GB2076432A - Cu-Ni coatings on ferrous substrates - Google Patents
Cu-Ni coatings on ferrous substrates Download PDFInfo
- Publication number
- GB2076432A GB2076432A GB8033335A GB8033335A GB2076432A GB 2076432 A GB2076432 A GB 2076432A GB 8033335 A GB8033335 A GB 8033335A GB 8033335 A GB8033335 A GB 8033335A GB 2076432 A GB2076432 A GB 2076432A
- Authority
- GB
- United Kingdom
- Prior art keywords
- alloy
- copper
- nickel
- coating
- rich
- 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- Withdrawn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
- 238000000576 coating method Methods 0.000 title claims description 20
- 229910002482 Cu–Ni Inorganic materials 0.000 title 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 title 1
- 239000000758 substrate Substances 0.000 title 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 42
- 229910000831 Steel Inorganic materials 0.000 claims abstract description 39
- 239000010959 steel Substances 0.000 claims abstract description 39
- 238000000034 method Methods 0.000 claims abstract description 25
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 22
- 229910052802 copper Inorganic materials 0.000 claims abstract description 21
- 239000010949 copper Substances 0.000 claims abstract description 21
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000001257 hydrogen Substances 0.000 claims abstract description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000000137 annealing Methods 0.000 claims abstract description 6
- 239000007789 gas Substances 0.000 claims abstract description 4
- 239000000956 alloy Substances 0.000 claims description 26
- 229910045601 alloy Inorganic materials 0.000 claims description 23
- 239000011248 coating agent Substances 0.000 claims description 19
- 238000000151 deposition Methods 0.000 claims description 9
- 230000007704 transition Effects 0.000 claims description 8
- 229910000570 Cupronickel Inorganic materials 0.000 claims description 6
- 230000008021 deposition Effects 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- YOCUPQPZWBBYIX-UHFFFAOYSA-N copper nickel Chemical compound [Ni].[Cu] YOCUPQPZWBBYIX-UHFFFAOYSA-N 0.000 claims description 4
- 239000011253 protective coating Substances 0.000 claims description 4
- 239000010935 stainless steel Substances 0.000 claims description 4
- 229910001220 stainless steel Inorganic materials 0.000 claims description 4
- 229910001339 C alloy Inorganic materials 0.000 claims description 3
- 229910000975 Carbon steel Inorganic materials 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 238000001465 metallisation Methods 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 238000005234 chemical deposition Methods 0.000 claims 1
- 238000004040 coloring Methods 0.000 claims 1
- QFXZANXYUCUTQH-UHFFFAOYSA-N ethynol Chemical group OC#C QFXZANXYUCUTQH-UHFFFAOYSA-N 0.000 claims 1
- 150000002431 hydrogen Chemical class 0.000 claims 1
- 239000010410 layer Substances 0.000 abstract description 27
- 230000007797 corrosion Effects 0.000 abstract description 16
- 238000005260 corrosion Methods 0.000 abstract description 16
- 239000011247 coating layer Substances 0.000 abstract description 4
- 238000009877 rendering Methods 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- 238000010285 flame spraying Methods 0.000 abstract 1
- 229910000792 Monel Inorganic materials 0.000 description 3
- 238000005275 alloying Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910000851 Alloy steel Inorganic materials 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- 229910000963 austenitic stainless steel Inorganic materials 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- -1 perborates Chemical class 0.000 description 1
- 150000003839 salts Chemical class 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
- C23C26/00—Coating not provided for in groups C23C2/00 - C23C24/00
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
- Solid-Phase Diffusion Into Metallic Material Surfaces (AREA)
- Coating By Spraying Or Casting (AREA)
- Physical Vapour Deposition (AREA)
- Electroplating Methods And Accessories (AREA)
Abstract
A method is disclosed for rendering steel articles corrosion resistant, wherein on the steel article surface two layers are deposited, one whereof comprises nickel and the other copper, the coated article being successively subjected to an annealing step at high temperature under a reducing gas atmosphere. interdiffusion of the Cu and Ni gives rise to a single coating layer with a compositional variation across its thickness. The layers may be initially applied by any known method e.g. electrochemical, chemical, flame spraying, plasma, etc. The annealing step may take place in an atmosphere containing hydrogen at a temperature of 950-1150 DEG C.
Description
SPECIFICATION
Method for making steel corrosion resistant
The present invention relates to a method adapted to make the steel corrosion-proof (resistant) and relates also to the products thus obtained.
More particularly, the present invention relates to a method or process for protecting products made of steel from corrosion phenomena in aqueous environments containing oxidizing salts such as perborates, hypoclorites, and the like and/or containing chloride ions.
As it is known, in such environments serious corrosion phenomena may appear. To overcome them, chrome-nickel stainless steels or steel objects having their surfaces nickel- or chromium-plated are commonly used.
However, the solutions hitherto used though they did lenghthen the service life of the respective metalic products and increase their resistance to the aforesaid corrosive environments, were not found completely satisfactory. Actually, in such corrosive environments, localized corrosion phenomena occur which, in case of products made of austenitic stainless steel, appear mostly in zones subjected to stress (stress corrosion) and due to the forming of activepassive couples (pitting and crevice corrosion). In the case of products having their surface coated (e.g.
nickel-plated) the more serious corrosion phenomena appear where scratches, fissures or cracks are present in the coating; at such defective points or zones where these localized phenomena may be generated, the steel base is corroded at an elevated rate and is rapidly put out of service.
Accordingly, the present invention sets out to provide a method for rendering corrosion proof or resistent products or articles made of steel, particularly those to be used in chlorinated and/orstrongly oxidizing environments, which corrosion resistance is durable even when local defects appear on the surface, such as inclusions, pitting, fissures, strain deformations and the like.
According to one aspect of the present invention there is provided a corrosion resistant steel product or article comprising a steel body wherein the surface thereof is coated by a protective coating consisting of a copper-nickel alloy.
According to another aspect of the invention there is further provided a method for making a corrosion resistant steel product or article comprising the steps of: depositing onto the surface of a steel body two metalic layers, one whereof being copper and the other of nickel, and heat treating said product by annealing at a temperature from 950 to 11 50 C, in a
reducing gas atmosphere in such a way asto obtain on said product surface a protective coating consisting of a copper-nickel alloy.
Thus the method according to the invention comprises a double deposition of a nickel layer and of a copper layer, which layers may be applied in any order. The deposition step of these layers may be carried out by any suitable method for depositing metals, such as by an electrochemical, or chemical method, oxyacetilene fiame, metalization, plasma and soon.
The steel body which effective to be treated by the instant method may be made of any type of steel, that is carbon steels, alloy or compound steels, stainless steels, special steels and so on.
The overall thickness of the two aforementioned layers may vary depending on the needs, from a minimum of one micron up to about 50 microns or even more. The relative thickness of the two layers, respectively of copper and nickel, may also vary according to the specific requirements and, for example for the copper layer, a suitable range is from 1 to 15 microns.
After depositing the two aforesaid layers, a heat alloying treatment is carried out, by annealing in an oven at a temperature from about 950 to about 1150"C under a reducing atmosphere. This latter may consist of pure hydrogen or, preferably, a mixture of hydrogen with nitrogen or argon, these mixtures having a minimum hydrogen percentage of 10%.
As a result of the heat treatment, the two layers of the coating become alloyed, that is an alloy is obtained therefrom as well as from the two layers and the base metal, i.e. the steel being treated. The composition of the obtained alloy will vary through the thickness of the coating and it will also vary depending on the deposition order of the layers. This first heat alloying treatment may be followed, if necessary, by a second heat treatment at high temperature under an atmosphere containing 2 or H2O or
CO2 or other suitable oxidizing agent to give a certain colour or different colours to the alloyed layer.
In an embodiment of the method, wherein there is firstly deposited the nickel layer and then the copper layer, at the end of the heat alloying treatment an external coating layer consisting of a copper rich alloy, that is of the cupronickel type, and an inner coating layer between the external layer and there ated steel body are obtained, said inner layer consisting of a nickel rich alloy, that is of the type commercially known as Monel. Furthermore, the annealing treatment will also lead to the formation of a transition layer on the surface of the steel body which transition layer is in direct contact with the first coating layer, in this case of nickel, due to the diffusion of the nickel in the steel and the formation of a nickel rich alloy steel.The product which is obtained in this case presents an alloyed layer (coating) having a galvanic potential (in the aforementioned oxidizing corrosive enviroments) which varies from more positive external values, at the outer surface of the formed coating, to less positive inner values, this variation being continuous and allowing for the coating forming noble materials to pass to the passivable material, that is the base body steel, in such a way as to provide an anodic protection of this latter.
In an alternative embodiment of the method, on said steel body, there is firstly deposited the copper layer and then the nickel layer. In this case, afterthe heat treatment, the obtained anti-corrosive coating will be formed by an outer or external layer composed of an alloy rich in nickel, that is, of the Monel type, and of an inner layer formed of an alloy of the
cupronickel type, that is an alloy more rich in copper.
The transition zone to the surface of the steel body,
under the anti-corrosive coating, will be in this case
obtained by diffusion of copper through the steel
and therefore it will consist of alloy of copper steel.
In this case an object protected against corrosion will
be obtained, the outer layer whereof, made of an
alloy of Monel type, presents an improved or
increased resistance to corrosive agents, while the transition zone on the surface of the steel under the coating has a copper content superior to the normal, which content may lead to an increased corrosion resistance thereby affording an intrinsic anodic protection.
Thus, by the method according to the present invention a product made of steel is obtained which is highly resistent to corrosion, particularly to corrosion in oxidating enviroment, and to corrosion from stress, pittings, fissures and soon. Furthermore,the product may develop, in case of necessity, an efficient anodic autoprotection, which guarantees to it a lenghthened service life even when localized corrosion phenomena appear.
Claims (17)
1. A corrosion resistant steel product or article, comprising a steel body, wherein the surface of said product is coated by a protective coating consisting of a copper-nickel alloy.
2. A product according to claim 1 comprising a transition zone to the surface of said steel body underlying said coating and comprising steel and a major amount of one of the two components of said alloy.
3. A product according to anyone of the preceding claims, wherein said coating has a copper and nickel content which is variable through the thickness thereof.
4. A product according to claim 3, wherein said coating comprises an external layer of said alloy more rich in copper and an inner layer of said alloy more rich in nickel, and wherein said transition zone comprises steel rich in nickel.
5. A product according to claim 3, wherein said coating comprises an external layer of said alloy more rich in nickel and an inner layer of said alloy more rich in copper, and wherein said transition zone comprises steel rich in copper.
6. A product according to anyone of the preceding claims, wherein said coating has a thickness from 1 to 50 microns.
7. A product according to anyone of the preceding claims, wherein said steel body comprises steel selected from carbon steels, alloy or compound steels, stainless steels and special steels.
8. A method for making a corrosion resistant steel product or article comprising the steps of: depositing onto the surface of a steel body two metallic layers, one whereof being of copper and the other of nickel, and heat treating said product by annealing at a temperature from 950 to 11 50 C in a reducing gas atmosphere in such a way as to obtain on said product surface a protective coating consisting of a copper-nickel alloy.
9. A method according to claim 8 wherein on the surface of said steel body underlying said coating a
transition zone is formed which comprises steel rich
in one of the components of said alloy.
10. A method according to anyone of claims 8 to
9 wherein the composition of said alloy varies
through the thickness of said coating.
11. A method according to anyone of claims 8 to
10 wherein nickel is deposited first and copper is
deposited successively and wherein said coating is
provided with an external layer comprising said
alloy more rich in copper and an inner layer compris fng said alloy more rich in nickel.
12. A method according to anyone of claims 8 to 10 wherein copper is deposited first and nickel is deposited successively and wherein said coating is provided with an external layer comprising said alloy more rich in nickel and an inner layer comprising said alloy more rich in copper.
13. A method according to anyone of claims 8 to 12 wherein said coating is formed with a thickness from 1 to about 50 microns.
14. A method according to anyone of claims 8 to 13 wherein said metal layer deposition stepcom- prises electrochemical, chemical deposition, oxyacetylene flame metalization, plasma deposition or their combinations.
15. A method according to anyone of claims 8 to 14 wherein said reducing gas is selected from hydrogen, and mixtures of hydrogen with nitrogen and argon containing at least 10% of hydrogen.
16. A method according to anyone of claims 8 to 15 characterized in that it is applicable to carbon steels, alloy or compound steels, stainless steels or special steels.
17. A method for colouring the alloyed layer obtained according to claims 8 to 15, by carrying out, after said treatment in a reducing atmosphere, a treatment at an identical temperature but in an oxidating atmosphere in the presence of 2 or H2O or CO2 or the like.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| IT20536/80A IT1129633B (en) | 1980-03-12 | 1980-03-12 | PROCEDURE FOR THE ANTI-CORROSIVE TREATMENT OF STEEL PRODUCTS |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| GB2076432A true GB2076432A (en) | 1981-12-02 |
Family
ID=11168414
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB8033335A Withdrawn GB2076432A (en) | 1980-03-12 | 1980-10-16 | Cu-Ni coatings on ferrous substrates |
Country Status (5)
| Country | Link |
|---|---|
| DE (1) | DE3039731A1 (en) |
| ES (2) | ES8202372A1 (en) |
| FR (1) | FR2478131A1 (en) |
| GB (1) | GB2076432A (en) |
| IT (1) | IT1129633B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0620292A2 (en) * | 1993-04-16 | 1994-10-19 | Shinko Kosen Kogyo Kabushiki Kaisha | Steel material for colored spring, method for producing colored spring, and colored spring |
| GB2320033A (en) * | 1996-12-05 | 1998-06-10 | Fmc Corp | Improvements in strength and wear resistance of mechanical components by adhering an alloy |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2521387B2 (en) * | 1991-12-25 | 1996-08-07 | 神鋼鋼線工業株式会社 | Manufacturing method of colored spring steel molded product |
| AT507894B1 (en) * | 2009-01-27 | 2010-09-15 | Andritz Hydro Gmbh | METHOD AND DEVICE FOR PRODUCING WORKPIECES WITH A STAINLESS STEEL SURFACE |
| DE102016218688A1 (en) | 2016-09-28 | 2018-03-29 | Bayerische Motoren Werke Aktiengesellschaft | Process for producing a hydrogen-carrying steel component for use in motor vehicles, hydrogen-carrying steel component and motor vehicle with a hydrogen-carrying steel component |
-
1980
- 1980-03-12 IT IT20536/80A patent/IT1129633B/en active
- 1980-10-16 GB GB8033335A patent/GB2076432A/en not_active Withdrawn
- 1980-10-21 DE DE19803039731 patent/DE3039731A1/en not_active Withdrawn
- 1980-10-27 ES ES496290A patent/ES8202372A1/en not_active Expired
- 1980-10-31 FR FR8023410A patent/FR2478131A1/en active Pending
-
1981
- 1981-11-05 ES ES506865A patent/ES506865A0/en active Granted
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0620292A2 (en) * | 1993-04-16 | 1994-10-19 | Shinko Kosen Kogyo Kabushiki Kaisha | Steel material for colored spring, method for producing colored spring, and colored spring |
| EP0620292A3 (en) * | 1993-04-16 | 1994-10-26 | Shinko Kosen Kogyo Kabushiki Kaisha | Steel material for colored spring, method for producing colored spring, and colored spring |
| US5455121A (en) * | 1993-04-16 | 1995-10-03 | Shinko Kosen Kogyo Kabushiki Kaisha | Steel material for a colored spring |
| GB2320033A (en) * | 1996-12-05 | 1998-06-10 | Fmc Corp | Improvements in strength and wear resistance of mechanical components by adhering an alloy |
| GB2320033B (en) * | 1996-12-05 | 2001-06-06 | Fmc Corp | Improvements in strength and wear resistance of mechanical components |
| US6403235B1 (en) | 1996-12-05 | 2002-06-11 | Fmc Corporation | Strength and wear resistance of mechanical components |
Also Published As
| Publication number | Publication date |
|---|---|
| ES496290A0 (en) | 1982-01-16 |
| IT1129633B (en) | 1986-06-11 |
| ES8206663A1 (en) | 1982-08-16 |
| ES8202372A1 (en) | 1982-01-16 |
| IT8020536A0 (en) | 1980-03-12 |
| FR2478131A1 (en) | 1981-09-18 |
| DE3039731A1 (en) | 1981-09-24 |
| ES506865A0 (en) | 1982-08-16 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| WAP | Application withdrawn, taken to be withdrawn or refused ** after publication under section 16(1) |