US2820750A - Electrolytic treatment of metals and alloys - Google Patents
Electrolytic treatment of metals and alloys Download PDFInfo
- Publication number
- US2820750A US2820750A US344670A US34467053A US2820750A US 2820750 A US2820750 A US 2820750A US 344670 A US344670 A US 344670A US 34467053 A US34467053 A US 34467053A US 2820750 A US2820750 A US 2820750A
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- United States
- Prior art keywords
- acid
- electrolyte
- solution
- alloys
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- 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
- 229910045601 alloy Inorganic materials 0.000 title claims description 14
- 239000000956 alloy Substances 0.000 title claims description 14
- 229910052751 metal Inorganic materials 0.000 title claims description 13
- 239000002184 metal Substances 0.000 title claims description 13
- 150000002739 metals Chemical class 0.000 title description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 26
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 17
- 239000001117 sulphuric acid Substances 0.000 claims description 17
- 235000011149 sulphuric acid Nutrition 0.000 claims description 17
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 15
- 239000008151 electrolyte solution Substances 0.000 claims description 15
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 13
- 239000000243 solution Substances 0.000 claims description 12
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 claims description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 9
- 239000000654 additive Substances 0.000 claims description 9
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 7
- 229910052804 chromium Inorganic materials 0.000 claims description 7
- 239000011651 chromium Substances 0.000 claims description 7
- 229910052759 nickel Inorganic materials 0.000 claims description 7
- 230000000996 additive effect Effects 0.000 claims description 6
- 239000000470 constituent Substances 0.000 claims description 6
- 229910052742 iron Inorganic materials 0.000 claims description 5
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- 239000010941 cobalt Substances 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 239000003792 electrolyte Substances 0.000 description 14
- 229940021013 electrolyte solution Drugs 0.000 description 12
- 229910000640 Fe alloy Inorganic materials 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000003754 machining Methods 0.000 description 3
- 238000007517 polishing process Methods 0.000 description 3
- 239000001533 (4R,6S)-2,4,6-trimethyl-1,3,5-dithiazinane Substances 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- FBMVFHKKLDGLJA-UHFFFAOYSA-N Thialdine Chemical compound CC1NC(C)SC(C)S1 FBMVFHKKLDGLJA-UHFFFAOYSA-N 0.000 description 2
- 150000002391 heterocyclic compounds Chemical class 0.000 description 2
- 150000002780 morpholines Chemical class 0.000 description 2
- 238000005498 polishing Methods 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- MPIQXJWUXWQCOS-UHFFFAOYSA-N C1(=CC=CC=C1)N1CCOCC1.N1CCOCC1 Chemical compound C1(=CC=CC=C1)N1CCOCC1.N1CCOCC1 MPIQXJWUXWQCOS-UHFFFAOYSA-N 0.000 description 1
- 229910000975 Carbon steel Inorganic materials 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- -1 aromatic amino compound Chemical class 0.000 description 1
- 238000005282 brightening Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- AXTNPHLCOKUMDY-UHFFFAOYSA-N chromium cobalt Chemical compound [Co][Cr][Co] AXTNPHLCOKUMDY-UHFFFAOYSA-N 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000002939 deleterious effect Effects 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 229910001235 nimonic Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 235000011007 phosphoric acid Nutrition 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25F—PROCESSES FOR THE ELECTROLYTIC REMOVAL OF MATERIALS FROM OBJECTS; APPARATUS THEREFOR
- C25F3/00—Electrolytic etching or polishing
- C25F3/16—Polishing
- C25F3/22—Polishing of heavy metals
Definitions
- This invention relates to improvements in the electrolytic treatment of metal surfaces wherein an electrolyte comprising a mixture of sulphuric acid and phosphoric acid or sulphuric acid alone, the electrolyte being of high acid concentration, is employed and the article to be polished is made the anode.
- the electrolyte has an acid concentration of at least 50% by weight of the electrolyte or more generally speaking has a combined sulphate and phosphate content which When expressed as sulphuric acid and phosphoric acid respectively represents at least 50% of the electrolyte and the ratio of sulphuric acid and phosphoric acid initially in the electrolyte exceeds 5:3.
- the proportion of the additive necessary is small and falls within the range of 0.3% to by weight of the electrolyte according to the particular additive or additives employed and the work the electrolyte is required to do.
- Polishing processes using an electrolyte according to the present invention can be carried out using current densities within the range of 0.3 to 5 amps. per square inch. Higher current densities may be used for treatment requiring greater metal removal, e. g. electro-machining.
- Example 3 stainless iron, 2. g. ferrous alloys having 17% chromium content.A current density of 1 amp per square inch and a temperature of 85 C.
- Example 5 An alloy in which the proportions of the main constituents are Ni75%, Cr20%, e. g. Nimoniz 8 0.-A current density of 2.0 amps. per square inch anc a temperature of 30 C.
- Example 6 An alloy in which the proportion of the main constituents are Ni%, Cr20%.A curren density of 1.0 amp. per square inch and a temperature 0: 30 C.
- the additives and processing conditions employed are related to the metal or alloy being treated and the resul desired.
- the time of treatment depends on the amoun of metal to be removed; thus for polishing the time taker in the foregoing examples would be about 10 minute: whilst for machining it might be 30 minutes or longer Further the current density employed can also be varied ac cording to the amount of metal to be removed.
- the water and metal content of the electrolyte depend: on its particular application and various forms of agitatioi may be employed as required.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electrical Discharge Machining, Electrochemical Machining, And Combined Machining (AREA)
- ing And Chemical Polishing (AREA)
Description
ELECTROLYTIC TREATMENT OF METALS AND ALLOYS Percy Allan Charlesworth, Adlington, England No Drawing. Application March 25, 1953 Serial No. 344,670
Claims. (Cl. 204-1405) This invention relates to improvements in the electrolytic treatment of metal surfaces wherein an electrolyte comprising a mixture of sulphuric acid and phosphoric acid or sulphuric acid alone, the electrolyte being of high acid concentration, is employed and the article to be polished is made the anode.
in the specification of my U. S. Patent No. 2,594,124 an electrolytic polishing process is described having an electrolyte based on a mixture of sulphuric acide or phosphoric acid or on sulphuric acid alone to which is added a small amount of the aromatic amino compound, e. g. aniline.
I have now found and this discovery forms the basis of the present invention that stainless steel and other ferrous alloys with chromium and/or nickel; plain carbon steels and similar ferrous alloys; nickel and its alloys; chromium and its alloys and cobalt and its alloys can be satisfactorily electrolytically treated for the purpose of brightening, polishing, electro-machining, shaping, cutting and stress relieving or the like using an electrolyte based on a mixture of sulphuric acid and phosphoric acid or on sulphuric acid alone to which a relatively small amount of a heterocyclic compound or compounds of the type in which the heterocyclic molecule contains at least one ring structure having present in the ring at least two heterocyclic atoms one of which is nitrogen.
Although the invention is not limited thereto, I have founnd that it is particularly advantageous when the electrolyte has an acid concentration of at least 50% by weight of the electrolyte or more generally speaking has a combined sulphate and phosphate content which When expressed as sulphuric acid and phosphoric acid respectively represents at least 50% of the electrolyte and the ratio of sulphuric acid and phosphoric acid initially in the electrolyte exceeds 5:3.
The proportion of the additive necessary is small and falls within the range of 0.3% to by weight of the electrolyte according to the particular additive or additives employed and the work the electrolyte is required to do.
Polishing processes using an electrolyte according to the present invention can be carried out using current densities within the range of 0.3 to 5 amps. per square inch. Higher current densities may be used for treatment requiring greater metal removal, e. g. electro-machining.
Generally a heterocyclic compound of the type referred to, to be satisfactory as an additive should saitsfy the following requirements:
(1) It should be effective at low concentrations, i. e. between 0.3% and 10% by weight of the electrolyte.
(2) It should have a reasonable life.
(3) Deleterious reaction products should be capable of removal from the electrolyte.
(4) It should not cause excessive frothing or foaming nor give ofi malodorous or toxic vapors during the polishing process.
The following compounds are illustrative of the type of 2,820,? Patented Jan. 21, 1952 molecular configuration of the additives: morpholine phenyl morpholine and thialdine, the structural formula of the latter compound being:
CH-NH S\ CHCHI CH-S Parts by weigh H2804 5. H PO 2i 2 to 3' Morpholine 2 t0 1 Example 1.-Stainless steel.--A current density of 1 amp. per square inch and a temperature of 50-60 C.
Example 2.Plain clarbon steels and low alloy steels A current density of 1 amp. per square inch and 2 temperature of 85 C.
Example 3.Stainless iron, 2. g. ferrous alloys having 17% chromium content.A current density of 1 amp per square inch and a temperature of 85 C.
Example 4.An alloy in which the proportions of the main constituents are Ni55%, Cr20%, C0-20% e. g. Nimonic 90.--A current density of 1.8 amps per square inch and a temperature of 30 C.
Example 5.An alloy in which the proportions of the main constituents are Ni75%, Cr20%, e. g. Nimoniz 8 0.-A current density of 2.0 amps. per square inch anc a temperature of 30 C.
Example 6.An alloy in which the proportion of the main constituents are Ni%, Cr20%.A curren density of 1.0 amp. per square inch and a temperature 0: 30 C.
The additives and processing conditions employed are related to the metal or alloy being treated and the resul desired. The time of treatment depends on the amoun of metal to be removed; thus for polishing the time taker in the foregoing examples would be about 10 minute: whilst for machining it might be 30 minutes or longer Further the current density employed can also be varied ac cording to the amount of metal to be removed.
The water and metal content of the electrolyte depend: on its particular application and various forms of agitatioi may be employed as required.
I claim:
1. A method of anodically removing metal from th surface of a metallic body belonging to the group con sisting of iron, nickel, chromium, cobalt and alloys 0 each, characterized by immersing at least a surface por tion of said metallic body in an electrolyte solution con taining at least 50% by weight of said solution of acir constiutents belonging to the group consisting of sulphurii acid and of a mixture of sulphuric and phosphoric acid, tht ratio of sulphuric acid in said mixture to phosphoric acit being greater than 5 to 3, said electrolyte solution alsr containing between 0.3% and 10% by weight of sair solution of an additive belonging to the group consisting o: morpholine and morpholine derivatives; and passing current through said metallic body and said electrolyte solution.
2. A method of anodically removing metal from the surface of a metallic body belonging to the group consistng of iron, nickel, chromium-cobalt and alloys of each, lharacterized by immersing at least a surface portion of aid metallic body in an electrolyte solution containing at least 50% by weight of said solution of acid constituents velonging to-the group consisting of sulphuric acid and f a mixture of sulphuric andpho'sphori'c acid, the ratio |f sulphuric acid in said mixture 'to phosphoric acid being ;reater than to 3, said;e lectrolyte solution also containng between 0.3% and by weight of said solution of morpholine; and passing cuflr'i'tthrough said metallic |ody and said electrolyte solutions 3. A methodof anodically removing metal from the 1 taining at least 50% by weight of said solution of sulurfa'ce of a metallic body belonging to the group. consistugpfiiron, nickel, chromium,'cobal t andyalloys of each, haracterized .by immersing at; leastua surface portion of aid metallic bodyinan electrolyte-solution containing at east 50% by weight of said solution of acid constituents belonging to the group consisting of sulphuric acid and of a mixture of sulphuric and phosphoric acid, the ratio of sulphuric acid in said mixture to phosphoric acid being greater than 5 to 3, said electrolyte solution also containing between 0.3% and 10% by weight of said solution of thialdine; and passing current through said metallic body andsaid electrolyte solution. 7
5. A method of anodically removing metal from the surface of a metallic body belonging to the group consisting of iron, nickel, chromium, cobalt and alloys of each, characterized by immersing at least a surface portion of said metallic body in an electrolyte solution conphuric acid, said electrolyte solution also-containing between 0.3% and 10% by weight of said solution of an additive belonging to the group consisting of morpholine and morpholine derivatives; and passing current through elonging to the group consisting of sulphur acid and of A mixture of sulphuric and phosphoric acid, the ratio of ulphuric'i acid-1 in said mixture to phosphoric acid being reater than Ste 3, said electrolyte solution also containng between 0.3% and 10% by weight of said solution of said metallic body and said electrolyte solution.
References Cited in the file of this patent UNITED STATES PATENTS
Claims (1)
1. A METHOD OF ANODICALLY REMOVING METAL FROM THE SURFACE OF A METALLIC BODY BELONGING TO THE GROUP CONSISTING OF IRON, NICKEL, CHROMIUM, COBALT AND ALLOYS OF EACH, CHARACTERIZED BY IMMERSIN AT LEAST A SURFACE PORTION OF SAID METALLIC BODY IN AN ELECTROLYTE SOLUTION CONTAINING AT LEAST 50* BY WEIGHT OF SAID SOLUTION OF ACID CONSTITUENTS BELONGING TO THE GROUP CONSISTING OF SULPHURIC ACID AND OF A MIXTURE OF SULPHURIC PHOSPHORIC ACID, THE RATIO OF SULPHURIC ACID IN SAID MIXTURE TO PHOSPHORIC ACID BEING GREATER THAN 5 TO 3, SAID ELECTROLYTE SOLUTION ALSO CONTAINING BETWEEN 0.3% AND 10% BY WEIGHT OF SAID SOLUTION OF AN ADDITIVE BELONGING TO THE GROUP CONSISTING OF MORPHOLINE AND MORPHOLINE DERIVATIVES, AND PASSING CURRENT THROUGH SAID METALLIC BODY AND SAID ELECTROLYTE SOLUTION.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US344670A US2820750A (en) | 1953-03-25 | 1953-03-25 | Electrolytic treatment of metals and alloys |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US344670A US2820750A (en) | 1953-03-25 | 1953-03-25 | Electrolytic treatment of metals and alloys |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US2820750A true US2820750A (en) | 1958-01-21 |
Family
ID=23351487
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US344670A Expired - Lifetime US2820750A (en) | 1953-03-25 | 1953-03-25 | Electrolytic treatment of metals and alloys |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US2820750A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0249650A1 (en) * | 1986-06-20 | 1987-12-23 | Poligrat Gmbh | Electrolyte for electrochemically polishing metal surfaces |
| US4935112A (en) * | 1988-04-07 | 1990-06-19 | Seneca Wire And Manufacturing Company | Continuous steel strand electrolytic processing |
| US5087342A (en) * | 1988-04-07 | 1992-02-11 | Seneca Wire And Manufacturing Company | Continuous steel strand electrolytic processing |
| WO1992020841A1 (en) * | 1991-05-15 | 1992-11-26 | Sandvik Ab | Etching process |
| DE10151180A1 (en) * | 2001-10-17 | 2003-04-30 | Norbert Nowack | Stripping coating containing nickel from metal article, e.g. of iron, steel, aluminum or alloy, uses chelant containing phosphonic acid groups under acid to neutral, oxidative conditions |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2349843A (en) * | 1941-06-14 | 1944-05-30 | American Steel & Wire Co | Electrolytic treatment of chromium alloys |
| US2411410A (en) * | 1941-06-14 | 1946-11-19 | American Steel & Wire Co | Electropolishing stainless steel |
| US2451341A (en) * | 1945-08-10 | 1948-10-12 | Westinghouse Electric Corp | Electroplating |
| US2594124A (en) * | 1946-09-12 | 1952-04-22 | Charlesworth Percy Allan | Electrolytic polishing of metals |
| GB683310A (en) * | 1950-05-09 | 1952-11-26 | Percy Allan Charlesworth | Improvements in the electrolytic polishing of metals |
| US2700020A (en) * | 1952-06-02 | 1955-01-18 | Houdaille Hershey Corp | Plating copper |
-
1953
- 1953-03-25 US US344670A patent/US2820750A/en not_active Expired - Lifetime
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2349843A (en) * | 1941-06-14 | 1944-05-30 | American Steel & Wire Co | Electrolytic treatment of chromium alloys |
| US2411410A (en) * | 1941-06-14 | 1946-11-19 | American Steel & Wire Co | Electropolishing stainless steel |
| US2451341A (en) * | 1945-08-10 | 1948-10-12 | Westinghouse Electric Corp | Electroplating |
| US2594124A (en) * | 1946-09-12 | 1952-04-22 | Charlesworth Percy Allan | Electrolytic polishing of metals |
| GB683310A (en) * | 1950-05-09 | 1952-11-26 | Percy Allan Charlesworth | Improvements in the electrolytic polishing of metals |
| US2700020A (en) * | 1952-06-02 | 1955-01-18 | Houdaille Hershey Corp | Plating copper |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0249650A1 (en) * | 1986-06-20 | 1987-12-23 | Poligrat Gmbh | Electrolyte for electrochemically polishing metal surfaces |
| US4935112A (en) * | 1988-04-07 | 1990-06-19 | Seneca Wire And Manufacturing Company | Continuous steel strand electrolytic processing |
| US5087342A (en) * | 1988-04-07 | 1992-02-11 | Seneca Wire And Manufacturing Company | Continuous steel strand electrolytic processing |
| WO1992020841A1 (en) * | 1991-05-15 | 1992-11-26 | Sandvik Ab | Etching process |
| US5380408A (en) * | 1991-05-15 | 1995-01-10 | Sandvik Ab | Etching process |
| DE10151180A1 (en) * | 2001-10-17 | 2003-04-30 | Norbert Nowack | Stripping coating containing nickel from metal article, e.g. of iron, steel, aluminum or alloy, uses chelant containing phosphonic acid groups under acid to neutral, oxidative conditions |
| DE10151180A8 (en) * | 2001-10-17 | 2010-03-18 | Nowack, Norbert, Prof. Dr.-Ing. | Process and solution for delamination of metallic objects with nickel corrosion protection coating |
| DE10151180B4 (en) * | 2001-10-17 | 2010-05-12 | Nowack, Norbert, Prof. Dr.-Ing. | Process and solution for delamination of metallic objects with nickel corrosion protection coating |
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