US3390970A - Diffusion cladding aluminum article with a diffused zinc coat - Google Patents
Diffusion cladding aluminum article with a diffused zinc coat Download PDFInfo
- Publication number
- US3390970A US3390970A US509465A US50946565A US3390970A US 3390970 A US3390970 A US 3390970A US 509465 A US509465 A US 509465A US 50946565 A US50946565 A US 50946565A US 3390970 A US3390970 A US 3390970A
- Authority
- US
- United States
- Prior art keywords
- zinc
- base
- metal
- diffused
- diffusion
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title description 32
- 229910052725 zinc Inorganic materials 0.000 title description 32
- 239000011701 zinc Substances 0.000 title description 32
- 238000009792 diffusion process Methods 0.000 title description 9
- 238000005253 cladding Methods 0.000 title description 8
- 229910052782 aluminium Inorganic materials 0.000 title description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title description 6
- 239000010953 base metal Substances 0.000 description 19
- 229910052751 metal Inorganic materials 0.000 description 17
- 239000002184 metal Substances 0.000 description 17
- 239000011248 coating agent Substances 0.000 description 12
- 238000000576 coating method Methods 0.000 description 12
- 238000000034 method Methods 0.000 description 11
- 238000010438 heat treatment Methods 0.000 description 6
- 238000000151 deposition Methods 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000006735 deficit Effects 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 239000000956 alloy Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 230000001747 exhibiting effect Effects 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 230000001788 irregular Effects 0.000 description 2
- 230000035515 penetration Effects 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 239000003082 abrasive agent Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- FJMNNXLGOUYVHO-UHFFFAOYSA-N aluminum zinc Chemical compound [Al].[Zn] FJMNNXLGOUYVHO-UHFFFAOYSA-N 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 238000004210 cathodic protection Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000009877 rendering Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 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
- C23C10/00—Solid state diffusion of only metal elements or silicon into metallic material surfaces
- C23C10/28—Solid state diffusion of only metal elements or silicon into metallic material surfaces using solids, e.g. powders, pastes
-
- 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
- C23C10/00—Solid state diffusion of only metal elements or silicon into metallic material surfaces
-
- Y—GENERAL 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S428/00—Stock material or miscellaneous articles
- Y10S428/922—Static electricity metal bleed-off metallic stock
- Y10S428/9265—Special properties
- Y10S428/933—Sacrificial component
-
- Y—GENERAL 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S428/00—Stock material or miscellaneous articles
- Y10S428/922—Static electricity metal bleed-off metallic stock
- Y10S428/9335—Product by special process
- Y10S428/936—Chemical deposition, e.g. electroless plating
-
- Y—GENERAL 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/12—All metal or with adjacent metals
- Y10T428/12458—All metal or with adjacent metals having composition, density, or hardness gradient
Definitions
- the present invention relates to an aluminous base metal article wherein the surface metal is preferentially sacrificial to the core metal, exhibiting a gradient of diffused zinc from the surface into the base metal.
- aluminous base metals are metallurgically and laminarly clad with other aluminous metals containing various additive metals such as silver, cadmium, platinum, barium, bismuth, tin, and zinc sufficient in concentration to impart to the cladding layer a more active potential than that of the core metal so as to direct sacrificial corrosive attack to the cladding in preference to the core.
- additive metals such as silver, cadmium, platinum, barium, bismuth, tin, and zinc
- aluminous base metals pertains to metals containing predominantly aluminum.
- the term thus includes elemental aluminum and the aluminum base alloys.
- reference in this specification to zinc for initial coating purposes refers to metals consisting predominantly of zinc, and also refers to compounds containing zinc which are reducible to zinc metal by the aluminum during the diffusion heat treatment.
- -It is the object of this invention to provide a method whereby zinc is diffused into the surface of an aluminous metal base rendering a greater electrode potential to said aluminum-zinc surface gradient so that any corrosive attack will be preferentially directed to the diffused zinc enriched surface rather than to the base.
- a further object is to provide a process whereby the zinc may be diffused into the surface of the base metal with little or no impairment of the physical properties of the base article.
- a related object is to provide aluminous base metal articles having a protective diffused zinc surface the electrode potential of which is greater than that of the aluminous base metal.
- This invention is based upon the discovery that the surface of an aluminous base metal can be given a substantially greater electrode potential than the base by depositing on the surface thereof a coating consisting essentially of zinc metal and diffusing such coating into the surface of the base by heat treating the coated article, thereby providing a zinc enriched surface and composition gradient such that when placed in a corroding atmosphere cathodic protection results in that galvanic attack is directed to the diffused zinc enriched surface in preference to the aluminous base. Diffusion cladding under the invention in this manner is accomplished without serious impairment of the physical properties of the base article.
- any aluminous base metal configuration is coated with zinc metal or alloy thereof by any one of various methods of deposition known to the art so as to provide an initial zinc coating of about 0.10 Ing /cm. to about 10.0 mg./cm.
- the coating is then diffused into the surface of the base by heat treating at a temperature within the range from about 500 F. to about 1100 F. for about 0.1 to about hours.
- the heat treatment is to be sufiicient to accomplish at least a 0.001 inch penetration having at least a 0.5 percent zinc concentration at said depth penetration.
- the invention is practiced with the deposited coating of zinc to be diffused being approximately 0.8 mg./cm. with heat treatment to effect diffusion being carried out at about 970 F. for about 5 hours.
- the application of heat treatment time and temperature to effect diffusion directly depends upon the initial zinc concentration per unit area of base metal surface, that is, an initial concentration in the lower limits of the aforementioned coating range of 0.10 mg./cm. to 10.0 mg/cm. will require a lower heat treatment temperature and time to achieve optimum results, whereas, a heavy initial coating within said range will require a greater temperature and time.
- the time and temperature combination in relation to one another is inverse, that is, heat treating at higher temperatures will require less time to effect proper diffusion of a given initial zinc coating than with lower temperatures.
- One method of deposition found to be particularly satisfactory to obtain the initial zinc coating for diffusion is a two step zinc immersion process whereby the aluminous base metal is first activated in a dilute aqueous NaOH solution and then immersion plated with zinc by simple displacement in an alkaline zincate solution.
- Other methods of deposition known to the art are also applicable to the invention to obtain the initial zinc coating, such as metal spraying, electrodeposition, and mechanical plating with metal powder using abrasives.
- Table I indicates preferable, but not limiting, combinations of initial zinc coating weights to heat treatment temperatures and time.
- This invention provides a simple and economically practical process whereby all or any desired part of the exposed surfaces of any configuration of aluminous base metal articles can be given an electrode potential greater than that of the underlying base by enriching said surface by diffusion of zinc to provide a sacrifical zinc diffused surface which in the presence of a corroding medium will preferentially bear corrosive attack.
- the process causes, and the product shows, little or no impairment of the physical properties of the core metal.
- An aluminous base metal article wherein the surface metal is preferentially sacrificial to the core metal, exhibiting ditfusion from the surface into the base metal of about 0.10 mg. to about 10.0 mg. of zinc per square centimeter of surface as a gradient in zinc concentration from said surface into the base metal such that the zinc concentration at 1 mil below the surface is at least 0.5 Weight percent.
Description
United States Patent 3,390,970 DIFFUSION CLADDING ALUMINUM ARTICLE WITH A DIFFUSED ZINC COAT Marvin R. Bothwell, Midland, Mich., assignor to The Dow Chemical Company, Midland, Mich., a corporation of Delaware No Drawing. Original application Aug. 20, 1962, Ser. No. 218,128, now Patent No. 3,268,358, dated Aug. 23, 1966. Divided and this application Oct. 21, 1965, Ser. No. 509,465
1 Claim. (Cl. 29-197) ABSTRACT OF THE DISCLOSURE The present invention relates to an aluminous base metal article wherein the surface metal is preferentially sacrificial to the core metal, exhibiting a gradient of diffused zinc from the surface into the base metal.
This is a division of application Ser. No. 218,128 filed Aug. 20, 1962, now Patent 3,268,358.
Under present art aluminous base metals are metallurgically and laminarly clad with other aluminous metals containing various additive metals such as silver, cadmium, platinum, barium, bismuth, tin, and zinc sufficient in concentration to impart to the cladding layer a more active potential than that of the core metal so as to direct sacrificial corrosive attack to the cladding in preference to the core. In practice however, metallurgical and laminar cladding are economically or technically limited to sheet or plate core metal, and are comparatively expensive when applied to tubular goods and cannot be applied to irregular configurations such as castings.
In view of the limitation in metallurgical and laminar cladding techniques there is needed in the art for a simple and economical process whereby aluminous base metals of substantially any irregular configuration, the surfaces of which, can be processed to obtain a sacrificial nonlaminar cladding of a higher electrode potential than that of the base metal which will, therefore, corrode in pref erence to the base when in contact with a corroding medium and prevent pitting and other type corrosion of the base metal.
Further reference in this specification to aluminous base metals pertains to metals containing predominantly aluminum. The term thus includes elemental aluminum and the aluminum base alloys. Also, reference in this specification to zinc for initial coating purposes refers to metals consisting predominantly of zinc, and also refers to compounds containing zinc which are reducible to zinc metal by the aluminum during the diffusion heat treatment.
-It is the object of this invention to provide a method whereby zinc is diffused into the surface of an aluminous metal base rendering a greater electrode potential to said aluminum-zinc surface gradient so that any corrosive attack will be preferentially directed to the diffused zinc enriched surface rather than to the base.
It is also the object of this invention to provide an economical process whereby zinc can be diffused into the surface of an aluminous base metal of any configuration.
A further object is to provide a process whereby the zinc may be diffused into the surface of the base metal with little or no impairment of the physical properties of the base article. A related object is to provide aluminous base metal articles having a protective diffused zinc surface the electrode potential of which is greater than that of the aluminous base metal.
This invention is based upon the discovery that the surface of an aluminous base metal can be given a substantially greater electrode potential than the base by depositing on the surface thereof a coating consisting essentially of zinc metal and diffusing such coating into the surface of the base by heat treating the coated article, thereby providing a zinc enriched surface and composition gradient such that when placed in a corroding atmosphere cathodic protection results in that galvanic attack is directed to the diffused zinc enriched surface in preference to the aluminous base. Diffusion cladding under the invention in this manner is accomplished without serious impairment of the physical properties of the base article.
In practicing the invention any aluminous base metal configuration is coated with zinc metal or alloy thereof by any one of various methods of deposition known to the art so as to provide an initial zinc coating of about 0.10 Ing /cm. to about 10.0 mg./cm. The coating is then diffused into the surface of the base by heat treating at a temperature within the range from about 500 F. to about 1100 F. for about 0.1 to about hours. In any case, the heat treatment is to be sufiicient to accomplish at least a 0.001 inch penetration having at least a 0.5 percent zinc concentration at said depth penetration. Preferably, the invention is practiced with the deposited coating of zinc to be diffused being approximately 0.8 mg./cm. with heat treatment to effect diffusion being carried out at about 970 F. for about 5 hours.
The application of heat treatment time and temperature to effect diffusion directly depends upon the initial zinc concentration per unit area of base metal surface, that is, an initial concentration in the lower limits of the aforementioned coating range of 0.10 mg./cm. to 10.0 mg/cm. will require a lower heat treatment temperature and time to achieve optimum results, whereas, a heavy initial coating within said range will require a greater temperature and time. The time and temperature combination in relation to one another however, is inverse, that is, heat treating at higher temperatures will require less time to effect proper diffusion of a given initial zinc coating than with lower temperatures.
One method of deposition found to be particularly satisfactory to obtain the initial zinc coating for diffusion is a two step zinc immersion process whereby the aluminous base metal is first activated in a dilute aqueous NaOH solution and then immersion plated with zinc by simple displacement in an alkaline zincate solution. Other methods of deposition known to the art are also applicable to the invention to obtain the initial zinc coating, such as metal spraying, electrodeposition, and mechanical plating with metal powder using abrasives.
Table I indicates preferable, but not limiting, combinations of initial zinc coating weights to heat treatment temperatures and time.
This invention provides a simple and economically practical process whereby all or any desired part of the exposed surfaces of any configuration of aluminous base metal articles can be given an electrode potential greater than that of the underlying base by enriching said surface by diffusion of zinc to provide a sacrifical zinc diffused surface which in the presence of a corroding medium will preferentially bear corrosive attack. In addition, the process causes, and the product shows, little or no impairment of the physical properties of the core metal.
I claim:
1. An aluminous base metal article wherein the surface metal is preferentially sacrificial to the core metal, exhibiting ditfusion from the surface into the base metal of about 0.10 mg. to about 10.0 mg. of zinc per square centimeter of surface as a gradient in zinc concentration from said surface into the base metal such that the zinc concentration at 1 mil below the surface is at least 0.5 Weight percent. V I
References Cited UNITED STATES PATENTS 8/1966 Bothwell 117-131 HYLAND BIZ-OT, Primar Examiner.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US509465A US3390970A (en) | 1962-08-20 | 1965-10-21 | Diffusion cladding aluminum article with a diffused zinc coat |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US218128A US3268358A (en) | 1962-08-20 | 1962-08-20 | Diffusion cladding |
| US509465A US3390970A (en) | 1962-08-20 | 1965-10-21 | Diffusion cladding aluminum article with a diffused zinc coat |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3390970A true US3390970A (en) | 1968-07-02 |
Family
ID=26912603
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US509465A Expired - Lifetime US3390970A (en) | 1962-08-20 | 1965-10-21 | Diffusion cladding aluminum article with a diffused zinc coat |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US3390970A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5476725A (en) * | 1991-03-18 | 1995-12-19 | Aluminum Company Of America | Clad metallurgical products and methods of manufacture |
| EP0834592A1 (en) * | 1996-09-30 | 1998-04-08 | Toyota Jidosha Kabushiki Kaisha | Aluminum product having metal diffusion layer, process for producing the same, and paste for metal diffusion treatment |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2987814A (en) * | 1957-01-25 | 1961-06-13 | Reynolds Metals Co | Process and product of zinc and aluminum lamination |
| US3046640A (en) * | 1957-12-04 | 1962-07-31 | Reynolds Metals Co | Process and product of zinc and aluminum lamination |
| US3268358A (en) * | 1962-08-20 | 1966-08-23 | Dow Chemical Co | Diffusion cladding |
-
1965
- 1965-10-21 US US509465A patent/US3390970A/en not_active Expired - Lifetime
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2987814A (en) * | 1957-01-25 | 1961-06-13 | Reynolds Metals Co | Process and product of zinc and aluminum lamination |
| US3046640A (en) * | 1957-12-04 | 1962-07-31 | Reynolds Metals Co | Process and product of zinc and aluminum lamination |
| US3268358A (en) * | 1962-08-20 | 1966-08-23 | Dow Chemical Co | Diffusion cladding |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5476725A (en) * | 1991-03-18 | 1995-12-19 | Aluminum Company Of America | Clad metallurgical products and methods of manufacture |
| US5669436A (en) * | 1991-03-18 | 1997-09-23 | Aluminum Company Of America | Method of continuously casting composite strip |
| EP0834592A1 (en) * | 1996-09-30 | 1998-04-08 | Toyota Jidosha Kabushiki Kaisha | Aluminum product having metal diffusion layer, process for producing the same, and paste for metal diffusion treatment |
| US5989734A (en) * | 1996-09-30 | 1999-11-23 | Toyota Jidosha Kabushiki Kaisha | Aluminum product having metal diffusion layer, process for producing the same, and paste for metal diffusion treatment |
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