US2827400A - Electroless deposition of vanadium alloys - Google Patents
Electroless deposition of vanadium alloys Download PDFInfo
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- US2827400A US2827400A US639605A US63960557A US2827400A US 2827400 A US2827400 A US 2827400A US 639605 A US639605 A US 639605A US 63960557 A US63960557 A US 63960557A US 2827400 A US2827400 A US 2827400A
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- vanadium
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- chromium
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- 230000008021 deposition Effects 0.000 title claims description 10
- 229910000756 V alloy Inorganic materials 0.000 title description 5
- 229910052751 metal Chemical class 0.000 claims description 34
- 239000002184 metal Chemical class 0.000 claims description 34
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical class [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 32
- 229910052720 vanadium Inorganic materials 0.000 claims description 28
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 19
- 229910052804 chromium Inorganic materials 0.000 claims description 19
- 239000011651 chromium Substances 0.000 claims description 19
- 239000010941 cobalt Substances 0.000 claims description 17
- 229910017052 cobalt Inorganic materials 0.000 claims description 17
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 17
- 150000003839 salts Chemical class 0.000 claims description 15
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 14
- 239000003795 chemical substances by application Substances 0.000 claims description 12
- 238000007772 electroless plating Methods 0.000 claims description 9
- 150000002500 ions Chemical class 0.000 claims description 9
- 239000008139 complexing agent Substances 0.000 claims description 6
- 235000006408 oxalic acid Nutrition 0.000 claims description 4
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical class O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 claims description 4
- 239000011260 aqueous acid Substances 0.000 claims description 3
- 239000006172 buffering agent Substances 0.000 claims description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 30
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 24
- 229910045601 alloy Inorganic materials 0.000 description 17
- 239000000956 alloy Substances 0.000 description 17
- 229910052759 nickel Inorganic materials 0.000 description 15
- 239000000758 substrate Substances 0.000 description 15
- 239000000243 solution Substances 0.000 description 14
- 238000000151 deposition Methods 0.000 description 13
- 229910052742 iron Inorganic materials 0.000 description 12
- 238000000034 method Methods 0.000 description 10
- GQZXNSPRSGFJLY-UHFFFAOYSA-N hydroxyphosphanone Chemical compound OP=O GQZXNSPRSGFJLY-UHFFFAOYSA-N 0.000 description 9
- 229940005631 hypophosphite ion Drugs 0.000 description 9
- 229910021645 metal ion Inorganic materials 0.000 description 6
- 230000002378 acidificating effect Effects 0.000 description 4
- 239000003638 chemical reducing agent Substances 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000007747 plating Methods 0.000 description 3
- 150000003681 vanadium Chemical class 0.000 description 3
- 229910001456 vanadium ion Inorganic materials 0.000 description 3
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 2
- 239000001509 sodium citrate Substances 0.000 description 2
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 229910001369 Brass Inorganic materials 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- -1 Sodium hypophosphites Chemical class 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 230000001464 adherent effect Effects 0.000 description 1
- 239000003637 basic solution Substances 0.000 description 1
- 239000010951 brass Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- HBXWYZMULLEJSG-UHFFFAOYSA-N chromium vanadium Chemical compound [V][Cr][V][Cr] HBXWYZMULLEJSG-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- LLESOAREQXNYOK-UHFFFAOYSA-N cobalt vanadium Chemical compound [V].[Co] LLESOAREQXNYOK-UHFFFAOYSA-N 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- UIAIMGWRADQHKY-UHFFFAOYSA-N iron vanadium Chemical compound [Fe][V][Fe] UIAIMGWRADQHKY-UHFFFAOYSA-N 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- HBVFXTAPOLSOPB-UHFFFAOYSA-N nickel vanadium Chemical compound [V].[Ni] HBVFXTAPOLSOPB-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 229910021653 sulphate ion 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
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/48—Coating with alloys
- C23C18/50—Coating with alloys with alloys based on iron, cobalt or nickel
-
- 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
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/48—Coating with alloys
Definitions
- electroless deposition as known in the art described a process wherein a metallic substrate is inserted in a bath containing, in aqueous solution, a salt (such as a chloride or sulphate) of a metal selected from the group composed of nickel, cobalt and chromium; a hypophosphite salt (such as sodium hypophosphite); and a suitable bufiering (pH controlling) agent (such as sodium acetate).
- nickel, cobalt or chromium is deposited as a pure metal on the surface of the substrate. While the mechanism of this process is not fully understood, it is believed that the hypophosphite ion continuously reduces the dissolved metal salt to the metallic state on the surface of the substrate by means of a catalytic action involving the surface.
- This process is defined as electroless plating or deposition to diderentiate it from the conventional electro-plating or electrolytic deposition technique.
- any metal of the group composed of iron, nickel, cobalt and chromium can be electrolessly deposited through use of known techniques or through the use of the technique disclosed in the above mentioned copending application.
- vanadium could be electrolessly deposited in a similar manner. Accordingly we attempted to deposit vanadium in this way. Our attempts were unsuccessful; apparently the activity of vanadium is so high that it will oxidize before deposition occurs. In any event, the vanadium could only be electrolessly deposited in the form of an oxide. However, we discovered that vanadium could be electrolessly codeposited with at least one metal from the group composed of iron, nickel, cobalt and chromium in the form of a vanadium alloy.
- Another object is to provide new and improved plating solutions out of which vanadium together with at least one metal from the group composed of iron, nickel, cobalt and chromium can be codeposited.
- Still another object is to provide a new and improved electroless deposition process for depositing alloys containing vanadium and at least one metal from the group composed of iron, nickel, cobalt and chromium upon the surface of a metal substrate.
- an electroless plating solution containing a vanadium salt soluble in the solution together with a soluble salt of at least one metal from the group composed if iron, nickel, cobalt and chromium.
- a bufiering agent and at least one reducing and complexing agent which maintains the positive ions of these salts in states of lowest ionic valence and at the same time forms at least one complex with these ions which is readily reducible to an alloy composed of vanadium and at least one metal from the group composed of iron, nickel, cobalt and chromium.
- a hypophosphite salt is then added together with a suitable buffering agent; the pH of the solution is adjusted to a selected range (either acidic or basic), and the metal substrate is inserted into the solution.
- the complex is then rapidlyreduced to the alloy on the substrate surface through action of the hypophosphite ion.
- vanadium When vanadium is to be codeposited with at least one metal in the group composed of nickel, cobalt and chromium, either acidic or basic solutions can be used. However, when vanadium is to be codeposited with iron, 3. basic bath must be used, as outlined in more detail in the above identified copending application.
- Any organic or inorganic compound which acts as a combined reducing and complexing agent can be used in the manner indicated providing that this compound is soluble in the plating solution and that the resultant complex can be readily reduced to the alloy.
- Typical compounds of this type for example include oxalic acid and its salts.
- All metal substrates which can be electrolessly plated with chromium can be plated in the manner set forth in this application.
- the passive metals must be flash coated (i. e. an electrolytic strike) with an extremely 'thin layer of an active metal, such as nickel, iron, and the like, before a subsequent electroless deposition can ensue.
- Example 1 A steel substrate was immersed in an aqueous electroless plating solution having the following composition:
- the bath was maintained at a temperature within the range .75 -90 C. and at a pH falling within the range 46. t was found that a dense, adherent, non-porous chromium-vanadium alloy layer was formed on the substrate surface and that the deposition rate was approximately 0.3 mil per hour. This alloy contained approximately by weight of chromium and 20% by weight of vanadium.
- a brass disc was flash coated (i. e. a strike coating) with nickel and then immersed in the same solution. The same operating conditions were established and the results were substantially identical.
- Example If a an electroless plating solution having the following com- ,3 i Grams/liter Sodium citrate 100 Sodium hypophosphite 1O aa aot-Hz Na VO '.l6H O -n 20 5 The'bath was maintained at a temperature within the range 75 90 C. and at a pH falling within therange 8-10. The results were substantially identical with Example I. V
- A'steel substrate was immersed in the same solution. Thesame operating conditions were established and the results were substantially the same. v The bath temperature was maintained'at a temperature between 75 90 C. and at a pH between 8-10.
- An ironvanadium alloy was deposited in'the same manner as indicated in the preceding examples This alloy contained approximately 84%; by weightof iron and 16% by weight of vanadium.
- Example III 20 Theprocess outlinedin Example I was-repeated using position: 7
- Example II V Grams/liter NiSQ .7H O 2 Sodium ac e 10 Sodium hypophosphites 10 K C O .H O 50 NaVO 5 30
- a vanadium-nickel alloy was deposited in the same manneras indicated in Example I. This alloy contained approximately 85% by Weight of nickeland about 15% by weight of vanadium.
- Example 1V V The process outlined in Example'llwas repeated using an electroless platingsolution having the following composition: v i 7 Grams/liter 40 CoCl2.2H 'O V 7 V NaH2P02 -Q Sodium citrate; NaVO V V, 5 V Na C O l-I O
- a cobalt-vanadium alloy was, deposited in the same manner. as indicated in EXampleII. This alloy contained approximately 90%: by'weight of cobalt anclabout 10% by weight of vanadium.
- a -zmethod for electrolessly depositing an alloy com- 7 a pleted; posed of vanadiumand at least one metal selected irom a the group consisting of niclrel, cobalt and chromium onto the surface of a metal substrate comprising the step of inserting said substrate into an electroless plating solution containing in aqueous acid solution hypophosphite ion and at least one oxalate complex containing ions of vanadium and said one metal in their lowest ionic valence states, said complex being readily reducible to said alloy at said surface under the action of said hypophosphite ion, whereby said alloy is electrolessly deposited on said sur- 0 face, the source of said hypophosphite ion having a concentration of about 50 grams per liter, the sources of said vanadium and said one metal having a combined concentration falling Within the approximate range 35-38 grams per liter, the source of :said oxalate having an approximate concentration of 50 g ranis
- An electroless plating bath containing in aqueous acidsolutiom-a source ofvanadiumions; asource of metal ions, the'metal f ro nwhich said metal ions are 7 the combined concentration of the vanadium saltand saidone metal saltialling within'the; approximate range 35-38; grams perliter; asource of hypophosphite ion having a concentration'of about 10 grams per liter; and at least one reducing and complexing agent which complexes said vanadium and metal ions in their lowest ionic valence states; said complex when reacted with hypophosphiteion atametal surface being readily. reduced to an alloy formed from vanadium and said metal, said agent being selected from the group consisting of oxalic acid and its salts,said agent having a concentration of about SO'grams per liter. 7
- An electroless plating bath containing in aqueous solution, a source of vanadium ions; a source of metal ions, the'me'tal fro'm'whichsaid'metal ions are produced being selected from the class consisting of nickel, cobalt and chromium, said vanadium and positive ions being maintained in their lowest ionic valence states, the combined concentration of the vanadium salt and said one metal salt falling Within the approximate range 35-38 grams per liter; 'a source ofhypophosphite ion having a concentration of about 10 grams per liter; a bufiering agent maintainingthe pH of said bath in, an acidicrange; and at leastone reducing and complexing agent; which complexes said vanadium and metal ions in their lowest ionic valence stat'e's,fsaid complex when reacted with hypophosphite ion at a m etal' surface being readily reduced to'an-alloy formed from vanadium and said'metal
- a bufiering agent to a bath: containing in aqueous solution hypophosphite ion and at least one oxalatecomplexcontaining' ions of vanadiumandsaidone metal in their lowest ionic valence states, said complex being readily reducible to said alloy'at said-surface under the having an approximate-concentration of 'SOgramS per a liter; insertingsaicl substrate into said bath: whereb' yithe electroless deposition" ensues; andmaintaining said within the acidic: range until said"deposition iscom- No references cited; 7
Description
United States Patent 2,827,400 ELECTROLESS DEPQSITIGN F VANADIUM ALLOYS Philip H. Eisenherg, Hicksvilie, and Douglas 0. Raleigh,
Flushing, N. Y., assignors to Sylvania Electric Products Inc., a corporafion of Massachusetts No Drawing. Uriginal application March 30, 1956, Serial No. 574,995. Divided and this application January 29, 1957, Serial No. 639,605
5 Claims. (Cl. 117-13tl) Our invention relates both to a process in which vanadium together wifla at least one metal selected from the group composed of iron, nickel, cobalt and chromium can be electrolessly codeposited on a suitable metallic substrate and to electroless plating solutions used in said process. This application is a division of application Serial No. 574,995, filed March 30, 1956.
The term electroless deposition as known in the art described a process wherein a metallic substrate is inserted in a bath containing, in aqueous solution, a salt (such as a chloride or sulphate) of a metal selected from the group composed of nickel, cobalt and chromium; a hypophosphite salt (such as sodium hypophosphite); and a suitable bufiering (pH controlling) agent (such as sodium acetate). In the ensuing reaction the nickel, cobalt or chromium is deposited as a pure metal on the surface of the substrate. While the mechanism of this process is not fully understood, it is believed that the hypophosphite ion continuously reduces the dissolved metal salt to the metallic state on the surface of the substrate by means of a catalytic action involving the surface.
It has been found that this reaction, which proceeds in the absence of an externally applied electric field, can take place when the pH of the bath is maintained within the acidic range, as for example a pH of 46 or alternatively within the basic range, as for example a pH of 8-10.
This process is defined as electroless plating or deposition to diderentiate it from the conventional electro-plating or electrolytic deposition technique.
In the copending application of Philip H. Eisenberg, Serial No. 561,670, filed January 26, 1956, there is disclosed a process for electrolessly depositing iron. Thus, any metal of the group composed of iron, nickel, cobalt and chromium can be electrolessly deposited through use of known techniques or through the use of the technique disclosed in the above mentioned copending application.
From theoretical considerations, we believed that vanadium could be electrolessly deposited in a similar manner. Accordingly we attempted to deposit vanadium in this way. Our attempts were unsuccessful; apparently the activity of vanadium is so high that it will oxidize before deposition occurs. In any event, the vanadium could only be electrolessly deposited in the form of an oxide. However, we discovered that vanadium could be electrolessly codeposited with at least one metal from the group composed of iron, nickel, cobalt and chromium in the form of a vanadium alloy.
Accordingly, it is an object of the present invention to provide a process for electrolessly codepositing vanadium together with at least one metal from the group composed of iron, nickel, cobalt and chromium.
Another object is to provide new and improved plating solutions out of which vanadium together with at least one metal from the group composed of iron, nickel, cobalt and chromium can be codeposited.
Still another object is to provide a new and improved electroless deposition process for depositing alloys containing vanadium and at least one metal from the group composed of iron, nickel, cobalt and chromium upon the surface of a metal substrate.
2,827,400 Patented Mar. 18, 1958 These and other objects will either be explained or will become apparent hereinafter.
In our invention there is provided an electroless plating solution containing a vanadium salt soluble in the solution together with a soluble salt of at least one metal from the group composed if iron, nickel, cobalt and chromium. To this is added a bufiering agent and at least one reducing and complexing agent which maintains the positive ions of these salts in states of lowest ionic valence and at the same time forms at least one complex with these ions which is readily reducible to an alloy composed of vanadium and at least one metal from the group composed of iron, nickel, cobalt and chromium. A hypophosphite salt is then added together with a suitable buffering agent; the pH of the solution is adjusted to a selected range (either acidic or basic), and the metal substrate is inserted into the solution. The complex is then rapidlyreduced to the alloy on the substrate surface through action of the hypophosphite ion.
When vanadium is to be codeposited with at least one metal in the group composed of nickel, cobalt and chromium, either acidic or basic solutions can be used. However, when vanadium is to be codeposited with iron, 3. basic bath must be used, as outlined in more detail in the above identified copending application.
Any organic or inorganic compound which acts as a combined reducing and complexing agent can be used in the manner indicated providing that this compound is soluble in the plating solution and that the resultant complex can be readily reduced to the alloy. Typical compounds of this type for example include oxalic acid and its salts.
All metal substrates which can be electrolessly plated with chromium can be plated in the manner set forth in this application. In this connection it will be understood that as in conventional chromium plating, the passive metals must be flash coated (i. e. an electrolytic strike) with an extremely 'thin layer of an active metal, such as nickel, iron, and the like, before a subsequent electroless deposition can ensue.
Our invention will now be explained with reference to the detailed examples which follow.
Example 1 A steel substrate was immersed in an aqueous electroless plating solution having the following composition:
The bath was maintained at a temperature within the range .75 -90 C. and at a pH falling within the range 46. t was found that a dense, adherent, non-porous chromium-vanadium alloy layer was formed on the substrate surface and that the deposition rate was approximately 0.3 mil per hour. This alloy contained approximately by weight of chromium and 20% by weight of vanadium.
A brass disc was flash coated (i. e. a strike coating) with nickel and then immersed in the same solution. The same operating conditions were established and the results were substantially identical.
Example If a an electroless plating solution having the following com- ,3 i Grams/liter Sodium citrate 100 Sodium hypophosphite 1O aa aot-Hz Na VO '.l6H O -n 20 5 The'bath was maintained at a temperature within the range 75 90 C. and at a pH falling within therange 8-10. The results were substantially identical with Example I. V
A'steel substrate was immersed in the same solution. Thesame operating conditions were established and the results were substantially the same. v The bath temperature was maintained'at a temperature between 75 90 C. and at a pH between 8-10. An ironvanadium alloy Was deposited in'the same manner as indicated in the preceding examples This alloy contained approximately 84%; by weightof iron and 16% by weight of vanadium.
Example III 20 Theprocess outlinedin Example I was-repeated using position: 7
V Grams/liter NiSQ .7H O 2 Sodium ac e 10 Sodium hypophosphites 10 K C O .H O 50 NaVO 5 30 A vanadium-nickel alloy was deposited in the same manneras indicated in Example I. This alloy contained approximately 85% by Weight of nickeland about 15% by weight of vanadium.
Example 1V V .The process outlined in Example'llwas repeated using an electroless platingsolution having the following composition: v i 7 Grams/liter 40 CoCl2.2H 'O V 7 V NaH2P02 -Q Sodium citrate; NaVO V V, 5 V Na C O l-I O A cobalt-vanadium alloy was, deposited in the same manner. as indicated in EXampleII. This alloy contained approximately 90%: by'weight of cobalt anclabout 10% by weight of vanadium.
A 'While vwe have shown and pointed out our invention as applied above, it will be apparent to those skilled in the art that many modifications can be made within the scope and sphere of our invention asdefined in the claims which follow.
Whatis claimed is:
1. An electroless platingbathcontaininguin aqueous acid solution, a vanadium'salt; asalt of at least one metal 7 selected from the group consisting of' nickel, cobalt and 'chromium, the positive'ionsof the vanadium and metal salts being intheir' lowest ionic valence state, the combined concentration of the vanadium salt and said one metal salt falling within the: approximate range 35-88 gramsperliter; a hypophosphite salt having aconcentration of about 10 grams per liter; a bufiering agent; and at least one'reducing'and complexing agent which maintains-said positive ions in their lowest valence states and also forms at least onercomplex'fwith said ions which isreadily reducible to an alloy' composed of vanadium and said selected metal when an'ele'ctroless deposition operationris intended; said'tagent.being selected from the group consistingof oxalic acid and its salts, said agent having. a concentration of about 50 gramsper liter:
2.1 A -zmethod for electrolessly depositing an alloy com- 7 a pleted; posed of vanadiumand at least one metal selected irom a the group consisting of niclrel, cobalt and chromium onto the surface of a metal substrate comprising the step of inserting said substrate into an electroless plating solution containing in aqueous acid solution hypophosphite ion and at least one oxalate complex containing ions of vanadium and said one metal in their lowest ionic valence states, said complex being readily reducible to said alloy at said surface under the action of said hypophosphite ion, whereby said alloy is electrolessly deposited on said sur- 0 face, the source of said hypophosphite ion having a concentration of about 50 grams per liter, the sources of said vanadium and said one metal having a combined concentration falling Within the approximate range 35-38 grams per liter, the source of :said oxalate having an approximate concentration of 50 g ranis per liter.
3. An electroless plating bath containing in aqueous acidsolutiom-a source ofvanadiumions; asource of metal ions, the'metal f ro nwhich said metal ions are 7 the combined concentration of the vanadium saltand saidone metal saltialling within'the; approximate range 35-38; grams perliter; asource of hypophosphite ion having a concentration'of about 10 grams per liter; and at least one reducing and complexing agent which complexes said vanadium and metal ions in their lowest ionic valence states; said complex when reacted with hypophosphiteion atametal surface being readily. reduced to an alloy formed from vanadium and said metal, said agent being selected from the group consisting of oxalic acid and its salts,said agent having a concentration of about SO'grams per liter. 7
p 4. An electroless plating bath containing in aqueous solution, a source of vanadium ions; a source of metal ions, the'me'tal fro'm'whichsaid'metal ions are produced being selected from the class consisting of nickel, cobalt and chromium, said vanadium and positive ions being maintained in their lowest ionic valence states, the combined concentration of the vanadium salt and said one metal salt falling Within the approximate range 35-38 grams per liter; 'a source ofhypophosphite ion having a concentration of about 10 grams per liter; a bufiering agent maintainingthe pH of said bath in, an acidicrange; and at leastone reducing and complexing agent; which complexes said vanadium and metal ions in their lowest ionic valence stat'e's,fsaid complex when reacted with hypophosphite ion at a m etal' surface being readily reduced to'an-alloy formed from vanadium and said'metal,
said agent'being selectedfrom the group consisting'ofoxalic acidafnd its salts, said agent having a concentrationof about 50 grams per liter. Y 7
5. "Am'ethod forelectrolessly depositing an alloy 'composed'of vanadium and at'least'onemeta'l selcctedflfrom the'group composed of nicl el, cobalt and chromium onto the-surface. ofa metal substrate comprising the steps of adding a bufiering agent to a bath: containing in aqueous solution hypophosphite ion and at least one oxalatecomplexcontaining' ions of vanadiumandsaidone metal in their lowest ionic valence states, said complex being readily reducible to said alloy'at said-surface under the having an approximate-concentration of 'SOgramS per a liter; insertingsaicl substrate into said bath: whereb' yithe electroless deposition" ensues; andmaintaining said within the acidic: range until said"deposition iscom- No references cited; 7
Claims (1)
1. AN ELECTROLESS PLATING BATH CONTAINING IN AQUEOUS ACID SOLUTION, A VANADIUM SALT; A SALT OF AT LEAST ONE METAL SELECTED FROM THE GROUP CONSISTING OF NICKEL, COBALT AND CHROMIUM, THE POSITIVE IONS OF THE VANADIUM AND METAL SALTS BEING IN THEIR LOWEST IONIC VALENCE STATE, THE COMBINED CONCENTRATION OF THE VANADIUM SALT AND SAID ONE METAL SALT FALLING WITHIN THE APPROXIMATE RANGE 35-38 GRAMS PER LITER; A HYPOPHOSPHITE SALT HAVING A CONCENTRATION OF BAOUT 10 GRAMS PER LITER; A BUFFERING AGENT; AND AT LEAT ONE REDUCING AAND COMPLEXING AGENT WHICH MAINTAINS SAID POSITIVE IONS IN THEIR LOWEST VALENCE STATES AND ALSO FORMS AT LEAST ONE COMPLEX WITH SAID IONS WHICH IS READILY REDUCIBLE TO AN ALLOY COMPOSED OF VANADIUM AND SAID SELECTED METAL WHEN AN ELECTROLESS DEPOSITION OPERATION IS INTENDED, SAID AGENT BEING SELECTED FROM THE GROUP CONSISTING OF OXALIC ACID AND ITS SALTS, SAID AGENT HAVING A CONCENTRATION OF ABOUT 50 GRAMS PER LITER.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US639605A US2827400A (en) | 1956-03-30 | 1957-01-29 | Electroless deposition of vanadium alloys |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US574995A US2828227A (en) | 1956-03-30 | 1956-03-30 | Electroless deposition of vanadium alloys |
US639605A US2827400A (en) | 1956-03-30 | 1957-01-29 | Electroless deposition of vanadium alloys |
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US2827400A true US2827400A (en) | 1958-03-18 |
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US639605A Expired - Lifetime US2827400A (en) | 1956-03-30 | 1957-01-29 | Electroless deposition of vanadium alloys |
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3147154A (en) * | 1961-05-25 | 1964-09-01 | Texaco Inc | Method of depositing metal-containing material onto an extended surface |
US4230751A (en) * | 1977-08-11 | 1980-10-28 | Kabushiki Kaisha Toyota | Treating composition, forming a mixed-carbide layer of Va-Group elements and of chromium on a ferrous-alloy surface and resulting product |
-
1957
- 1957-01-29 US US639605A patent/US2827400A/en not_active Expired - Lifetime
Non-Patent Citations (1)
Title |
---|
None * |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3147154A (en) * | 1961-05-25 | 1964-09-01 | Texaco Inc | Method of depositing metal-containing material onto an extended surface |
US4230751A (en) * | 1977-08-11 | 1980-10-28 | Kabushiki Kaisha Toyota | Treating composition, forming a mixed-carbide layer of Va-Group elements and of chromium on a ferrous-alloy surface and resulting product |
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