22 | 1976-11-26 | Ota Toshuki | Process for coating aluminum with inorganic substance |
JPS5481132A (en) * | 1977-12-13 | 1979-06-28 | Teikoku Kako Kk | Steel materials for use in ferroconcretes |
JPS54148139A (en) * | 1978-04-24 | 1979-11-20 | Nippon Steel Corp | Bolt set excellent in ease to paint, corrosion resistance, lubricativity, and co-turning inhibition |
US4592958A (en) * | 1983-01-18 | 1986-06-03 | Sermatech | Coated part, coating therefor and method of forming same |
-
1987
- 1987-08-03 JP JP62192591A patent/JPH0730459B2/ja not_active Expired - Lifetime
-
1988
- 1988-08-03 BR BR8803842A patent/BR8803842A/pt not_active IP Right Cessation
- 1988-08-03 EP EP88112601A patent/EP0302465A3/de not_active Withdrawn
- 1988-08-03 AU AU20386/88A patent/AU606726B2/en not_active Ceased
- 1988-08-31 MX MX012534A patent/MX170165B/es unknown
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR884852A (fr) * | 1940-05-10 | 1943-08-30 | Opel Adam Ag | Procédé pour protéger contre la rouille la surface intérieure des réservoirs àessence et des canalisations pour combustibles liquides |
FR2219245A1 (de) * | 1973-02-27 | 1974-09-20 | Parker Ste Continentale | |
JPS51136539A (en) * | 1975-05-22 | 1976-11-26 | Ota Toshuki | Process for coating aluminum with inorganic substance |
JPS5481132A (en) * | 1977-12-13 | 1979-06-28 | Teikoku Kako Kk | Steel materials for use in ferroconcretes |
JPS54148139A (en) * | 1978-04-24 | 1979-11-20 | Nippon Steel Corp | Bolt set excellent in ease to paint, corrosion resistance, lubricativity, and co-turning inhibition |
US4592958A (en) * | 1983-01-18 | 1986-06-03 | Sermatech | Coated part, coating therefor and method of forming same |
Non-Patent Citations (4)
Title |
---|
CHEMICAL ABSTRACTS, vol. 86, 1977, page 330, abstract no. 94697h, Columbus, Ohio, US; & JP-A-76 136 539 (T. OTHA) 26-11-1976 * |
CHEMICAL ABSTRACTS, vol. 89, no. 18, October 1978, page 216, abstract no. 150457f, Columbus, Ohio, US; V.F. KARPOV et al.: "Method of producing protective aluminum coatings on steel in vacuo", & VYSSH. MASHINOSTR. 1978, 58(7), 74-6 * |
PATENT ABSTRACTS OF JAPAN, vol. 3, no. 100 (C-56), 24th August 1979, page 167 C 56; & JP-A-54 81 132 (MITSUBISHI KASEI KOGYO K.K.) 28-06-1979 * |
PATENT ABSTRACTS OF JAPAN, vol. 4, no. 12 (C-72), 29th January 1980, page 126 C 71; & JP-A-54 148 139 (NIPPON SEITETSU K.K.) 20-11-1979 * |
Cited By (27)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0991365A4 (de) * | 1997-04-30 | 2000-04-12 | Medquest Products Inc | Elektrochirurgische klinge mit einem leitenden nicht klebendem überzug |
EP0991365A1 (de) * | 1997-04-30 | 2000-04-12 | Medquest Products, Inc. | Elektrochirurgische klinge mit einem leitenden nicht klebendem überzug |
DE10014035B4 (de) * | 2000-03-22 | 2006-07-13 | Electro Chemical Engineering Gmbh | Gefärbte Konversionsschicht, eine Lösung zu ihrer Herstellung sowie ihre Verwendung |
US7678465B2 (en) | 2002-07-24 | 2010-03-16 | Applied Thin Films, Inc. | Aluminum phosphate compounds, compositions, materials and related metal coatings |
US8124184B2 (en) | 2002-07-24 | 2012-02-28 | Applied Thin Films, Inc. | Aluminum phosphate compounds, compositions, materials and related metal coatings |
US7682700B2 (en) | 2002-08-14 | 2010-03-23 | Applied Thin Films, Inc. | Aluminum phosphate compounds, compositions, materials and related composites |
US7311944B2 (en) | 2002-12-23 | 2007-12-25 | Applied Thin Films, Inc. | Aluminum phosphate coatings |
AU2003304644B2 (en) * | 2003-11-19 | 2010-09-30 | Applied Thin Films, Inc. | Aluminum phosphate compounds, compositions, materials and related metal coatings |
WO2005061218A1 (en) * | 2003-11-19 | 2005-07-07 | Applied Thin Films, Inc. | Aluminum phosphate compounds, compositions, materials and related metal coatings |
US8551897B2 (en) | 2005-06-30 | 2013-10-08 | Unifrax I Llc | Inorganic fiber |
US7887917B2 (en) | 2005-06-30 | 2011-02-15 | Unifrax I Llc | Inorganic fiber |
EP1743955A3 (de) * | 2005-07-15 | 2007-01-24 | NHK Spring Co., Ltd. | Stahlteil mit hervorragendem Korrosionswiderstand und Korrosionsermüdungswiderstand, sowie Oberflächendbehandlung zur Herstellung |
EP1743955A2 (de) | 2005-07-15 | 2007-01-17 | NHK Spring Co., Ltd. | Stahlteil mit hervorragendem Korrosionswiderstand und Korrosionsermüdungswiderstand, sowie Oberflächendbehandlung zur Herstellung |
US8497018B2 (en) | 2010-01-27 | 2013-07-30 | Applied Thin Films, Inc. | High temperature stable amorphous silica-rich aluminosilicates |
CN103044995A (zh) * | 2013-01-28 | 2013-04-17 | 陈立晓 | 一种柴油机排气管道高温涂料 |
US9567256B2 (en) | 2013-03-15 | 2017-02-14 | Unifrax I Llc | Inorganic fiber |
US9919954B2 (en) | 2013-03-15 | 2018-03-20 | Unifrax I Llc | Inorganic fiber |
CN103741195A (zh) * | 2013-12-23 | 2014-04-23 | 南通恒新金属工艺科技有限公司 | 钢丝电解磷化处理装置 |
CN103741195B (zh) * | 2013-12-23 | 2016-06-15 | 南通恒新金属工艺科技有限公司 | 钢丝电解磷化处理装置 |
US9708214B2 (en) | 2014-07-16 | 2017-07-18 | Unifrax I Llc | Inorganic fiber with improved shrinkage and strength |
US10023491B2 (en) | 2014-07-16 | 2018-07-17 | Unifrax I Llc | Inorganic fiber |
US10301213B2 (en) | 2014-07-16 | 2019-05-28 | Unifrax I Llc | Inorganic fiber with improved shrinkage and strength |
US9556063B2 (en) | 2014-07-17 | 2017-01-31 | Unifrax I Llc | Inorganic fiber with improved shrinkage and strength |
US9926224B2 (en) | 2014-07-17 | 2018-03-27 | Unifrax I Llc | Inorganic fiber with improved shrinkage and strength |
US9919957B2 (en) | 2016-01-19 | 2018-03-20 | Unifrax I Llc | Inorganic fiber |
US11203551B2 (en) | 2017-10-10 | 2021-12-21 | Unifrax I Llc | Low biopersistence inorganic fiber free of crystalline silica |
US10882779B2 (en) | 2018-05-25 | 2021-01-05 | Unifrax I Llc | Inorganic fiber |
Also Published As
Publication number | Publication date |
---|---|
BR8803842A (pt) | 1989-02-21 |
AU2038688A (en) | 1989-02-09 |
MX170165B (es) | 1993-08-10 |
JPH0730459B2 (ja) | 1995-04-05 |
AU606726B2 (en) | 1991-02-14 |
JPS6436774A (en) | 1989-02-07 |
EP0302465A3 (de) | 1990-01-31 |
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