US2475981A - Process for blackening copper and copper alloys - Google Patents
Process for blackening copper and copper alloys Download PDFInfo
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- US2475981A US2475981A US687697A US68769746A US2475981A US 2475981 A US2475981 A US 2475981A US 687697 A US687697 A US 687697A US 68769746 A US68769746 A US 68769746A US 2475981 A US2475981 A US 2475981A
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- Prior art keywords
- copper
- blackening
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- alloys
- black
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title description 23
- 229910052802 copper Inorganic materials 0.000 title description 23
- 239000010949 copper Substances 0.000 title description 23
- 238000000034 method Methods 0.000 title description 16
- 229910000881 Cu alloy Inorganic materials 0.000 title description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 24
- 229910052751 metal Inorganic materials 0.000 description 12
- 239000002184 metal Substances 0.000 description 12
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 11
- 238000000576 coating method Methods 0.000 description 11
- 239000003513 alkali Substances 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 229910045601 alloy Inorganic materials 0.000 description 9
- 239000000956 alloy Substances 0.000 description 9
- 239000011248 coating agent Substances 0.000 description 9
- QDHHCQZDFGDHMP-UHFFFAOYSA-N Chloramine Chemical compound ClN QDHHCQZDFGDHMP-UHFFFAOYSA-N 0.000 description 8
- 238000009835 boiling Methods 0.000 description 8
- 125000001174 sulfone group Chemical group 0.000 description 7
- 125000003118 aryl group Chemical group 0.000 description 5
- 159000000000 sodium salts Chemical class 0.000 description 5
- 229910001369 Brass Inorganic materials 0.000 description 4
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 4
- 239000010951 brass Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 231100001261 hazardous Toxicity 0.000 description 3
- 235000011121 sodium hydroxide Nutrition 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 2
- 239000000908 ammonium hydroxide Substances 0.000 description 2
- DMFGNRRURHSENX-UHFFFAOYSA-N beryllium copper Chemical compound [Be].[Cu] DMFGNRRURHSENX-UHFFFAOYSA-N 0.000 description 2
- 238000004880 explosion Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 241000331231 Amorphocerini gen. n. 1 DAD-2008 Species 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
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- FXYAIULQRMTOIY-UHFFFAOYSA-L [OH-].[Na+].[Na+].[O-]Cl=O Chemical compound [OH-].[Na+].[Na+].[O-]Cl=O FXYAIULQRMTOIY-UHFFFAOYSA-L 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 1
- 150000008041 alkali metal carbonates Chemical class 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000001342 alkaline earth metals Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 229910052790 beryllium Inorganic materials 0.000 description 1
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 229910001919 chlorite Inorganic materials 0.000 description 1
- 229910052619 chlorite group Inorganic materials 0.000 description 1
- QBWCMBCROVPCKQ-UHFFFAOYSA-N chlorous acid Chemical compound OCl=O QBWCMBCROVPCKQ-UHFFFAOYSA-N 0.000 description 1
- 229940116318 copper carbonate Drugs 0.000 description 1
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000004922 lacquer Substances 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000002420 orchard Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000011253 protective coating Substances 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- UKLNMMHNWFDKNT-UHFFFAOYSA-M sodium chlorite Chemical compound [Na+].[O-]Cl=O UKLNMMHNWFDKNT-UHFFFAOYSA-M 0.000 description 1
- 229960002218 sodium chlorite Drugs 0.000 description 1
- -1 sulphone chloramide compound Chemical class 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- 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
- C23C22/60—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 alkaline aqueous solutions with pH greater than 8
- C23C22/63—Treatment of copper or alloys based thereon
Definitions
- This invention relates to-a process for blackening copper and copper alloys and has for its object the attainment of highly successful results in producing a black coating on such metal parts without the disadvantagesattendant upon the use of baths heretofore used'for this purpose.
- Black copper oxide films have been producedon copper and copper alloys by a number of methods. This black oxide is a durable coating and adheres tenaciously to the base metal. The black oxide film, moreover, can be produced in either a dull or shiny finish.
- the baths formerly used to produce the black copper oxide coatings have had many disadvantages.
- One commonly used bath compound of copper carbonate and ammonium hydroxide is diificult to operate because of the sensitivity of the bath to deficiencies or excesses of ammonium hydroxide. The bath also has a short life and must be discarded when used for only a short time.
- Another type ofbath composed of caustic soda and sodium chlorite produces a satisfactory black copper oxide coating, but has the disadvantage of being composed partly of a hazardous sub stancesodium chlorite. This material is especially hazardous in the dry state as it is a powerful oxidizing agent. Wood, cloth, paper and other common packaging materials are rendered highly inflammable by the sodium hydroxide-sodium chlorite mixture.
- a bath comprising a water solution of a Water soluble salt of an aryl sulphone monochloramide made alkaline with a strong water soluble alkali is free of the objections above mentioned and is effective for use suitable for use in a copper blackening bath.
- Baths for blackeningcopper employing this material can vary widely in proportion, yet give a suitable black. As little as by weight of the sulphone monochloramide and A; of water soluble alkali give excellent blackening baths. Large amounts also produce satisfactory baths and the amounts are limited by the solubilities of the components. However, there is no advantage in the use of higher concentrations and because of economic reasons I prefer the more dilute solutions.
- the strong water soluble alkalies acceptable for this composition are those of the alkali metal and alkaline earth metal groups. While the carbonates of some of these are satisfactory, the alkali metal hydroxides appear to be most suitable.
- Example N0 1.--For copper Two parts by weight of the sodium salt of benzenesulphonemonochloramide and two parts by weight of sodium hydroxide are dissolved in parts by weight of water. This solution is heated to a temperature of F. and the piece of copper to be coated previously cleaned by the customary mechanical and chemical methods is immersed in the bath for a period of from 5 to 15 minutes. Upon removing the copper piece from the bath, it is rinsed in water for a sulficient length of time to remove completely any residue from the alkaline bath and is then dried. A durable, velvety, jet black coating which adheres tenaciously to the copper piece will be present on its surface. This coating can be made shiny by logues as part of the molecule, to be especially 55 gentlebuffing orby means of oil or wax finishes.
- Example No. 3 For beryllium copper "i'Iwo j'pa'rts by weight of the sodium salt :of benzene tsulphone monochloramide "and four partsi by weight of sodium carbonate are dissolve'd'iin 100partszby weight oflwater; This solution ris heated to a temperature "of 200 F. andia-pi'ece of beryllium copper to be coated, previously'eleaned byithe customary mechanical and chemical methods is a immersed in 'the bath for aipverio'd of fromf5ito'15 minutes.
- the temperature may-vary widely and theirate' of blackening w'ill be relativelylow at lthellowerl temperatures and high at the' higherttemperatures. I have 'found that :temperatures aslow as 1.125? .F.'wi1l produce .a satisfactory black, but is time consuming. Temperatures 'ibetween 1175 "and boiling zwill :be iiound to "be mvstasuitabl'e for blackening baths.
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- 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
Patented July 12, 1949 PROCESS FOR BLACKENING COPPER AND COPPER ALLOYS Isaac Laird Newell, Wethersfield, Conn., assignor to Heatbath Corporation, Indian Orchard,
Mass, a corporation of Massachusetts No Drawing. Application'August 1, 1946, Serial No. 687,697
9 Claims.
This invention relates to-a process for blackening copper and copper alloys and has for its object the attainment of highly successful results in producing a black coating on such metal parts without the disadvantagesattendant upon the use of baths heretofore used'for this purpose.
Up to the present time, the art of blackening copper and copper alloys-has been confined for the most part to processes which give an oxide or sulphide film on the surface. While the baths to produce the black sulphide films are comparatively simple and easy to operate, non-toxic and free from explosion and fire hazard, the film is, however, rather soft, and its adhesion to the metal surface is poor. Moreover, the sulphide film can only be produced satisfactorily on copper or alloys very high in copper. Other copper alloys would need to be copper plated before blackening. A protective coating of lacquer or wax is necessary to preserve the sulphide film and insure its permanence.
Black copper oxide films have been producedon copper and copper alloys by a number of methods. This black oxide is a durable coating and adheres tenaciously to the base metal. The black oxide film, moreover, can be produced in either a dull or shiny finish. However, the baths formerly used to produce the black copper oxide coatings have had many disadvantages. One commonly used bath compound of copper carbonate and ammonium hydroxide is diificult to operate because of the sensitivity of the bath to deficiencies or excesses of ammonium hydroxide. The bath also has a short life and must be discarded when used for only a short time.
Another type ofbath composed of caustic soda and sodium chlorite produces a satisfactory black copper oxide coating, but has the disadvantage of being composed partly of a hazardous sub stancesodium chlorite. This material is especially hazardous in the dry state as it is a powerful oxidizing agent. Wood, cloth, paper and other common packaging materials are rendered highly inflammable by the sodium hydroxide-sodium chlorite mixture.
I have discovered that a bath comprising a water solution of a Water soluble salt of an aryl sulphone monochloramide made alkaline with a strong water soluble alkali is free of the objections above mentioned and is effective for use suitable for use in a copper blackening bath. One compound of this group particularly suitable from the standpoint of commercial use, is the sodium salt of benzenesulphonemonochloramide. This organic compound is not hazardous from the standpoint of fires and explosion in either the dry state or in solution. Baths for blackeningcopper employing this material can vary widely in proportion, yet give a suitable black. As little as by weight of the sulphone monochloramide and A; of water soluble alkali give excellent blackening baths. Large amounts also produce satisfactory baths and the amounts are limited by the solubilities of the components. However, there is no advantage in the use of higher concentrations and because of economic reasons I prefer the more dilute solutions.
Among the strong water soluble alkalies acceptable for this composition are those of the alkali metal and alkaline earth metal groups. While the carbonates of some of these are satisfactory, the alkali metal hydroxides appear to be most suitable.
Of the copper alloys tested with this bath, I have found those containing zinc, lead, tin, phosphorus, silver, aluminum, silicon and beryllium to give unusually good black coatings. 'I do not limit myself, however, to the alloys mentioned above, and this list is given to show the wide range of alloys which may be blackened by my process.-
'Herewith are given by way of example several specific disclosures of my process for the black coating of copper and two of its principal alloys.
Example N0. 1.--For copper Two parts by weight of the sodium salt of benzenesulphonemonochloramide and two parts by weight of sodium hydroxide are dissolved in parts by weight of water. This solution is heated to a temperature of F. and the piece of copper to be coated previously cleaned by the customary mechanical and chemical methods is immersed in the bath for a period of from 5 to 15 minutes. Upon removing the copper piece from the bath, it is rinsed in water for a sulficient length of time to remove completely any residue from the alkaline bath and is then dried. A durable, velvety, jet black coating which adheres tenaciously to the copper piece will be present on its surface. This coating can be made shiny by logues as part of the molecule, to be especially 55 gentlebuffing orby means of oil or wax finishes.
3 Example No. 2.--For brass (85% copper, 15% zinc) Two parts by weight of the sodium salt of toluenesulphonemonochloramide and two parts by weight of potassium hydroxide are dissolved in 100 partss-by weight of water. "This solution is heatedto boiling, and the piece'of brass to be coated, previously cleaned by the customary mechanical and chemical methods is immersed in the bath for a period of from,.5-.to :15 minutes. Upon removing the brass piece from the-bath, it is rinsed in water vfor a sufficient length of time to remove completely any residue' frcvm thealka line bath and is then dried. "A- durablefvelvety, jet black coating which adheres tenaciouslyto the brass piece will be presentLoh its :surface. This coating can be made shiny by gentle bufling or by means of oil or wax finishes.
Example No. 3.For beryllium copper "i'Iwo j'pa'rts by weight of the sodium salt :of benzene tsulphone monochloramide "and four partsi by weight of sodium carbonate are dissolve'd'iin 100partszby weight oflwater; This solution ris heated to a temperature "of 200 F. andia-pi'ece of beryllium copper to be coated, previously'eleaned byithe customary mechanical and chemical methods is a immersed in 'the bath for aipverio'd of fromf5ito'15 minutes. Upon-removingithe piecefifrom-the' bath, itiis rinsed in water for-a sufficient length *oftime to remove oompletely any residuetfrom the alkaline bath and is thendried. 1A durable,velvety, jet blacktcoating whichadheres 'tenaciously to the piece will' be presentron' its surface. .This coating canbema'de 'shinyibyfgentle.buffing or by imeans 'of-ioil or waxfinishes.
It is to be understood that the organic-ashlphone :monochlorami'des given in' the above examples areinot'confinedto the examples cite d but may be interchanged. Moreover, other organic sulphone 'monochloramides'of this *type may b'ersubstituted. In. likemanner the alkalies used may be interchanged.
The "temperature of the bath forthe blackening 'operationrzis 'notlimited to those :giverrin" the examples. The temperature may-vary widely and theirate' of blackening w'ill be relativelylow at lthellowerl temperatures and high at the' higherttemperatures. I have 'found that :temperatures aslow as 1.125? .F.'wi1l produce .a satisfactory black, but is time consuming. Temperatures 'ibetween 1175 "and boiling zwill :be iiound to "be mvstasuitabl'e for blackening baths.
1. The process of blackening copper and its alloys in which the metal isimmersed in a solution consisting of 2 parts of the sodium salt .of benzene sulphone "monochloramide, 2 parts of sodium hydroxide and 100'parts otwat'er', said solution being. heatedto a temperature between 175 Rand boiling, and the metal iheldin'said solutionfor'a sufficient time toproduce'the des'ireddepth of color.
'2 Thepro'cess Iof blackening copper and its allbys in whichthemetal is immersed in asolution consisting-of 'a water solution of a'water solublesalt of an aryl sulphone monochloramide made'alkaline-with a strong water solublefixed alkali, said 'solution bein'gheate'd to a temperature i between 175 -'F. and T boiling and l the metal heldiin isaid-solution for a sufiici'ent time to -producezthe desired zdepth 'pfiblack.
:siul'he pro'cesslof 'claim z izriwhicmtm propor 4 tion of aryl sulphone monochloramide to the strong water soluble fixed alkali is 1:1.
4. The process of blackening copper and its alloys in which the metal is immersed in a solution consisting of a water solution of a water soluble .salt of an aryl sulphone-monochloramide made alkaline with a strong watersoluble fixed alkali in which the organic group of the sulphone chloramide compound consists of a homologue of benzene, said solution being heated to a tem- :perature between'1'75" F. and boiling and the metal held in said solution for a sufficient time :to produce .thedesired depth of black.
fiiTheexprocess .of blackening copper and its alloysiinwhichithe.metal is immersed in a solution consisting of .a water solution of the sodium .salt of benzene'sulphone monochloramide made alkaline with a strong water soluble fixed alkali,
, saidrsolution being heated to a temperature between 175 F. and boiling and the metal held in SaidfSOIUtiOII'fOI a sufiicient time to produce the desired depth :of black,
-;6. The process of blackening copper and its alloys sin which thelmetal. is immersed in a .solution consisting of a water solution of thesodium salt of toluenesulphonemonochloramide made alkaline withastrong water soluble .fixed alkali, said-" solution .beinghea-ted .to a temperature-between 1-75" F. and vboiling and the metal-heldin said solutionrior a sufficient time .to producelthe desired depth of black. v
-7. The process of blackening copper and its alloys'in whichthe metal is immersed in a solution consisting of a water-soluti0n of a water solublesalt of an aryl sulphonemonochloramide made alkalinewith an alkali metal hydroxide, said solution beingiheated vto a temperature between 175 F. an'd'boiling and themetal heldvin said solution for a sufficient time to produce the desired depth of .black'.
8. The process of claim 6..in whichtheproportion of organic sulphonevmonochloramide to alkali .met'al hydroxide is 1.2.1 and the r solution strength l is 4 parts by weight .of: said. compounds to:100 parts by weight of water.
9..-' 1he,,process of blackening copper andits alloys intwhich the metal islimmersed in asolution consisting of a water solutionof a water soluble-salt of-an-aryl sulphone monochloramide made alkaline with an' alkali metal carbonate,
.said solution being-heated to 1 a temperature between .1.'l5- F. and .boiling and the metal held in said solution .for .asuflicient time. to produce the-desired depth of black.
ISAAC LAIRD NEWELL.
' REFERENCES CITED The :Iollowing :reierenlces are: of record in vthe file of this patent:
UNITED" STATES PATENTS Number I Name. Date 1,650,124 Gunzler et -.al. Nov. 22,.1927 1,769,852 vOgden July 1, 1930 1,890,603 Feibelmann in"... Deep 13, 1932 -1,892,548 Feibelmann 1-.-- Dec. -27, 1932 .1.,a9'4;5e9. -Mirau4-. a Jan, .17, 1933 "23641993 Meyer .Dec. .12, 1944 :EOREIGNTPATENTS Number Country v Date.
4239164 '=Germany 'May 12, 1926 5903376; *-France' Marf27, 1925 $47566 T "Germany 1 July 711937
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US687697A US2475981A (en) | 1946-08-01 | 1946-08-01 | Process for blackening copper and copper alloys |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US687697A US2475981A (en) | 1946-08-01 | 1946-08-01 | Process for blackening copper and copper alloys |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US2475981A true US2475981A (en) | 1949-07-12 |
Family
ID=24761447
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US687697A Expired - Lifetime US2475981A (en) | 1946-08-01 | 1946-08-01 | Process for blackening copper and copper alloys |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US2475981A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2579752A (en) * | 1950-03-11 | 1951-12-25 | Newell Isaac Laird | Process for blackening iron and steel and composition of matter therefor |
| DE974502C (en) * | 1950-11-21 | 1961-01-19 | Metallgesellschaft Ag | Process for the production of uniform, firmly adhering sulfide films on metals, in particular iron and steel |
| US4195124A (en) * | 1976-04-26 | 1980-03-25 | Sekisui Kagaku Kogyo Kabushiki Kaisha | Solar radiation energy absorber |
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| US1890603A (en) * | 1928-03-01 | 1932-12-13 | Heyden Chem Fab | Composition of bleaching agents |
| US1892548A (en) * | 1930-04-20 | 1932-12-27 | Feibelmann Richard | Compound and process for treating vegetable and animal fibers and fabrics |
| US1894539A (en) * | 1930-06-23 | 1933-01-17 | Heyden Chem Fab | Composition for disinfecting and bleaching and method of making the same |
| DE647566C (en) * | 1930-04-20 | 1937-07-07 | Chem Fab Pyrgos G M B H | Process for treating textile fabrics |
| US2364993A (en) * | 1942-12-29 | 1944-12-12 | Walter R Meyer | Process for blackening copper or copper alloy surfaces |
-
1946
- 1946-08-01 US US687697A patent/US2475981A/en not_active Expired - Lifetime
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE423464C (en) * | 1922-10-26 | 1926-05-12 | Chem Fab Von Heyden Akt Ges Fa | Process for bleaching fabrics |
| FR590876A (en) * | 1924-02-22 | 1925-06-24 | Alsacienne De Prod Chim Soc | New medium for bleaching, laundry and other similar uses |
| US1650124A (en) * | 1924-10-18 | 1927-11-22 | Winthrop Chem Co Inc | Stable mixture yielding salts of halogensulfonamids |
| US1769852A (en) * | 1927-06-27 | 1930-07-01 | Kodel Radio Corp | Method of producing rectifying units |
| US1890603A (en) * | 1928-03-01 | 1932-12-13 | Heyden Chem Fab | Composition of bleaching agents |
| US1892548A (en) * | 1930-04-20 | 1932-12-27 | Feibelmann Richard | Compound and process for treating vegetable and animal fibers and fabrics |
| DE647566C (en) * | 1930-04-20 | 1937-07-07 | Chem Fab Pyrgos G M B H | Process for treating textile fabrics |
| US1894539A (en) * | 1930-06-23 | 1933-01-17 | Heyden Chem Fab | Composition for disinfecting and bleaching and method of making the same |
| US2364993A (en) * | 1942-12-29 | 1944-12-12 | Walter R Meyer | Process for blackening copper or copper alloy surfaces |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2579752A (en) * | 1950-03-11 | 1951-12-25 | Newell Isaac Laird | Process for blackening iron and steel and composition of matter therefor |
| DE974502C (en) * | 1950-11-21 | 1961-01-19 | Metallgesellschaft Ag | Process for the production of uniform, firmly adhering sulfide films on metals, in particular iron and steel |
| US4195124A (en) * | 1976-04-26 | 1980-03-25 | Sekisui Kagaku Kogyo Kabushiki Kaisha | Solar radiation energy absorber |
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