AU606726B2 - Method for ceramic coating on metals - Google Patents
Method for ceramic coating on metals Download PDFInfo
- Publication number
- AU606726B2 AU606726B2 AU20386/88A AU2038688A AU606726B2 AU 606726 B2 AU606726 B2 AU 606726B2 AU 20386/88 A AU20386/88 A AU 20386/88A AU 2038688 A AU2038688 A AU 2038688A AU 606726 B2 AU606726 B2 AU 606726B2
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- AU
- Australia
- Prior art keywords
- coating
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- ceramic
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- 238000005524 ceramic coating Methods 0.000 title claims description 40
- 229910052751 metal Inorganic materials 0.000 title claims description 40
- 239000002184 metal Substances 0.000 title claims description 40
- 238000000034 method Methods 0.000 title claims description 40
- 150000002739 metals Chemical class 0.000 title description 11
- 238000000576 coating method Methods 0.000 claims description 41
- 239000011248 coating agent Substances 0.000 claims description 40
- 239000000758 substrate Substances 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 19
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 14
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 claims description 13
- 229910052782 aluminium Inorganic materials 0.000 claims description 11
- -1 aluminum ion Chemical class 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 11
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 11
- 230000003647 oxidation Effects 0.000 claims description 9
- 238000007254 oxidation reaction Methods 0.000 claims description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 7
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 7
- 229910052910 alkali metal silicate Inorganic materials 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- 229940085991 phosphate ion Drugs 0.000 claims description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 claims description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 2
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- 229940005989 chlorate ion Drugs 0.000 claims description 2
- 229910001453 nickel ion Inorganic materials 0.000 claims description 2
- 239000003643 water by type Substances 0.000 claims description 2
- 101000808896 Caenorhabditis elegans Potential E3 ubiquitin-protein ligase ariadne-2 Proteins 0.000 claims 1
- 101150039033 Eci2 gene Proteins 0.000 claims 1
- 101000608745 Phytolacca americana Lectin-B Proteins 0.000 claims 1
- 150000001340 alkali metals Chemical class 0.000 claims 1
- 238000012360 testing method Methods 0.000 description 21
- 239000000463 material Substances 0.000 description 14
- 239000007788 liquid Substances 0.000 description 13
- 239000000919 ceramic Substances 0.000 description 10
- 229910019142 PO4 Inorganic materials 0.000 description 7
- 230000032798 delamination Effects 0.000 description 7
- 238000011156 evaluation Methods 0.000 description 7
- 239000010452 phosphate Substances 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 229910017119 AlPO Inorganic materials 0.000 description 5
- 229910000831 Steel Inorganic materials 0.000 description 5
- 230000002378 acidificating effect Effects 0.000 description 5
- 238000005229 chemical vapour deposition Methods 0.000 description 5
- 239000010959 steel Substances 0.000 description 5
- 238000005260 corrosion Methods 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 4
- 239000007921 spray Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 239000008199 coating composition Substances 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 229920001296 polysiloxane Polymers 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 229910010293 ceramic material Inorganic materials 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 150000001247 metal acetylides Chemical class 0.000 description 2
- 150000004767 nitrides Chemical class 0.000 description 2
- 238000010422 painting Methods 0.000 description 2
- 238000012552 review Methods 0.000 description 2
- 229910021332 silicide Inorganic materials 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- 229910021653 sulphate ion Inorganic materials 0.000 description 2
- TUBQDCKAWGHZPF-UHFFFAOYSA-N 1,3-benzothiazol-2-ylsulfanylmethyl thiocyanate Chemical compound C1=CC=C2SC(SCSC#N)=NC2=C1 TUBQDCKAWGHZPF-UHFFFAOYSA-N 0.000 description 1
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- QYEXBYZXHDUPRC-UHFFFAOYSA-N B#[Ti]#B Chemical compound B#[Ti]#B QYEXBYZXHDUPRC-UHFFFAOYSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 229910016006 MoSi Inorganic materials 0.000 description 1
- 241001590997 Moolgarda engeli Species 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910033181 TiB2 Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical compound [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000007739 conversion coating Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 229910000403 monosodium phosphate Inorganic materials 0.000 description 1
- 235000019799 monosodium phosphate Nutrition 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000005488 sandblasting Methods 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000002076 thermal analysis method Methods 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 238000011179 visual inspection Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
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
Landscapes
- 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)
- General Chemical & Material Sciences (AREA)
- Electrochemistry (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
- Chemical Treatment Of Metals (AREA)
- Laminated Bodies (AREA)
Description
ecla ll.i-i_ i-lx. c Form COMMONWEALTH OF AUSTRALIA PATENTS ACT 1952-69 CODMPLETE SP~ECIFICATION
IOFIIGINALI
Class I t. Class Application Number: Lodged.
20386/88 3rd August 1988 ~1 Ft ittin the seaion 49 and is correct for prilting. .Wvm Complete Specification Lodged: Accepted: Published: 0 ,Pfiprity: 0 0P 0 P0 0 0 Ot o 0 o po 09 oP 0 o 0 0 o p Nlame of Applicant: NIHON PARKERIZING COMPANY, LTD.
o 4 t 0 o P 9ddress of Applicant: o 0 0 P 0 0 A.tual Inventor: aress for Service: 0000a 00 0 0 0 0 a0 YOSHIO MORIYA, SOLIET KOIZUMI, MASANORI KANDA and YASUNOBIJ MATSUSHIME EDWD. WATERS SONS, 5o0 QUEEN STREET, MELBOURNE, AUSTRALIA, 3000.
Complete Specification for the invention entitled: METHOD FOR CERAMIC COATING ON METALS The folowing statement is a full description of this irniention, Including the best method of performing It known to L j I i i -la-
SPATENT
Case m 4649 P+A If SMETHOD FOR CERAMIC COATING ON METALS BACKGROUND OF THE INVENTION 1. Field of the Invention: The present invention is a method for ceramic coating of j metals.
In recent years, interest has arisen in ceramic coatings which do not delaminate under high temperature exposure.
2. Statement of Related Art: In recent years metals which require higher heat resistance and oxidation resistance are treated with ceramic coatings.
According to the report entiilea "Review of Ceramic Coating Technologies in Tenrs of Development Attitudes Towards Utilization to New Industrial Fields", published by Japan Industrial Technology Association In March 1985, pages 206-209, ceramic coatings with carbides such as TiC, SiC, nitrides such as TiN, Si13N 4 borides such as TiB2, oxides such as A120 3 or silicides such as MoSi 2 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-inplace (coating-baking) methods and the likes -1- In the case of basing-in-place processes, one method is to treat a metal coated with frit at a temperature as high as 677-871 0 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. The "Review on Ceramic Coatings" discloses that, in the case of metal alcoholate type coating material, a satisfactory cc-ting can be applied to the substrate with alkali cleaning alone (page 25); in the case of alkali-metal silicate type coating material, reaction with the substrate metal is required in addition to sand blasting to provide a rough surface for adhesion of the coating. In the case of coating material for high temperature use, chemical combination should take place between the ceramic and the metal.
SRecently, a new heat-resistant coating material of the silicone type has been placed on the market. 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 advantage; of the material is the capability of the film to follow the expansiorn of the zubstrate metal.
In all of the known methods with perhaps the exception of the CVD process, 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 too by oxidation of the substrate metal when exposed to high temperature.
To overcome these problems, attempts have been made to enhance the reaction between the coating material (ceramic) and the metal. However, since this method relies upon the type of metal and the coating material's composition, there are inherent limits in the method.
An object of the present invention is to provide a method for i i i I ceramic coating of metals; which coated metals can be used at high tempersa re without delamination. A further object of the invention is to provide a coating which protects the metal substrate from oxidation.
BRIEF DESCRIPTION OF THE INVENTION Applicants have unexpectedly discovered that forming an aluminum phosphate coating over a metal substrate before forming a coating with a ceramic material effectively suppresses substrate metal oxidation as well as improves the resistance to delamination of the ceramic coating at high temperatures.
The metal article comprising the aluminum phosphate coated metal substrate with the ceramic coating overlay also comprises the invention.
DETAILED DESCRIPTION OF THE INVENTION Other than in the operating examples, or where otherwise indicated, all numbers expressing quantities of ingredients or reaction conditions used herein are to be understood as modified in all instances by the term "about".
The term "aluminum phosphate coating" as used herein 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 (A1PO 4 -xH 2 0.
Jap.Pat.Pub. SHO 53-6945/1978 is incorporated herein by 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.
We discovered that an alumin'n 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 thermalI analysis up to 500 0 C of an aluminum phosphate coating obtained according to the method described in the above-cited patent publication. The coating of al1umi num phosphate is amorphouF AlPO 4 -xH 2 O, undergoes loss of x-H 2 O at about 150 0 C to 200 0
C
(weight loss of about then up to about 500 0 C it is the stable form of AlPO 4 The thermal analysis shows that the loss of adsorbed water and crystal water takes place respectively at 50-100 0 C and at about 150 0 C but at over 200 0 C no weight change occurs. This is an indication of the thermal stability of AlPO 4 In the present invention, the drying of the aluminum phosphate coating is not critical. With air-drying of the film, residual moistuI'q and water of crystallization are removed during baking tithout affecting thd adhesion of the ceramic coating.
Ouring baking of the ceramic coating or chemical vapor too. deposition, the temperature of the substrate rise5 and the moisture is removed. The AlP0 4 provides a base for high adhesion '2with the cerami~c coating. The AlPO 4 undergoes no further decomfposition than the above-mentioned dehydration.
If a ceramic coating Is deposited on cleaned metal surfaces to according to knowo methods, the metal surface is oxidized when subjected to the heat resistance test and is accompanied by delamination of the ceramic coating.
In the case of a ceramic coating deposited over an aluminum 2 25 phosphate coating, when subjected to the heat resistance test, such a ceramic coating is free of delamination and oxidation of the metal sub,5trate is suppressed. By the present process, the function of a ceramic coating primarily aimed at improved heat resistance can be enhanced further.
The composition containing aluminum ion for use In forming the AIP0 4 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 9/l, preferably 0.2 to 3 g/1. When less than about 0.01 9/1 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. As an example, a liquid mixture prepared by addition of an aluminum compound to phosphoric acid is adjusted to pH =1.5-5.0 by means of caustic soda, caustic potassium, anmnonia or the like. When the pH is less thant about 1.5, the metal being treated receives a large amount 0 00a.of etching. When the pH is above about 5.0, prEcipitation of alu- 0 00 ,minum phosphate and aluminum hydroxide take place in the treating 00 15 bath.
It is also useful to add as an oxidizer or a coating for- 0000 mation accelerator a nitrate Ion in an amount of from 0 to about g/l preferably 1 to 5 g/l chlorate ion in an amount of from 0 to about 20 gil preferably 1 to 5 g/l or nickel ion in an amount of f rom 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.
0,The metals to which the method of the present invention is applicable are those metallic materials which require inmproved heat resistance and which can be etched by phosphoric acid.
Metals such as iron, steel, stainless steel, heat-resistant steel, 0 0 M Valuminum, aluminum alloy, etc., can be treated by the method of 0000 the present invention.
00 0 000 The metal substrate can be coated with the AlPO 4 coating by: 1) an imm~ersion in or spraying with an acidic phosphate liquid mixture at a temperature 30 to 900C for 1 to 5 minutes. The process is similar to the conventional conversion coating treatment.
2) an alternating' current electrolytic conversion treatment where both electrodes ire a work piece or the opposite
I
electrode is a material such as graphite, aluminum or stainless steel. The electrodes are generally spaced a distance of from 20 to 500 mm. Current density is in the range of from 0.1 to 20A/dm 2 preferably 3 to 5A/dm 2 The electrolysis time can be from 5 sec. to 5 min.
3) a cathodic electrolytic conversion treatment where the work piece to be treated is the cathode and the opposite electrode is a conductive material such as graphite, aluminum, stainless steel and the like. A combination of an electrolytic conversion treatment and an immersion or spray conversion treatment can be used.
The coating formed is dried and preferably baked at a tem- 0 6a perature above about 150 0
C.
doom 00 With respect to ceramic applied over the A1P0 4 coating, there is no specific restriction placed on the ceramic coating com- S0 positions as long as their heat resistance can withstand the 04. 0 baking temperature and high temperature use contemplated.
o. 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.
,0 The baking-in-place (coating/baking) process of the present invention for ceramic coating can provide a coating film with 25 adhesion to the substrate comparable to that provided by conventional CVD processes.
In the CVD process 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 30 about 200 to about 400 0 C is also useful. A similar effect occurs in the ion sputtering process or flame spray process.
The present invention is described in more detail by way of the following Examples which are provided for illustration only and are not limiting.
a a o a o a a 0,'a a., o a 2 o a tao a EXAMPLE 1 Conversion treatment Test piece: SPCC steel sheet (70 x 150 x 0.8 rmm) was used.
The composition of the treating liquid was as follows: P0 4 3 229.8 g/l A1 3 0.9 g/l N0 3 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 immiersed in the treating liould for 3 minutes. The treating liquid was maintained at a temperature of 60 0 C. The test piece was removed from the treating liquid, rinsed with water and dried.
A coating weighing 1 9/m 2 was formed on the test piece.
The test piece was dip-coated with GLASCA 90 (a product of is ?ichiban R&D Ltd., metal alcoholate type: colorless transparent, ceramic component: alkoxysilane then baked at 150 0 C for 30 minutes to form a colorless, transparent ceramic coating. The film thickness was 5,M111.
EXAMPLE 2 Electrolytic treatment An SPCC steel sheet (70 x 150 x 0.8 mmr) test piece which was priously surface cleaned was subject to a'n electrolytic treatment In a liquid of the composition P0 4 3 25.0 g/1 A1 3 1.2 g/1l N03 9.0 g/l The liquid was neutralized with sod t ium hydroxide tao 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 a current density of 5A/dm 2 for 30 seconds. The opposite electrode was a graphite plate at an electrode distance of 40 nm and electrode ratio of 1:1. After the elertrolytic coating, the test piece was rinsed with water and dried.
A ceramic coating as in Example 1 was applied to the coated test piece.
-7- For comparison, a ceramic coating as in Example 1 was applied to a test piece without precoating (the steel sheet was surfacecleaned with a cleaner).
The test pieces: without precoating, and Example 1 and Example 2, were heated in an oven at 250 0 C, 400 0 C or 500 0 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.
As can be seen from the test results, forming an aluminum phosphate coating prior to applying a ceramic coating provides for oo,° improved adhesion of the coating at high temperature and the o°0 discoloring of the substrate which is associated with oxidation of 00o 15 the metal is also suppressed. The effect is due to the heat o0 o 0 resistance provided by the aluminum phosphate coating.
o o 0 0 0o a
O
0 t 0 I 0 0 0 t 00 0 0 a e 00 o 000 0 t0 TABLE 1 APPEARANCE AFTER HEAT RESISTANCE TEST 250 0 C 2 hrs 400 0 C 2 hrs 500 0 C 2 hirs not delaminated 70% delaminated entirely without del ami nated precoatingl slight blueing blueing blueing not delaminated not delarninated not delarninated Example I no blueing no blueing slight blueing not delaminated not delaminated not delaminated Example 2 no blueing no blueing no blueing
IC_
EXAMPLE 3 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 method 1. Corrosion resistance a. Method: salt fog spray test b. Evaluation: according to ASTM-D714-56 except that evaluation was made by substituting rust development in place of blistering in the evaluation standard a Rating of rust size: ooO (excellent) 10 no change 0 large rust (poor) a 0a o0 O 15 Rust area: (excellent) F min.density M MD D over S°0o entire surface (poor) S0 0 2. Evaluation of heat resistance o a. Method: After receiving the base coat and ceramic coating, test pieces were heated to various temperatures and cooled to room temperature.
b. Evaluation: visual inspection of the ceramic coating for 0 0 Soo adhesion and change of color of the °o a0 underlying substrate material Rating on coating adhesion: 0 00 S00o 25 (excellent) 5 no delamination 0 delamination on entire surface (poor) Change of substrate material: 0000 oo.0 (excellent) 5 no change 0 blueing (poor) 0o D The ceramic coatings described in Table 2 were applied by dipping; baking was done under respective conditions shown In Table 2. Table 3 shows the results of the tests.
TABLE 2 CERAMIC COATING AND BAKING CONDITIONS No. Trade name (maker) Outline of composition Baking condition GLASCA 90 metal alcoholate 1 (Nichiban R&D) (ceramic component 150 C x 20 min.
alkoxysilane) CRM-100 alkali silicate type 2 (Okuno Chemical (ceramic component 200 0 C x 5 min.
Industries Co.Ltd) S102) MOF Ti-Film alkali metal salt type 3 (Tokyo Ohka Ind.) (ceramic component 500°C x 30 min.
2 Sil-B Coat alkali silicate type 4 (Central Glass) (ceramic component 180°C x 5 min.
S102) CM2000 (Matsushita denatured silica type 250 0 C x 20 min.
Electric) -11- -1 TABLE 3 CORROSION RESISTANCE AND HEAT RESISTANCE corrosion resi stancehetrssac heat resistance *1 4 pretreatment ceramilc coating 250 0
C
x 2 hr 5001C x 2 h 72 hr 2r 144 hr 20h 240 htwithout GLASCA 90 VF 0 -5 5 0 0 pretreatment CRM 100 IF 0 -5 5 2 2 MOF Ti-Film 10 0 -5 5 4 4 method GLASCA 90 10 8MiD 4?AD 5 5 5 according to CRM 100 10 8D 20 5 5 5 Example 1 MOF TI-Film 10 5F 0 5 5 5 method GLASCA 90 10 9F 3MD 5 5 5 according to CRM 100 10 6D 0 5 5 4 4 Example 2 MOF TI-Film 10 8HD 20 5 5 5 Remark; A evaluation of adhesion B evaluation of substrate change -12-
Claims (6)
- 2. A process of claim 1 wherein the chemical conversion treatment or electrolytic treatment is conducted in an aqueous phosphoric acid mixture containing from ab~st 0.01 to abett 10 grams/liter aluminum ion and from *abeot- 1.0 to abe-t-100 grams/liter phosphate ion at a pH of from about 1.5 to
- 3. A method of claim 2 wherein the phosphoric acid mixture contains from abo4t. 0.2 to-abet 3 grams/liter aluminum ion and from about= to b&but- 50 grams/liter phosphate ion.
- 4. A method of claim 3 wherein the phosphoric acid mixture additionally contains from -a4et 0 to -4tet 20 grams/liter nitrate ion. A method of claim 3 wherein the phosphoric acid mixture additionally contains from about 0 to about 20 grams/liter chlorate ion or from abet-0 to abeto-5 grams/liter nickel ion. 0000 0o oo o o 0 00 0 0 0 o oo 0 00 0 0o o0000 0 0 0 0 Q 00 o0 0 a0 00 0 DO0 00 0 00 0 00 0 0 0 0 00 o oo 6. A temperature and oxidations resistant article comprising a metal substrate, an aluminum phosphate coating on said substrate and a ceramic coating overlying the aluminum phosphate coating. 0000 0 0000 00 0 0 0 0 0 00
- 7. A product of the process of claim 1.
- 8. A product of the process of claim 2.
- 9. An article of claim 6 wherein the ceramic coating is formed from at least one composition selected from the group consisting of alkoxy- silanes, alkali metal silicates, alkali metal type T102 and dena- tured silica. I, DATED this 2nd day of August 1988. iNIHON PARKERIZING COMPANY, LTD. Sster tty Lb rain tm wecci e \'15 PL B O N EDWD. WATERS SONS tPue o i c" PATENT ATTORNEYS tho s peci.ilatid 'idln&ari 2 MELBOURNE. VIC. 3000. J.(ho y),r
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62192591A JPH0730459B2 (en) | 1987-08-03 | 1987-08-03 | Ceramic coating method on metal |
| JP62-192591 | 1987-08-03 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| AU2038688A AU2038688A (en) | 1989-02-09 |
| AU606726B2 true AU606726B2 (en) | 1991-02-14 |
Family
ID=16293823
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| AU20386/88A Ceased AU606726B2 (en) | 1987-08-03 | 1988-08-03 | Method for ceramic coating on metals |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP0302465A3 (en) |
| JP (1) | JPH0730459B2 (en) |
| AU (1) | AU606726B2 (en) |
| BR (1) | BR8803842A (en) |
| MX (1) | MX170165B (en) |
Families Citing this family (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5925043A (en) * | 1997-04-30 | 1999-07-20 | Medquest Products, Inc. | Electrosurgical electrode with a conductive, non-stick coating |
| DE10014035B4 (en) * | 2000-03-22 | 2006-07-13 | Electro Chemical Engineering Gmbh | Colored conversion layer, a solution for their preparation and their use |
| 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 |
| WO2005003033A2 (en) | 2002-12-23 | 2005-01-13 | Applied Thin Films, Inc. | Aluminum phosphate coatings |
| CA2546628A1 (en) * | 2003-11-19 | 2005-07-07 | Applied Thin Films, Inc. | Aluminum phosphate compounds, compositions, materials and related metal coatings |
| EP1910595B1 (en) | 2005-06-30 | 2018-08-08 | Unifrax I LLC | Phosphate coated inorganic fiber and methods of preparation and use |
| JP5153063B2 (en) | 2005-07-15 | 2013-02-27 | 日本発條株式会社 | Steel surface treatment method |
| JP2008106340A (en) * | 2006-10-27 | 2008-05-08 | Nhk Spring Co Ltd | Aluminum phosphate-based chemical conversion treatment liquid for steel and its production method |
| US8497018B2 (en) | 2010-01-27 | 2013-07-30 | Applied Thin Films, Inc. | High temperature stable amorphous silica-rich aluminosilicates |
| CN103044995A (en) * | 2013-01-28 | 2013-04-17 | 陈立晓 | High temperature coating for diesel engine exhaust air duct |
| PL2969989T3 (en) | 2013-03-15 | 2019-10-31 | Unifrax I Llc | Inorganic fiber |
| CN103741195B (en) * | 2013-12-23 | 2016-06-15 | 南通恒新金属工艺科技有限公司 | Electrolytic phosphating of steel wires processes device |
| ES2744914T3 (en) | 2014-07-16 | 2020-02-26 | Unifrax I Llc | Inorganic fiber with improved shrinkage and strength |
| US10023491B2 (en) | 2014-07-16 | 2018-07-17 | Unifrax I Llc | Inorganic fiber |
| KR102289267B1 (en) | 2014-07-17 | 2021-08-11 | 유니프랙스 아이 엘엘씨 | Inorganic fiber with improved shrinkage and strength |
| US9919957B2 (en) | 2016-01-19 | 2018-03-20 | Unifrax I Llc | Inorganic fiber |
| CN111448173A (en) | 2017-10-10 | 2020-07-24 | 尤尼弗瑞克斯 I 有限责任公司 | Low Biopersistent Inorganic Fibers Free of Crystalline Silica |
| US10882779B2 (en) | 2018-05-25 | 2021-01-05 | Unifrax I Llc | Inorganic fiber |
| CN110438485A (en) * | 2019-07-29 | 2019-11-12 | 吴俊杰 | A kind of phosphatization treatment system of PVC spray-bonding craft |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR884852A (en) * | 1940-05-10 | 1943-08-30 | Opel Adam Ag | Method for protecting the interior surface of gasoline tanks and liquid fuel lines from rust |
| JPS536945B2 (en) * | 1973-02-27 | 1978-03-13 | ||
| 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/en not_active Expired - Lifetime
-
1988
- 1988-08-03 EP EP88112601A patent/EP0302465A3/en not_active Withdrawn
- 1988-08-03 AU AU20386/88A patent/AU606726B2/en not_active Ceased
- 1988-08-03 BR BR8803842A patent/BR8803842A/en not_active IP Right Cessation
- 1988-08-31 MX MX012534A patent/MX170165B/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| EP0302465A3 (en) | 1990-01-31 |
| MX170165B (en) | 1993-08-10 |
| BR8803842A (en) | 1989-02-21 |
| JPS6436774A (en) | 1989-02-07 |
| JPH0730459B2 (en) | 1995-04-05 |
| EP0302465A2 (en) | 1989-02-08 |
| AU2038688A (en) | 1989-02-09 |
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