US3236752A - Method of alloying prosphorus and nickel in a fused salt bath - Google Patents
Method of alloying prosphorus and nickel in a fused salt bath Download PDFInfo
- Publication number
- US3236752A US3236752A US270772A US27077263A US3236752A US 3236752 A US3236752 A US 3236752A US 270772 A US270772 A US 270772A US 27077263 A US27077263 A US 27077263A US 3236752 A US3236752 A US 3236752A
- Authority
- US
- United States
- Prior art keywords
- nickel
- article
- salt bath
- fused salt
- alkali metal
- 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
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims description 30
- 238000000034 method Methods 0.000 title claims description 20
- 229910052759 nickel Inorganic materials 0.000 title claims description 15
- 150000003839 salts Chemical class 0.000 title claims description 15
- 238000005275 alloying Methods 0.000 title description 3
- 238000000576 coating method Methods 0.000 claims description 17
- 239000011248 coating agent Substances 0.000 claims description 13
- 229910001514 alkali metal chloride Inorganic materials 0.000 claims description 7
- 229910052783 alkali metal Inorganic materials 0.000 claims description 6
- 150000001340 alkali metals Chemical class 0.000 claims 2
- 229910001096 P alloy Inorganic materials 0.000 description 9
- OFNHPGDEEMZPFG-UHFFFAOYSA-N phosphanylidynenickel Chemical compound [P].[Ni] OFNHPGDEEMZPFG-UHFFFAOYSA-N 0.000 description 9
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 7
- 239000011574 phosphorus Substances 0.000 description 7
- 229910052698 phosphorus Inorganic materials 0.000 description 7
- 239000000203 mixture Substances 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 4
- 229910045601 alloy Inorganic materials 0.000 description 4
- 239000000956 alloy Substances 0.000 description 4
- 229910002804 graphite Inorganic materials 0.000 description 4
- 239000010439 graphite Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- MOMKYJPSVWEWPM-UHFFFAOYSA-N 4-(chloromethyl)-2-(4-methylphenyl)-1,3-thiazole Chemical compound C1=CC(C)=CC=C1C1=NC(CCl)=CS1 MOMKYJPSVWEWPM-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 235000011164 potassium chloride Nutrition 0.000 description 2
- 239000001103 potassium chloride Substances 0.000 description 2
- 239000011253 protective coating Substances 0.000 description 2
- 235000019983 sodium metaphosphate Nutrition 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- OQZCJRJRGMMSGK-UHFFFAOYSA-M potassium metaphosphate Chemical compound [K+].[O-]P(=O)=O OQZCJRJRGMMSGK-UHFFFAOYSA-M 0.000 description 1
- 229940099402 potassium metaphosphate Drugs 0.000 description 1
- ZLMJMSJWJFRBEC-BJUDXGSMSA-N potassium-38 Chemical compound [38K] ZLMJMSJWJFRBEC-BJUDXGSMSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-AKLPVKDBSA-N potassium-42 Chemical compound [42K] ZLMJMSJWJFRBEC-AKLPVKDBSA-N 0.000 description 1
- 239000011780 sodium chloride Substances 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
- C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C8/40—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using liquids, e.g. salt baths, liquid suspensions
- C23C8/42—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using liquids, e.g. salt baths, liquid suspensions only one element being applied
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D9/00—Electrolytic coating other than with metals
- C25D9/04—Electrolytic coating other than with metals with inorganic materials
- C25D9/08—Electrolytic coating other than with metals with inorganic materials by cathodic processes
Definitions
- an object of this invention is to provide a simple, economical method of forming a hard, corrosionresistant coating of nickel-phosphorus alloy on a nickelsurfaced article. Another object is to provide a method of forming nickel-phosphorus alloy coatings of any desired thickness on nickel-surfaced articles.
- the article or piece to be coated with nickel-phosphorus alloy is either fabricated from nickel, or is nickel-plated by any suitable process, so as to provide a nickel surface into which phosphorus may be diffused.
- a fused salt bath is prepared by melting a mixture of an alkali metal metaphosphate and one or more alkali metal chlorides in a container of suitable size and shape.
- the alkali metal metaphosphate provides the required elemental phosphorus, and should comprise at least about 2% by weight of the total mixture. Preferably, it comprises about 7% to about 100% by weight of the total mixture, to insure that the phosphorus concentration is sufficient to achieve the desired diffusion within a con venient length of time.
- the alkali metal chlorides serve as diluents capable of lowering the melting point of the mixture. They may be present up to about 98% by weight of the total mixture; for the reason discussed above, it is preferred that they comprise about 93% or less of the mixture.
- the fused salt bath is maintained at a temperature within the range of about 400 C. to about 1000" C.
- the temperature may be maintained between about 400 C. and about 700 C., thus effecting a savings in the heat required for operation of the bath.
- the nickel-surfaced article to be coated is immersed in the fused salt bath. If a thin coating less than about 0.0005 inch of nickel-phosphorus alloy is desired, the article is kept immersed in the bath for a short time and then removed. The time is not critical and may range from about 5 seconds to about 5 minutes. After removal from the bath, the article is cooled in air to about room temperature, washed in flowing water to remove any salts adhering thereto, and dried.
- the fused salt bath is electrolyzed, with the immersed article connected as the cathode.
- the current density is adjusted within the range of about one ampere to about 200 amperes per square decimeter of surface of the article. In general, a current density of about 10 amperes to about amperes per square decimeter is preferred, since densities below about 10 amperes per square decimeter require inconveniently long plating times, while densities above about 100 amperes per square decimeter result in coatings that are porous and dark in color.
- Example I About 10 grams of sodium metaphosphate, 74 grams of potassium chloride, and 38 grams of sodium chloride were melted together in a graphite crucible, and maintained at a temperature of about 600 C. to about 900 C. A nickel-plated sheet was immersed in the bath for about one minute, removed, cooled in air to about room temperature, washed in water, and dried. The coating had a hardness of about 580 Knoop.
- Example II About 10 grams of potassium metaphosphate, 74 grams of potassium chloride, and 42 grams of lithium chloride were melted together in a graphite crucible, and maintained at a temperature of about 400 C. to about 700 C. A nickel-plated sheet was immersed in the bath and connected as the cathode, the graphite crucible being the anode. A direct current of about 25 amperes to about 50 amperes per square decimeter of surface of the immersed sheet was passed through the bath for one hour, after which the sheet was removed, air-cooled, washed in water, and dried. The coating had a hardness of about 580 Knoop.
- Example 111 About grams of sodium metaphosphate was melted in a graphite crucible and maintained at a temperature of about 800 C. to about 1000 C. Using a nickel sheet as cathode, the bath was electrolyzed at a current density of about 25 amperes to about 50 amperes per square decimeter of surface of the sheet for about one hour. The sheet was then removed, air-cooled, to about room temperature, washed under flowing water, and dried. The coating hardness tested to about 580 Knoop.
- the present invention provides a simple, economical method of forming hard, protective coatings of nickel-phosphorus alloy on nickel or nickel-plated articles.
- the method enables one to deposit coatings of any desired thickness in a controllable manner.
- the method of forming a coating of nickelphosphorus alloy on an article having a nickel surface which comprises treating said article in a fused salt bath consisting essentially of an alkali metal metaphosphate and up to about 98% by weight of alkali metal chlorides.
- the method of forming a coating of nickelphosphorus alloy on an article having a nickel surface which comprises electrolyzing a fused salt bath consisting essentially of an alkali metal metaphosphate and up to about 98% by weight of alkali metal chlorides in an electrolytic cell in which said article is cathodic.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Electrochemistry (AREA)
- Mechanical Engineering (AREA)
- Electroplating And Plating Baths Therefor (AREA)
Description
United States Patent 3,236,752 METHOD OF ALLOYING PROSPHORUS AND NICKEL IN A FUSED SALT BATH Dwight E. Couch, Boulder City, Nev., assignor to the United States of America as represented by the Secretary of Commerce No Drawing. Filed Apr. 4, 1963, Ser. No. 270,772 5 Claims. (Cl. 204-39) This invention relates to a method of alloying phosphorus and nickel, and more particularly relates to a method of forming a coating of nickel-phosphorus alloy on articles having nickel surfaces.
There are various known methods of forming hard, protective coatings of nickel-phosphorus alloy on articles, in which nickel and phosphorus are co-deposited to form the alloy. Since many articles are fabricated from nickel, or are normally nickel-plated during the manufacture thereof, it would be desirable to provide a method of diffusing phosphorus into the nickel surfaces thereof, to provide the desired coating of nickel-phosphorus alloy.
Accordingly, an object of this invention is to provide a simple, economical method of forming a hard, corrosionresistant coating of nickel-phosphorus alloy on a nickelsurfaced article. Another object is to provide a method of forming nickel-phosphorus alloy coatings of any desired thickness on nickel-surfaced articles.
These and other objects are attained in accordance with this invention by a process in which phosphorus is deposited out of a molten salt bath onto a nickel-surfaced article.
Other objects, advantages and features of the present invention will become more apparent from the following description of a preferred embodiment thereof.
In accordance with this invention, the article or piece to be coated with nickel-phosphorus alloy is either fabricated from nickel, or is nickel-plated by any suitable process, so as to provide a nickel surface into which phosphorus may be diffused.
Further, in accordance with this invention, a fused salt bath is prepared by melting a mixture of an alkali metal metaphosphate and one or more alkali metal chlorides in a container of suitable size and shape. The alkali metal metaphosphate provides the required elemental phosphorus, and should comprise at least about 2% by weight of the total mixture. Preferably, it comprises about 7% to about 100% by weight of the total mixture, to insure that the phosphorus concentration is sufficient to achieve the desired diffusion within a con venient length of time. The alkali metal chlorides serve as diluents capable of lowering the melting point of the mixture. They may be present up to about 98% by weight of the total mixture; for the reason discussed above, it is preferred that they comprise about 93% or less of the mixture.
The fused salt bath is maintained at a temperature within the range of about 400 C. to about 1000" C. When moderate amounts of the alkali metal chloride diluents are employed, the temperature may be maintained between about 400 C. and about 700 C., thus effecting a savings in the heat required for operation of the bath.
The nickel-surfaced article to be coated is immersed in the fused salt bath. If a thin coating less than about 0.0005 inch of nickel-phosphorus alloy is desired, the article is kept immersed in the bath for a short time and then removed. The time is not critical and may range from about 5 seconds to about 5 minutes. After removal from the bath, the article is cooled in air to about room temperature, washed in flowing water to remove any salts adhering thereto, and dried.
ice
If thicker coatings of nickel-phosphorus alloy are desired to be formed on the nickel-surfaced article, the fused salt bath is electrolyzed, with the immersed article connected as the cathode. The current density is adjusted within the range of about one ampere to about 200 amperes per square decimeter of surface of the article. In general, a current density of about 10 amperes to about amperes per square decimeter is preferred, since densities below about 10 amperes per square decimeter require inconveniently long plating times, while densities above about 100 amperes per square decimeter result in coatings that are porous and dark in color. In most instances, an operating density of about 25 amperes to about 50 amperes per square decimeter has proved to be satisfactory, resulting in the formation of about 0.007 inch to about 0.010 inch of alloy coating per hour of electrolysis. After the desired thickness of coating has been formed, the article is removed from the bath and cooled, washed, and dried as described above.
The following examples illustrate the invention.
Example I About 10 grams of sodium metaphosphate, 74 grams of potassium chloride, and 38 grams of sodium chloride were melted together in a graphite crucible, and maintained at a temperature of about 600 C. to about 900 C. A nickel-plated sheet was immersed in the bath for about one minute, removed, cooled in air to about room temperature, washed in water, and dried. The coating had a hardness of about 580 Knoop.
Example II About 10 grams of potassium metaphosphate, 74 grams of potassium chloride, and 42 grams of lithium chloride were melted together in a graphite crucible, and maintained at a temperature of about 400 C. to about 700 C. A nickel-plated sheet was immersed in the bath and connected as the cathode, the graphite crucible being the anode. A direct current of about 25 amperes to about 50 amperes per square decimeter of surface of the immersed sheet was passed through the bath for one hour, after which the sheet was removed, air-cooled, washed in water, and dried. The coating had a hardness of about 580 Knoop.
Example 111 About grams of sodium metaphosphate was melted in a graphite crucible and maintained at a temperature of about 800 C. to about 1000 C. Using a nickel sheet as cathode, the bath was electrolyzed at a current density of about 25 amperes to about 50 amperes per square decimeter of surface of the sheet for about one hour. The sheet was then removed, air-cooled, to about room temperature, washed under flowing water, and dried. The coating hardness tested to about 580 Knoop.
From the foregoing it will be appreciated that the present invention provides a simple, economical method of forming hard, protective coatings of nickel-phosphorus alloy on nickel or nickel-plated articles. The method enables one to deposit coatings of any desired thickness in a controllable manner.
Since various modifications of the process as described can be made within the scope of the invention, it is intended that the invention not be limited to the details of the specific processes disclosed, except as defined by the appended claims.
What is claimed is:
1. The method of forming a coating of nickelphosphorus alloy on an article having a nickel surface which comprises treating said article in a fused salt bath consisting essentially of an alkali metal metaphosphate and up to about 98% by weight of alkali metal chlorides.
2. The method defined in claim 1, wherein the temperature of said fused salt bath is in the range of about 400 C. to about 1000 C.
3. The method of forming a coating of nickelphosphorus alloy on an article having a nickel surface which comprises electrolyzing a fused salt bath consisting essentially of an alkali metal metaphosphate and up to about 98% by weight of alkali metal chlorides in an electrolytic cell in which said article is cathodic.
4. The method defined in claim 3, wherein the temperature of said fused salt bath is in the range of about 400 C. to about 1000 C.
References Cited by the Examiner UNITED STATES PATENTS 7/1935 McCauley l48-6.1l 1/1942 MacKay 1486.11
WINSTON A. DOUGLAS, Primary Examiner.
G. KAPLAN, Assistant Examiner.
Claims (2)
1. THE METHOD OF FORMING A COATING OF NICKELPHOSPHORUS ALLOY ON AN ARTICLE HAVING A NICKEL SURFACE WHICH COMPRISES TREATING SAID ARTICLE IN A FUSED SALT BATH WHICH COMPRISES TREATING SAID ARTICLE IN A FUSED SALT BATH CONSISTING ESSENTIALLY OF AN ALKALI METAL METAPHOSPHATE AND UP TO ABOUT 98% BY WEIGHT OF ALKALI METAL CHLORIDES.
3. THE METHOD OF FORMING A COATING OF NICKELPHOSPHORUS ALLOY ON AN ARTICLE HAVING A NICKEL SURFACE WHICH COMPRISES ELECTROLYZING A FUSED SALT BATH CONSISTING ESSENTIALLY OF AN ALKALI METAL METAPHOSPHATE AND UP TO ABOUT 98% BY WEIGHT OF ALKALI METAL CHLORIDES IN AN ELECTROLYTIC CELL IN WHICH SAID ARTICLE IS CATHODIC.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US270772A US3236752A (en) | 1963-04-04 | 1963-04-04 | Method of alloying prosphorus and nickel in a fused salt bath |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US270772A US3236752A (en) | 1963-04-04 | 1963-04-04 | Method of alloying prosphorus and nickel in a fused salt bath |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3236752A true US3236752A (en) | 1966-02-22 |
Family
ID=23032740
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US270772A Expired - Lifetime US3236752A (en) | 1963-04-04 | 1963-04-04 | Method of alloying prosphorus and nickel in a fused salt bath |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US3236752A (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2007978A (en) * | 1933-06-19 | 1935-07-16 | Roy B Mccauley | Metal with phosphide case and process of producing same |
| US2271374A (en) * | 1935-08-13 | 1942-01-27 | Rust Proofing Company | Process of coating metal surfaces |
-
1963
- 1963-04-04 US US270772A patent/US3236752A/en not_active Expired - Lifetime
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2007978A (en) * | 1933-06-19 | 1935-07-16 | Roy B Mccauley | Metal with phosphide case and process of producing same |
| US2271374A (en) * | 1935-08-13 | 1942-01-27 | Rust Proofing Company | Process of coating metal surfaces |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US2746888A (en) | Method of forming titanium coating on refractory body | |
| US2828251A (en) | Electrolytic cladding process | |
| US1971761A (en) | Protection of metals | |
| US2929766A (en) | Plating of iridium | |
| US3024174A (en) | Electrolytic production of titanium plate | |
| US2805192A (en) | Plated refractory metals | |
| US2821505A (en) | Process of coating metals with bismuth or bismuth-base alloys | |
| US2990343A (en) | Chromium alloy plating | |
| US3203879A (en) | Method for preparing positive electrodes | |
| NO115607B (en) | ||
| US2950233A (en) | Production of hard surfaces on base metals | |
| US3697390A (en) | Electrodeposition of metallic boride coatings | |
| US3236752A (en) | Method of alloying prosphorus and nickel in a fused salt bath | |
| US3827954A (en) | Electrodeposition of metallic boride coatings | |
| US3111464A (en) | Electrodeposition of chromium and chromium alloys | |
| CA1158596A (en) | Composition and method for electrodeposition of black nickel | |
| US2623848A (en) | Process for producing modified electronickel | |
| US2985567A (en) | Electrodeposition of black chromium coatings | |
| US2921888A (en) | Electroplating titanium ano titanium alloys | |
| US2807575A (en) | Method of electroplating aluminum | |
| US2594933A (en) | Process for electrodepositing hard nickel plate | |
| US2418970A (en) | Process of electrolytically depositing iron and iron alloys | |
| US3247083A (en) | Method of chromium electrodeposition | |
| US2796392A (en) | Process and electrolyte for the electrodeposition of zirconium | |
| WO1998046809A1 (en) | A method for electroplating with a refractory metal |