US2902394A - Protective metal coating compositions and method of coating - Google Patents
Protective metal coating compositions and method of coating Download PDFInfo
- Publication number
- US2902394A US2902394A US598762A US59876256A US2902394A US 2902394 A US2902394 A US 2902394A US 598762 A US598762 A US 598762A US 59876256 A US59876256 A US 59876256A US 2902394 A US2902394 A US 2902394A
- Authority
- US
- United States
- Prior art keywords
- per liter
- acid
- grams per
- chromium
- concentrate
- 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
- 238000000034 method Methods 0.000 title claims description 5
- 229910052751 metal Inorganic materials 0.000 title description 13
- 239000002184 metal Substances 0.000 title description 13
- 239000008199 coating composition Substances 0.000 title description 3
- 239000011248 coating agent Substances 0.000 title description 2
- 238000000576 coating method Methods 0.000 title description 2
- 230000001681 protective effect Effects 0.000 title description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 48
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 32
- 229910052804 chromium Inorganic materials 0.000 claims description 17
- 239000011651 chromium Substances 0.000 claims description 17
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 16
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 12
- 239000011701 zinc Substances 0.000 claims description 12
- 229910052725 zinc Inorganic materials 0.000 claims description 12
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Chemical compound O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 claims description 10
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 8
- 229910017604 nitric acid Inorganic materials 0.000 claims description 8
- 239000012141 concentrate Substances 0.000 description 18
- 235000011054 acetic acid Nutrition 0.000 description 14
- 229960000583 acetic acid Drugs 0.000 description 14
- 229940107218 chromium Drugs 0.000 description 14
- 235000012721 chromium Nutrition 0.000 description 14
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 14
- 229940032330 sulfuric acid Drugs 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 239000003638 chemical reducing agent Substances 0.000 description 8
- 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 8
- 229940074355 nitric acid Drugs 0.000 description 7
- 229940001482 sodium sulfite Drugs 0.000 description 7
- 235000010265 sodium sulphite Nutrition 0.000 description 7
- 239000002253 acid Substances 0.000 description 6
- 238000005260 corrosion Methods 0.000 description 6
- 230000007797 corrosion Effects 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 229910000906 Bronze Inorganic materials 0.000 description 4
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 4
- 239000010974 bronze Substances 0.000 description 4
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 238000011282 treatment Methods 0.000 description 2
- 101150114104 CROT gene Proteins 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- PQUCIEFHOVEZAU-UHFFFAOYSA-N Diammonium sulfite Chemical compound [NH4+].[NH4+].[O-]S([O-])=O PQUCIEFHOVEZAU-UHFFFAOYSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 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
- 229910001229 Pot metal Inorganic materials 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- XYXNTHIYBIDHGM-UHFFFAOYSA-N ammonium thiosulfate Chemical compound [NH4+].[NH4+].[O-]S([O-])(=O)=S XYXNTHIYBIDHGM-UHFFFAOYSA-N 0.000 description 1
- ZETCGWYACBNPIH-UHFFFAOYSA-N azane;sulfurous acid Chemical compound N.OS(O)=O ZETCGWYACBNPIH-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 150000001845 chromium compounds Chemical class 0.000 description 1
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical class [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 1
- 238000004512 die casting Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- GRWZHXKQBITJKP-UHFFFAOYSA-N dithionous acid Chemical class OS(=O)S(O)=O GRWZHXKQBITJKP-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- HEZHYQDYRPUXNJ-UHFFFAOYSA-L potassium dithionite Chemical compound [K+].[K+].[O-]S(=O)S([O-])=O HEZHYQDYRPUXNJ-UHFFFAOYSA-L 0.000 description 1
- BHZRJJOHZFYXTO-UHFFFAOYSA-L potassium sulfite Chemical compound [K+].[K+].[O-]S([O-])=O BHZRJJOHZFYXTO-UHFFFAOYSA-L 0.000 description 1
- 235000019252 potassium sulphite Nutrition 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- JVBXVOWTABLYPX-UHFFFAOYSA-L sodium dithionite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])=O JVBXVOWTABLYPX-UHFFFAOYSA-L 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- DHCDFWKWKRSZHF-UHFFFAOYSA-N sulfurothioic S-acid Chemical compound OS(O)(=O)=S DHCDFWKWKRSZHF-UHFFFAOYSA-N 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
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/24—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing hexavalent chromium compounds
- C23C22/30—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing hexavalent chromium compounds containing also trivalent chromium
Definitions
- Another object of the invention is to provide a composition of the type described which produces enhanced corrosion protection on Zinc surfaces.
- Another object of the invention is to provide a new and improved method of producing excellent bronze corrosion resistant finishes on zinc surfaced articles. Other objects will appear hereinafter.
- new and improved metal finishing coating compositions are prepared by intimately mixing chromic acid, a reducing agent capable of reducing a minor proportion of the chromic acid to a state in which the chromium is present as trivalent chromium, acetic acid, sulfuric acid and nitric acid.
- This composition is initially prepared as a concentrate, preferably by mixing together chromic anhydride, sodium sul fite, acetic acid, sulfuric acid, nitric acid and water. The concentrate is then diluted in actual practice With a relatively large quantity of water so that the final bath which is employed as a finishing composition for metal surfaces only contains around 1.5% to 4% by volume of the original concentrate.
- the amount of chromium present in the concentrate preferably varies from a minimum of about 200 grams per liter to the saturation solubility in the concentrate at a temperature around 20 C.
- the maximum amount of sodium sulfite in the concentrate previously described should not exceed about 50 grams per liter.
- the ratio of reducing agent to chromic acid in the concentrate should provide preferably at least 1 gram per liter and not more than 11 grams'per liter of trivalent chromium.
- the ratio of sulfuric acid to acetic' acid is rather critical and should be approximately 2:1 on a weight basis.
- the minimum amount of acetic acid is about 20 grams per liter and the maximum amount of acetic acid preferably does not exceed about 40 grams; per liter, the minimum amount of sulfuric acid is about scribed preferably should not be less than 150 grams per liter nor more than 300 grams per liter- In the final metal finishing bath prepared by dilution.
- the amountof chromium should be within the range of 3 grams to grams per liter, preferably 15 to 90 grams per liter.
- the ratio of S0; :CrO; should be Within the range of about 1:4 to about 1:16 with optimum results being obtained at about 55:20.
- the treating hath made by diluting the concentrate in the manner previously described Will contain about 0.3 gram per liter to about 0.6 gram per liter of acetic acid and about 0.6 gram per liter to about 1.2 grams per liter of sulfuric acid.
- the nitric acid in the treating bath will be about 2.25 grams per liter to about 4.5 grams per liter.
- the weight ratio of sulfuric acid to acetic acid in the metal finishing bath will be the same as the weight ratio in the concentrate, namely, approximately 2:1.
- the trivalent chromium in the treating bath should preferably be at least 0.015 gram per liter and not more than about 4.4 grams per liter.
- sodium sulfite other reducing agents can .be used which are capable of reducing hexavalent chro mium compounds to trivalent chromium compounds in' acidic solutions, but it is desirable to employ reducing agents which do not form insoluble by-products with the acid of the acidic aqueous solution.
- reducing agents are sodium thiosulfate, sodium hydrosulfite, potassium sulfite, postassium thiosulfate, potassium hydrosulfite, ammonium sulfite, ammonium thiosulfate, and ammonium hydrosulfite.
- the hydrosulfites are also commonly referred to as hyposulfites.
- Other reducing agents which reduce chromic acid in acid solution can be used. Reducing agents such as calcium sullite are undesirable because of the formation of insoluble calcium sulfate.
- the invention is especially useful in providing a beautiful bronze color and enhanced corrosion resistance to Zinc die castings and to other zinc surfaced articles.
- An important advantage of the invention is that the metal to be treated can be immersed in the treating solution as previously described and requires no further treatment other than rinsing with Water. In many types of chromic acid treatments heretofore proposed a secondary treatment is required. By the practice of the invention it is possible to produce zinc surfaced articles which show a high resistance to the formation of white corrosion products.
- ThGf-BXPI'GSSiOHJ zincsurfaced article is employed herein to cover any article having an exterior surface of'zinoregardlss ofwli'ether the article itselfis made of zinc, a ferrous metal or some other metal capable of being coated-with zinc.
- grams p'er liter of nitric acid the weight ratio of sulfuricacid” to acetic acidbeing approximately 23 1 and 1' the weight'ratio ofS'OL; ":CrOt beingv within the rangeoflz4to 1116.
- An acidic aqueous 'metal'treating solution consisting essentially of an aqueous solutionof'chromic acid containing about 15m 90 'grams per liter of chromium ofwhich at least about (LOIS-gram per liter but 'not more than about 4.4 grams per liter is chromium in a trivalent.
- a concentrate adapted to be added to water to produce an aqueous metal? treating solution consisting essentially of an aqueous solution of chromic aeid containing-- chromium in" an? amount- 1 from about 200 grams per'litertothesaturatiorr solubility in the solution -at2v0-? l 0f: which at least 1' grampent liter and not more-: than 1:1- gratn'sper' handsstrivalnt chromium, the remainder being, chromium" in.
Landscapes
- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Treatment Of Metals (AREA)
Description
United States Patent PROTECTIVE METAL COATING COMPOSITIONS AND METHOD OF COATING Bruno R. Jeremias, Detroit, Mich., assignor to Poor & Company, Chicago, 11]., a corporation of Delaware No Drawing. Application July 19, 19.56
Serial NO. 598,762 g 8 Claims. (Cl. 1486.21)
and improved corrosion protecting metal finishing com- 1 position which produces a beautiful bronze color on zinc surfaces, for example, die cast zinc articles.
Another object of the invention is to provide a composition of the type described which produces enhanced corrosion protection on Zinc surfaces.
Another object of the invention is to provide a new and improved method of producing excellent bronze corrosion resistant finishes on zinc surfaced articles. Other objects will appear hereinafter.
In accordance with the invention new and improved metal finishing coating compositions are prepared by intimately mixing chromic acid, a reducing agent capable of reducing a minor proportion of the chromic acid to a state in which the chromium is present as trivalent chromium, acetic acid, sulfuric acid and nitric acid. This composition is initially prepared as a concentrate, preferably by mixing together chromic anhydride, sodium sul fite, acetic acid, sulfuric acid, nitric acid and water. The concentrate is then diluted in actual practice With a relatively large quantity of water so that the final bath which is employed as a finishing composition for metal surfaces only contains around 1.5% to 4% by volume of the original concentrate.
The best mode contemplated for the practice of the invention is illustrated by the following composition which constitutes the concentrate:
Ingredients: Grams per liter Chromic anhydride (CrO 401.0 Sodium sulfite (Na SO- 7.5 Acetic acid 22.5 Sulfuric acid 45.0 Nitric acid 228.0
the remainder being water.
When this composition is diluted with water so that the resultant bath contains 1.5% to 4% by volume of the initial concentrate the said bath is an excellent corrosion protecting composition and provides a beautiful bronze finish on Zinc surfaced articles. The general procedure in providing such a finish on such articles is to immerse the articles in the bath at ordinary temperatures (70 F. to 90 F.) for a period of 5 to 15 seconds, then rinse the article with Water and dry.
In the practice of the invention the amount of chromium present in the concentrate preferably varies from a minimum of about 200 grams per liter to the saturation solubility in the concentrate at a temperature around 20 C.
In the previously described concentrate it is desirable that not more than A: of the chromium initially present in the hexavalent state be reduced to the trivalent state.
Thus if sodium sulfite is used as the reducing agent the maximum amount of sodium sulfite in the concentrate previously described should not exceed about 50 grams per liter. The ratio of reducing agent to chromic acid in the concentrate should provide preferably at least 1 gram per liter and not more than 11 grams'per liter of trivalent chromium. l i
The ratio of sulfuric acid to acetic' acid is rather critical and should be approximately 2:1 on a weight basis. In the concentrate the minimum amount of acetic acid is about 20 grams per liter and the maximum amount of acetic acid preferably does not exceed about 40 grams; per liter, the minimum amount of sulfuric acid is about scribed preferably should not be less than 150 grams per liter nor more than 300 grams per liter- In the final metal finishing bath prepared by dilution.
of the concentrate the amountof chromium should be within the range of 3 grams to grams per liter, preferably 15 to 90 grams per liter. The ratio of S0; :CrO; should be Within the range of about 1:4 to about 1:16 with optimum results being obtained at about 55:20. The treating hath made by diluting the concentrate in the manner previously described Will contain about 0.3 gram per liter to about 0.6 gram per liter of acetic acid and about 0.6 gram per liter to about 1.2 grams per liter of sulfuric acid. The nitric acid in the treating bath will be about 2.25 grams per liter to about 4.5 grams per liter. The weight ratio of sulfuric acid to acetic acid in the metal finishing bath will be the same as the weight ratio in the concentrate, namely, approximately 2:1. The trivalent chromium in the treating bath should preferably be at least 0.015 gram per liter and not more than about 4.4 grams per liter.
Instead of the sodium sulfite other reducing agents can .be used which are capable of reducing hexavalent chro mium compounds to trivalent chromium compounds in' acidic solutions, but it is desirable to employ reducing agents which do not form insoluble by-products with the acid of the acidic aqueous solution. Other examples of preferred reducing agents are sodium thiosulfate, sodium hydrosulfite, potassium sulfite, postassium thiosulfate, potassium hydrosulfite, ammonium sulfite, ammonium thiosulfate, and ammonium hydrosulfite. The hydrosulfites are also commonly referred to as hyposulfites. Other reducing agents which reduce chromic acid in acid solution can be used. Reducing agents such as calcium sullite are undesirable because of the formation of insoluble calcium sulfate.
The reduction reaction between the chromate radical of the chromic acid and the sulfite radical which occurs when a sulfite such as sodium sulfite is mixed with the chromic acid in the presence of water can be expressed by the following equation:
The invention is especially useful in providing a beautiful bronze color and enhanced corrosion resistance to Zinc die castings and to other zinc surfaced articles. An important advantage of the invention is that the metal to be treated can be immersed in the treating solution as previously described and requires no further treatment other than rinsing with Water. In many types of chromic acid treatments heretofore proposed a secondary treatment is required. By the practice of the invention it is possible to produce zinc surfaced articles which show a high resistance to the formation of white corrosion products.
ThGf-BXPI'GSSiOHJ zincsurfaced article is employed herein to cover any article having an exterior surface of'zinoregardlss ofwli'ether the article itselfis made of zinc, a ferrous metal or some other metal capable of being coated-with zinc. "Ihe expression. zinc platedai ti'cleffis employedfhe'rein to describe a zincncoatedr articleinfwhich' the zinc coatinghas' been applid' by, an. electroplatingfprocess;
The invention is. hereby, claimed'as follows ll Alpr'ocessofffinishing'zincsurfaced articles wliicli compri'Sestreatin'gtlie surfaces of such articles with an? aqeuous solution of chromic :acid containing? 1090" grarn's'pe'r liter of"'cliromiiiiriof which at least OLOlS gram per liter but not more than about'4i4 grams per literis'chl'oiniuni in a tiiyalent-"state, the remainder being chromiumyin a hexayalnt'st'ate,, Ol'3fto' T6 gram per Iiter'of acetic acid} 0161a 1.2"grams per liter of sulfuric acid,lcand.about2l Sgrianis per liter to 4.5 grams perli'te'r"of'ni't'ric;acid,' the weight ratio of sulfuric acid to acetic acid being approximately 231 and'the weight ratio of S0 :CrO; beingywithin the range of about l:4 to 131'6.
2f A'p'roce's'sas claimed in claim l'in which the article tobe'treatedis'fimmersed in said aqueous solution atIa,
state',.th'e"remainder being chromium in a liexavalent; 35
grams per liter of sulfuric acid and about 2.5 to 4.5
state, 0.3to 016' gram per liter'of acetioacir 016'to 1.2
grams p'er liter of nitric acid," the weight ratio of sulfuricacid" to acetic acidbeing approximately 23 1 and 1' the weight'ratio ofS'OL; ":CrOt beingv within the rangeoflz4to 1116.
5i An acidic aqueous 'metal'treating solution consisting essentially of an aqueous solutionof'chromic acid containing about 15m 90 'grams per liter of chromium ofwhich at least about (LOIS-gram per liter but 'not more than about 4.4 grams per liter is chromium in a trivalent.
, 4? grams" per" liter of sulfuric acid" and" about 215% 4:5 grams per liter of nitric acid, the weight ratio of sulfuric, acid to acetic acid being approximately 2:1 and the weight ratio of SO; !CIO4 being within the range of 1:4 to 1:16.
6. A concentrate adapted to be added to water to produce an aqueous metal? treating solution, said concentrate consisting essentially of an aqueous solution of chromic aeid containing-- chromium in" an? amount- 1 from about 200 grams per'litertothesaturatiorr solubility in the solution -at2v0-? l 0f: which at least 1' grampent liter and not more-: than 1:1- gratn'sper' litristrivalnt chromium, the remainder being, chromium" in. a hertavalent state;'20"to lflvgramsperr'liter of'acetic acid, 41) to grams per liter ofsulfiiridacid and to 300 grams per liter of nitricfiacidithe weightiratio of sulfuric acid to acetic acid being approximately 2:1 and the weight ratio of S0 ":CrO being within the range of-1 :4to 1:16.
7- A concentrate; as claimed: in claim- 6 in which--= sodium sulfite is :present. in an amount sufiicient; to, pro duce trivalent i chromium within the proportions stated-.2.
8. An acidic aqueous metal treating: concentrate; adap ted tube-diluted with. waterto form a metaliprotecting material,= said concentratehaving the following, approximate compositionr Ingredients? Grams per liter" Chro'm'ic'anhydrideI(CrO)T 401:0 Sodium sulfi'te (Na @80 7:5 Acetic-acid 22(5 Sulfuric acid?" t 45:0. Nitric-acid 228.0
the remainder being water.
. References"Gited-in-tlie 'file of this patent UNITEDSTATES-PATENTS 2,035,380 Wilhelm' Mar. 24, 1936" 2523,9251 Ostran der' Feb; 17, 1953 2,796,372 Chester'feflall June 18; T V EOREI-GNPATENTS 586,517 Great'Britair'r Mar; 21; 1947" 489,887 Great'Bfitain': July 2, 1947 852,634 Germany, Oct, 16,, 19 52:
UNITED STATES PATENT @FFICE CERTIFICATE OF EGRRECTIGN Patent Noa 2,902,394 September 1, 1959 Bruno Re Jeremias It is hereby certified that error appears in the-printed specification of the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.
Column 3, line 35, for "acetic acir" read acetic acid,-- line 4'7, after "state" insert a comma; column 4., line 46, list of references cited, under "FOREIGN PATENTS" for "489,887" read 589,887
Signed and sealed this 23rd day of February 1969 (SEAL) Attest:
KARL Ha AXLINE ROBERT C. WATSON Attesting Officer Commissioner of Patents
Claims (1)
1. A PROCESS OF FINISHING ZINC SURFACED ARTICLES WHICH COMPRISES TREATING THE SURFACES OF SUCH ARTICLES WITH AN AQEUOUS SOLUTION OF CHROMIC ACID CONTAINING 3 TO 90 GRAMS PER LITER OF CHROMIUM OF WHICH AT LEAST 0.015 GRAM PER LITER BUT NOT MORE THAN ABOUT 4.4 GRAMS PER LITER IS CHROMIUM IN A TRIVALENT STATE, THE REMAINDER BEING CHROMIUM, IN A HEXAVALENT STATE, 0.3 TO 0.6 GRAM PER LITER OF ACETIC ACID, 0.6 TO 1.2 GRMAS PER LITER OF SULFURIC ACID, AND ABOUT 2.25 GRAMS PER LITER OF 4.5 GRAMS PER LITER OF NITRIC ACID, THE WEIGHT RATIO OF SULFURIC ACID TO ACETIC ACID BEING APPROXIMATELY 2:1 AND THE WEIGHT RATIO OF SO4--:CRO4--BEING WITHIN THE RANGE OF ABOUT 1:4 TO 1:16.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US598762A US2902394A (en) | 1956-07-19 | 1956-07-19 | Protective metal coating compositions and method of coating |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US598762A US2902394A (en) | 1956-07-19 | 1956-07-19 | Protective metal coating compositions and method of coating |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US2902394A true US2902394A (en) | 1959-09-01 |
Family
ID=24396814
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US598762A Expired - Lifetime US2902394A (en) | 1956-07-19 | 1956-07-19 | Protective metal coating compositions and method of coating |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US2902394A (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3090710A (en) * | 1959-05-27 | 1963-05-21 | Hooker Chemical Corp | Method and solution for producing chromate coatings on zinc and zinc alloys |
| US3147153A (en) * | 1960-12-09 | 1964-09-01 | M & T Chemicals Inc | Process for providing a chromate coating on zinc and cadmium surface |
| US3210220A (en) * | 1962-07-30 | 1965-10-05 | Norman E Clegg | Process for coating stainless steel |
| US4161409A (en) * | 1978-03-06 | 1979-07-17 | Louis Schiffman | Corrosion inhibitive pigment |
| US6537678B1 (en) | 2000-09-20 | 2003-03-25 | United Technologies Corporation | Non-carcinogenic corrosion inhibiting additive |
| EP1493846A1 (en) | 2003-06-30 | 2005-01-05 | United Technologies Corporation | Corrosion inhibiting additive and corrosion inhibiting coating |
| DE102004001945A1 (en) * | 2004-01-14 | 2005-08-11 | Ina-Schaeffler Kg | Black passivation of zinc or zinc alloy surfaces |
| US20070228332A1 (en) * | 2006-04-04 | 2007-10-04 | United Technologies Corporation | Chromate free waterborne corrosion resistant primer with non-carcinogenic corrosion inhibiting additive |
| US20090004486A1 (en) * | 2007-06-27 | 2009-01-01 | Sarah Arsenault | Corrosion inhibiting additive |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2035380A (en) * | 1933-05-13 | 1936-03-24 | New Jersey Zinc Co | Method of coating zinc or cadmium base metals |
| GB489887A (en) * | 1937-06-11 | 1938-08-05 | Harold Victor Scott | Improvements in draught, weather and like excluders for use on doors, windows and like closures |
| GB586517A (en) * | 1944-04-20 | 1947-03-21 | Taylor Frank | Improvements in or relating to the protective surface treatment of zinc, zinc coated and zinc alloy articles |
| DE852634C (en) * | 1946-01-17 | 1952-10-16 | United Chromium | Immersion process for the formation of transparent surface protection coatings on zinc |
| US2628925A (en) * | 1947-06-24 | 1953-02-17 | Rheem Mfg Co | Bright corrosion resistant coating of metals |
| US2796372A (en) * | 1953-05-07 | 1957-06-18 | Poor & Co | Corrosion protecting metal finishing composition |
-
1956
- 1956-07-19 US US598762A patent/US2902394A/en not_active Expired - Lifetime
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2035380A (en) * | 1933-05-13 | 1936-03-24 | New Jersey Zinc Co | Method of coating zinc or cadmium base metals |
| GB489887A (en) * | 1937-06-11 | 1938-08-05 | Harold Victor Scott | Improvements in draught, weather and like excluders for use on doors, windows and like closures |
| GB586517A (en) * | 1944-04-20 | 1947-03-21 | Taylor Frank | Improvements in or relating to the protective surface treatment of zinc, zinc coated and zinc alloy articles |
| DE852634C (en) * | 1946-01-17 | 1952-10-16 | United Chromium | Immersion process for the formation of transparent surface protection coatings on zinc |
| US2628925A (en) * | 1947-06-24 | 1953-02-17 | Rheem Mfg Co | Bright corrosion resistant coating of metals |
| US2796372A (en) * | 1953-05-07 | 1957-06-18 | Poor & Co | Corrosion protecting metal finishing composition |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3090710A (en) * | 1959-05-27 | 1963-05-21 | Hooker Chemical Corp | Method and solution for producing chromate coatings on zinc and zinc alloys |
| US3147153A (en) * | 1960-12-09 | 1964-09-01 | M & T Chemicals Inc | Process for providing a chromate coating on zinc and cadmium surface |
| US3210220A (en) * | 1962-07-30 | 1965-10-05 | Norman E Clegg | Process for coating stainless steel |
| US4161409A (en) * | 1978-03-06 | 1979-07-17 | Louis Schiffman | Corrosion inhibitive pigment |
| US6537678B1 (en) | 2000-09-20 | 2003-03-25 | United Technologies Corporation | Non-carcinogenic corrosion inhibiting additive |
| EP1493846A1 (en) | 2003-06-30 | 2005-01-05 | United Technologies Corporation | Corrosion inhibiting additive and corrosion inhibiting coating |
| US7341677B2 (en) | 2003-06-30 | 2008-03-11 | United Technologies Corporation | Non-carcinogenic corrosion inhibiting additive |
| DE102004001945A1 (en) * | 2004-01-14 | 2005-08-11 | Ina-Schaeffler Kg | Black passivation of zinc or zinc alloy surfaces |
| US20070228332A1 (en) * | 2006-04-04 | 2007-10-04 | United Technologies Corporation | Chromate free waterborne corrosion resistant primer with non-carcinogenic corrosion inhibiting additive |
| US7972533B2 (en) | 2006-04-04 | 2011-07-05 | United Technologies Corporation | Chromate free waterborne corrosion resistant primer with non-carcinogenic corrosion inhibiting additive |
| US20090004486A1 (en) * | 2007-06-27 | 2009-01-01 | Sarah Arsenault | Corrosion inhibiting additive |
| US10774428B2 (en) | 2007-06-27 | 2020-09-15 | Raytheon Technologies Corporation | Method for corrosion inhibiting additive |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US2364993A (en) | Process for blackening copper or copper alloy surfaces | |
| US2902394A (en) | Protective metal coating compositions and method of coating | |
| US2106904A (en) | Coating malleable non-noble heavy metals | |
| US2577887A (en) | Activation of oxalate metal coating compositions | |
| US2460896A (en) | Composition for blackening copper and copper alloy surfaces | |
| US1911537A (en) | Eobebt r | |
| US2904414A (en) | Formulation for producing a protective bright chemically polished surface on zinc and cadmium | |
| US3843430A (en) | Chromate-free bright dip for zinc and cadmium surfaces | |
| US3106484A (en) | Metal treating | |
| GB586517A (en) | Improvements in or relating to the protective surface treatment of zinc, zinc coated and zinc alloy articles | |
| CA1206852A (en) | Process and composition for phosphating metal surfaces | |
| US2271375A (en) | Process of coating metal surfaces | |
| US3338755A (en) | Production of phosphate coatings on metals | |
| US2548419A (en) | Method for production of lustrous zinc | |
| US2796372A (en) | Corrosion protecting metal finishing composition | |
| US3181976A (en) | Phosphating process and composition | |
| US3090710A (en) | Method and solution for producing chromate coatings on zinc and zinc alloys | |
| US2628925A (en) | Bright corrosion resistant coating of metals | |
| US2067214A (en) | Method of coating metal | |
| US2499231A (en) | Method of producing surface conversion coatings on zinc | |
| US3400021A (en) | Conversion coating compositions and method | |
| US2557509A (en) | Composition and process for protecting ferrous metals from rusting in moist air | |
| US2431728A (en) | Treatment of ferrous metals to improve resistance to rusting | |
| US2314887A (en) | Method of coating metal and material | |
| US2121520A (en) | Maintenance of phosphate coating baths |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| AS | Assignment |
Owner name: BRENT CHEMICALS CORPORATION, A CORP. OF DE. Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNOR:STAUFFER CHEMICAL COMPANY;REEL/FRAME:003837/0384 Effective date: 19810202 |