US2513237A - Method of protection of magnesium and magnesium-base alloys - Google Patents
Method of protection of magnesium and magnesium-base alloys Download PDFInfo
- Publication number
- US2513237A US2513237A US763159A US76315947A US2513237A US 2513237 A US2513237 A US 2513237A US 763159 A US763159 A US 763159A US 76315947 A US76315947 A US 76315947A US 2513237 A US2513237 A US 2513237A
- Authority
- US
- United States
- Prior art keywords
- magnesium
- manganese
- parts
- electrolyte
- acids
- 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
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 title claims description 27
- 239000011777 magnesium Substances 0.000 title claims description 26
- 229910052749 magnesium Inorganic materials 0.000 title claims description 25
- 238000000034 method Methods 0.000 title claims description 9
- 229910045601 alloy Inorganic materials 0.000 title description 5
- 239000000956 alloy Substances 0.000 title description 5
- 239000002253 acid Substances 0.000 claims description 19
- 239000003792 electrolyte Substances 0.000 claims description 18
- 239000000243 solution Substances 0.000 claims description 18
- 150000007513 acids Chemical class 0.000 claims description 16
- 239000010953 base metal Substances 0.000 claims description 13
- 239000007864 aqueous solution Substances 0.000 claims description 12
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Chemical compound O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 claims description 9
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 8
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 6
- RGVLTEMOWXGQOS-UHFFFAOYSA-L manganese(2+);oxalate Chemical compound [Mn+2].[O-]C(=O)C([O-])=O RGVLTEMOWXGQOS-UHFFFAOYSA-L 0.000 claims description 5
- 239000007795 chemical reaction product Substances 0.000 claims description 4
- 239000004020 conductor Substances 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 150000002681 magnesium compounds Chemical class 0.000 claims description 4
- 230000001681 protective effect Effects 0.000 claims description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 3
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 3
- XLYOFNOQVPJJNP-PWCQTSIFSA-N Tritiated water Chemical compound [3H]O[3H] XLYOFNOQVPJJNP-PWCQTSIFSA-N 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 229910052748 manganese Inorganic materials 0.000 description 13
- 239000011572 manganese Substances 0.000 description 13
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 12
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 8
- 238000000576 coating method Methods 0.000 description 8
- 150000003839 salts Chemical class 0.000 description 8
- SOCTUWSJJQCPFX-UHFFFAOYSA-N dichromate(2-) Chemical compound [O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O SOCTUWSJJQCPFX-UHFFFAOYSA-N 0.000 description 7
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 7
- 238000005260 corrosion Methods 0.000 description 6
- 230000007797 corrosion Effects 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 5
- 239000011656 manganese carbonate Substances 0.000 description 5
- 229940093474 manganese carbonate Drugs 0.000 description 5
- 235000006748 manganese carbonate Nutrition 0.000 description 5
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 description 5
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 description 5
- 229910002092 carbon dioxide Inorganic materials 0.000 description 4
- 238000005868 electrolysis reaction Methods 0.000 description 4
- GKYPBYNKDZIVED-UHFFFAOYSA-N [Mn+2].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O Chemical compound [Mn+2].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O GKYPBYNKDZIVED-UHFFFAOYSA-N 0.000 description 3
- 229940077744 antacid containing magnesium compound Drugs 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 150000002697 manganese compounds Chemical class 0.000 description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910000861 Mg alloy Inorganic materials 0.000 description 1
- 101100513612 Microdochium nivale MnCO gene Proteins 0.000 description 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 1
- -1 chrome anhydride Chemical class 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- YFDWDAIVRZETEB-UHFFFAOYSA-L hydroxy-(hydroxy(dioxo)chromio)oxy-dioxochromium manganese Chemical compound [Mn].[Cr](=O)(=O)(O)O[Cr](=O)(=O)O YFDWDAIVRZETEB-UHFFFAOYSA-L 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- 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
Definitions
- the present invention concerns the treatment of objects made of magnesium metal-or alloys composedprincipa-lly (e. .g. "-85% or-more) of magnesium, for forming said objects a or coating which can protect said articles from corrosion.
- magnesium in the pure state and to a somewhat less extent alloys which contain magnesium associated ialloyed) with small amounts (up to (1 0% or 1'5'%, more or less) of other common metals, e. g.
- Mn, Zn, A1, rare earth metals, etc are "prone to become 'oxidizedor corroded by continued exposure to damp air, air containing traces of acid vapors, air-containing moisture and salts, or sea water, river water, lake water, etc, and efforts havedongbeen made to protect such magnesium or "magnesium alloys, from such oxidation and corrosion.
- the present invention covers such protection.
- magnesimn-base metal will be used to cover such metal and alloys-as discussed above.
- the objects may be cast, forged, machined, rolled, etc. and maybe of any appropriate sizes and may be completely made, or not, as desired.
- Thearticles should 1 first be degreased, cleaned, washed and dried, which steps may be carried out according to proc- 'esses already known.
- MgO is to a slight extent capable of being dissolved by water, especially water containing usual amounts of carbon dioxide in solution.
- Most so-called" insoluble magnesium salts are *likewise subject to attack by water especia'lly 'water containing usual amounts ofcarbon dioxide inrsolution.
- the electrolyte is 'a solution of manganese dichromate, MnCrzOq.
- This solution should have a pH between 2 and '5, and preferably between 3 and 4.
- a pH of close to 3:5 is preferable and produces the best results.
- solution is preferably made by dissolving 10 to 100 grams of chrome anhydride, *CrOz in a liter of water, and adding manganese carbonate thereto,- to give the desired pH.
- the CO2 of the carbonate is liberated into the atmosphere.
- the carbonic acid does not act to injure themagnesiu-m.
- 'Manganese' dioxide preferably in a freshly precipitated state can be similarly dissolved in the chromic acid solution, preferably heated. A part of the oxygen content of-the 'dioxide is liberated during the reaction.
- Manganese carbonate is the preferred compound to use.
- Manganese carbonate, MnCCDa is readily obtainable, is relatively :cheap sand is easily and promptly ⁇ dissolved rbyachromic acid solutions and the action of the .chromic acid "thereupon can substantially 10 about 15 minutes.
- .10 range 5 to 7 parts (preferably 5.5 tov 6.5,) of.man-
- Manganese dichromate MnCIzOv is sufficiently soluble. It will be'under stood that the ratio of manganese compound to C10; as set forth herein is about the proper proportion for the formation of the MnCrzO-z, with perhaps'a slight excess of CrO3.
- the electrolyte may contain between 2.66% and 12% (e. g. 4% to l0%)' of manganese bichromate (based'on the whole electrolyte).
- I- give thefollowing' examplesr
- Two electrodes (each a machined plate-like object of magnesium metal), of approximately equal size and equal surface area are immersed in a bath made from 7.5'parts CIO3 and 4.7 parts MIlCOa in .100 parts of solution. This gives a solution of manganese bichromate, MnCrzOv (perhaps combined with some water).
- the two electrodes were connected to the A. C. circuit, at 15 volts, and an alternating current of 4 amperes per square decimeter was allowed to flow through the cell for The electrolyte was at room temperature (about l8-20 0.), throughout said treatment.
- the coatings are less good as the pH of the electrolyte is above or below the optimum of 3.5. With lower pH, the coatings are somewhat more porous. This can be somewhat offsetby agood painting.
- the coatings can also be somewhat improved by a subsequent boiling in sodium silicate solution or by treatment in hot molten parafiin, as shown in my copending patent applications.
- the strength-of the alternating current can vary between 1.5 and 12 amperes at a voltage between'4 and 40 volts.
- the duration of the .A. C. electrolytic treatment can vary substantially. A treatment for 15 to minutes is usually sufiicient to give a sufficiently thick coating.
- a process of protecting magnesium-base metalobjects in an electrolyte which consists essentially of; an. aqueous solution which is the liquid reaction product made by dissolving at least one substance selected from the group consisting of manganese carbonate, manganese dioxide and manganese oxalate, which substance contains from. about 2.4 to about 3.4 parts by weight of the element manganese, in an aqueous solution of chromic acid alone, containing the equivalent of10 parts by weight of chromic anhydride in about 100 to 1,000 partsby weight of water, and
- a process of protecting magnesium-base metal objects which comprises dissolving a substance. selected from the. group consisting of manganese carbonate, manganese dioxide and manganese oxalate, which substance contains about 2.6 toabout 3.1 parts of the element manganese, in an aqueous solution of chromic acid -alone,.containing the equivalent of 10 parts of chromic anhydride, and applying said solution, while the latter is free from more than traces of acids which are capable of chemically attacking metallic magnesium and dissolving same, and free from more than traces of salts of such acids, andwhile such solution has a pH value of about '3.5,' as an electrolytic bath in which is placed a pair electrodes, at least one of which is such a magnesium-base metal object and the other electrodebeing'formed of an electrically conductive materialwhich is insolube in said electrolyte, and applying to such electrodes an alternating electric current of about 4 amperes' per square decimeter oi surface of said magnesium-base metal object being treated,
- a process which comprises applying an alternating electric current to an electrolytic cell containing a pair of electrodes in an electrolyte, at least one of said electrodes being an object composed of magnesium-base metal, and the other electrode being an electrically conductive material which is insoluble in said electrolyte, and in which said electrolyte consists essentially of an aqueous solution of manganese dichromate having a pH value between about 2 and about 5.
- the said alternatin electric current being between about 1.5 and 12 amperes per square decimeter of surface of said magnesium-base metal object being treated, and at a voltage between about 4 and about 40 volts, and -continuing said treatment until a good protective film has been formed on said object.
Landscapes
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electroplating And Plating Baths Therefor (AREA)
- Chemical Treatment Of Metals (AREA)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR221022X | 1938-09-22 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US2513237A true US2513237A (en) | 1950-06-27 |
Family
ID=8881587
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US763159A Expired - Lifetime US2513237A (en) | 1938-09-22 | 1947-07-23 | Method of protection of magnesium and magnesium-base alloys |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US2513237A (en, 2012) |
| CH (1) | CH221022A (en, 2012) |
| DE (1) | DE749368C (en, 2012) |
| GB (1) | GB571271A (en, 2012) |
| NL (1) | NL56499C (en, 2012) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR702266A (fr) * | 1929-09-16 | 1931-04-03 | Siemens Elektro Osmose G M B H | Procédé de formation sur des métaux légers de revêtements protecteurs résistant à la corrosion |
| US2114734A (en) * | 1935-03-30 | 1938-04-19 | Robert W Buzzard | Bath for and method of coating magnesium and its alloys |
| FR832002A (fr) * | 1937-01-16 | 1938-09-20 | Procédé de protection par voie électrolytique du magnésium et des alliages riches en magnésium, contre la corrosion | |
| US2206028A (en) * | 1936-11-27 | 1940-07-02 | Robert W Buzzard | Anodic treatment of magnesium |
| US2463483A (en) * | 1939-01-31 | 1949-03-01 | Frasch Jean | Protection of metallic objects by galvanic action |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE635720C (de) * | 1935-06-01 | 1936-09-25 | Siemens & Halske Akt Ges | Verfahren zur Herstellung von Schutzueberzuegen auf Magnesium und seinen Legierungen |
-
0
- NL NL56499D patent/NL56499C/xx active
-
1939
- 1939-09-19 GB GB26169/39A patent/GB571271A/en not_active Expired
- 1939-09-21 CH CH221022D patent/CH221022A/fr unknown
- 1939-09-21 DE DEF87438D patent/DE749368C/de not_active Expired
-
1947
- 1947-07-23 US US763159A patent/US2513237A/en not_active Expired - Lifetime
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR702266A (fr) * | 1929-09-16 | 1931-04-03 | Siemens Elektro Osmose G M B H | Procédé de formation sur des métaux légers de revêtements protecteurs résistant à la corrosion |
| US2114734A (en) * | 1935-03-30 | 1938-04-19 | Robert W Buzzard | Bath for and method of coating magnesium and its alloys |
| US2206028A (en) * | 1936-11-27 | 1940-07-02 | Robert W Buzzard | Anodic treatment of magnesium |
| FR832002A (fr) * | 1937-01-16 | 1938-09-20 | Procédé de protection par voie électrolytique du magnésium et des alliages riches en magnésium, contre la corrosion | |
| US2463483A (en) * | 1939-01-31 | 1949-03-01 | Frasch Jean | Protection of metallic objects by galvanic action |
Also Published As
| Publication number | Publication date |
|---|---|
| NL56499C (en, 2012) | |
| CH221022A (fr) | 1942-05-15 |
| GB571271A (en) | 1945-08-17 |
| DE749368C (de) | 1944-11-22 |
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