US2460898A - Process and composition for coloring copper and copper alloy surfaces - Google Patents
Process and composition for coloring copper and copper alloy surfaces Download PDFInfo
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- US2460898A US2460898A US562053A US56205344A US2460898A US 2460898 A US2460898 A US 2460898A US 562053 A US562053 A US 562053A US 56205344 A US56205344 A US 56205344A US 2460898 A US2460898 A US 2460898A
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title description 26
- 229910052802 copper Inorganic materials 0.000 title description 26
- 239000010949 copper Substances 0.000 title description 26
- 238000004040 coloring Methods 0.000 title description 21
- 229910000881 Cu alloy Inorganic materials 0.000 title description 15
- 238000000034 method Methods 0.000 title description 12
- 239000000203 mixture Substances 0.000 title description 12
- 239000000243 solution Substances 0.000 description 25
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 23
- 159000000011 group IA salts Chemical class 0.000 description 23
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 22
- QBWCMBCROVPCKQ-UHFFFAOYSA-N chlorous acid Chemical class OCl=O QBWCMBCROVPCKQ-UHFFFAOYSA-N 0.000 description 12
- 229910001919 chlorite Inorganic materials 0.000 description 11
- 229910052619 chlorite group Inorganic materials 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 10
- 150000003839 salts Chemical class 0.000 description 10
- 239000003513 alkali Substances 0.000 description 9
- 239000007864 aqueous solution Substances 0.000 description 8
- 235000011118 potassium hydroxide Nutrition 0.000 description 7
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 description 7
- 235000019818 tetrasodium diphosphate Nutrition 0.000 description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- -1 brass Chemical compound 0.000 description 6
- 235000011121 sodium hydroxide Nutrition 0.000 description 6
- 239000003518 caustics Substances 0.000 description 5
- 239000003086 colorant Substances 0.000 description 5
- 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 4
- 229910021538 borax Inorganic materials 0.000 description 4
- UKLNMMHNWFDKNT-UHFFFAOYSA-M sodium chlorite Chemical compound [Na+].[O-]Cl=O UKLNMMHNWFDKNT-UHFFFAOYSA-M 0.000 description 4
- 229960002218 sodium chlorite Drugs 0.000 description 4
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 4
- 235000010339 sodium tetraborate Nutrition 0.000 description 4
- 239000004328 sodium tetraborate Substances 0.000 description 4
- 239000008247 solid mixture Substances 0.000 description 4
- 239000004115 Sodium Silicate Substances 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- 235000019795 sodium metasilicate Nutrition 0.000 description 3
- 239000001488 sodium phosphate Substances 0.000 description 3
- 229910052911 sodium silicate Inorganic materials 0.000 description 3
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 3
- 235000019801 trisodium phosphate Nutrition 0.000 description 3
- 229910000406 trisodium phosphate Inorganic materials 0.000 description 3
- 229910001369 Brass Inorganic materials 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000010951 brass Substances 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 229940077239 chlorous acid Drugs 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- OSVXSBDYLRYLIG-UHFFFAOYSA-N dioxidochlorine(.) Chemical compound O=Cl=O OSVXSBDYLRYLIG-UHFFFAOYSA-N 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 229940072033 potash Drugs 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 235000015320 potassium carbonate Nutrition 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 238000011282 treatment Methods 0.000 description 2
- NDNUANOUGZGEPO-UHFFFAOYSA-N (s)-2-propylpiperidine Chemical compound CCCC1CCCCN1 NDNUANOUGZGEPO-UHFFFAOYSA-N 0.000 description 1
- 241000282836 Camelus dromedarius Species 0.000 description 1
- 239000004155 Chlorine dioxide Substances 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- 229910001209 Low-carbon steel Inorganic materials 0.000 description 1
- 241001124569 Lycaenidae Species 0.000 description 1
- 241001275902 Parabramis pekinensis Species 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
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 201000001493 benign recurrent intrahepatic cholestasis Diseases 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
- QXIKMJLSPJFYOI-UHFFFAOYSA-L calcium;dichlorite Chemical class [Ca+2].[O-]Cl=O.[O-]Cl=O QXIKMJLSPJFYOI-UHFFFAOYSA-L 0.000 description 1
- 235000019398 chlorine dioxide Nutrition 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 235000014987 copper Nutrition 0.000 description 1
- 239000007799 cork Substances 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 210000003298 dental enamel Anatomy 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical compound [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 description 1
- 235000011180 diphosphates Nutrition 0.000 description 1
- UQGFMSUEHSUPRD-UHFFFAOYSA-N disodium;3,7-dioxido-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane Chemical compound [Na+].[Na+].O1B([O-])OB2OB([O-])OB1O2 UQGFMSUEHSUPRD-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000004922 lacquer Substances 0.000 description 1
- 235000012054 meals Nutrition 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 231100000989 no adverse effect Toxicity 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 238000009527 percussion Methods 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000011833 salt mixture Substances 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 239000012047 saturated solution Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- POWFTOSLLWLEBN-UHFFFAOYSA-N tetrasodium;silicate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-][Si]([O-])([O-])[O-] POWFTOSLLWLEBN-UHFFFAOYSA-N 0.000 description 1
- 239000001993 wax 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 the coloring of copper and copper alloy surfaces.
- .I produce these and other colors on copper and copper alloy surfaces by a process which comprises contacting the surface with an aqueous solution containing an alkali or alkaline earth metal chlorite, e. g. sodium, potassium, and calcium chlorites, and an alkaline salt.
- the alkali and alkaline earth metal chlorites are salts of chlorous acid and when chemically pure are essentially neutral in reaction.
- the surface to be cc]- ored is immersed in the salt solution.
- alkaline salts which may be employed in the process of my invention may be mentioned: sodium carbonate, sodium metasilicate, sodium tetraborate, trisodium phosphate, tetrasodium pyrophosphate, sodium sesquisilicate, sodium orthosilicate, and the corresponding potassium and alkaline earth compounds where they are water-soluble. If desired, the process may be executed using a plurality of alkaline salts and/r chlorites.
- a strong alkali such as sodium or potassium hydroxide
- the presence of substantial amounts of a strong alkali such as sodium or potassium hydroxide in the coloring solution is without harmful efiect, in fact maybe advantageous particularly where it is desired to accomplish the coloring as rapidly as possible or to impart colors other than shades of brown, for example, a bluish, purplish, or greenish color.
- the exact color produced on the surface treated depends upon various factors including the composition of the surface, the particular salts being employed, the concentration of the salts, the temperature at which the solution is maintained, and the contact or treating time. tions necessary to achieve a particular color can be readily determined by simple experiments well 2 within the skill of those experienced in the metal coloring art.
- chlorite- 10 g./l., alkaline salt-20 g./l. chlorite g./l., alkaline saltg./l.
- the tank In making up the solution, the tank is usually lied about three-quarters full of water after hich the pre-inixed salts are added with stirng until they are completely dissolved. The mk is then filled to the operatinglevel with iditional water.
- composition does not involve the risk of lorine dioxide liberation that would be involved the chloritehandled separately were so spilled.
- the composition ty include substantial amounts, i.e. up to 50%, sodium or potassium hydroxide.
- composition conning 2 parts alkaline salt per part chlorlte is ded to water to form the coloring solution in a proportion of about 1 lb. for each gallon of ter.
- Cleancan he done with alkaline cleaners, vapor or or-solvent de-greasers, or by emulsion clean-
- the cleaning is not as critical as that for ting, but it is recommended to the end of ining uniform coloring that the surface be med to the extent that water when placed on surface remains thereon as a continuous film at least one minute without separating into plets i. e.. no water-break.
- the work is preferably roughly rinsed after cleaning and then dipped :odiu'm cyanide solution as in the instance of itroplated copper.
- I can usually produce'the [red color on pure copper and high copper iys in from 1 to 10 minutes. In some cases 4 less than 30 seconds is suilicient. Low copper alloys may require as long as 20 minutes. After coloring, the work should be thoroughly rinsed in running cold water and then in hot water if it 5 is to be dried.
- the work may be subjected to various after-treatments such as tumbling in saw-dust, corn cob drying meal, or
- paraffin coated ground cork Where the work must withstand severe outdoor weathering, it is advisable to augment the protective effect of the finish with either lacquer, oil, or wax.
- the herein described process is suitable for coloring all copper alloys containing as little as 60% of copper.
- 60:40, 65:35, 70:30, 80:20, and 90:10 brasses are readily colored, as well as tin bronzes, silicon bronzes, beryllium coppers, and phosphor bronzes. Pure copper whether cast,
- the process is also applicable to the coloring of electrolytically deposited brass alloys where the nominal copper content or the alloy is 60% or more.
- a solid composition in finely divided form adapted for use in aqueous solution to color copper surfaces or surfaces of copper alloys con taining not less than 60% copper which consists of about 1 part by weight of an alkali metal chlorlte and from about 1 to about 2.5 parts by weight of an alkaline salt having an alkalinity equal to or greater than that of tetrasodium pyrophosphate but less than that of caustic soda 40 or potash.
- a solid composition in finely divided form' adapted for use in aqueous solution to color copper surfaces or surfaces of copper alloys comprising not less than 60% copper which consists of about 1 part by weight of sodium chlorlte and about 2 parts by weight of an alkaline salt having an alkalinity equal to or greater than that of tetrasodiumpyrophosphate but less than that of caustic sodayor potash.
- a process for coloring copper surfaces and surfaces of copper alloys containing not less than 60% copper which comprises contacting the surface with an aqueous solution consisting essentially of water. a chlorlte of the group consisting of alkali and alkaline earth metal chlo-.
- an alkaline salt having an alkalinity equal to,”or greater than, that of tetrasodium pyrophosphate but less than that of caustic soda or caustic potash, in proportions by weight within the range of 1 to 2.5 parts of the alkaline salt per part of the chlorlte, and 0 to 50%, based on the total weight of the chlorlte and alkaline salt, of a caustic alkali, the concentration of the salts in the solution being within the range of 4 grams per liter to saturation.
- a process for coloring copper surfaces and A surfaces of copper alloys containing not less than V 60% copper whichcomprises immersing the surface in a hot aqueous solution consisting essentially of water, an alkali metal salt of chlorous acid, an alkaline salt having'an alkalinity equal to, or greater than, that of tetrasodium pyrophosphate but less, than that of caustic soda or caustic potash, in proportions by weight within the range of 1 to 2.5 parts of the alkaline salt per part of the chlorite, the concentration of the salts in the solution being within the range of 4 grams per liter to saturation.
- a process for coloring copper surfaces and surfaces of copper alloys containing not less than 60% copper which comprises immersing the surface in a hot aqueous solution consisting essentially of water, sodium chlorite and an alkaline salt having an alkalinity equal to, or greater than, that of tetrasodium pyrophosphate but less than that of caustic soda or caustic potash, in proportions by weight of about 1 to 2, the concentration of the chlorlte in the solution being within the range of 10 grams per liter to 80 grams per liter.
- a solid composition in finely divided form adapted for use in aqueous solutions to color copper surfaces and surfaces of copper alloys containing not less than 60% copper the composition consisting essentially of a chlorite of the group consisting of the alkali and alkaline earth metal chlorites, an alkaline salt having an alkalinity equal to, or greater than, that of tetrasodium pyrophosphate, but less than that 01 caustic soda or caustic potash, in proportions by weight within the range of 1 to 2.5 parts of the alkaline salt per part of the chlorite, and 0 to 50% based on the total weight 01' the chlorite and alkaline salt of a caustic alkali.
- a solid composition in finely divided form for use in aqueous solution to color copper surfaces or surfaces of copper alloys containing not less than 60% copper the composition consisting essentially of an alkali metal chlorite, an alkaline salt having an alkalinity equal to, or greater than, that of tetrasodlum pyrophosphate but less than that of caustic soda or caustic potash, in proportions by weight within the range of 1 to 2.5 parts of the alkaline salt per part of the chlorite, and 0 to 50% based on the total weight of the chlorite and alkaline salt of a caustic alkali.
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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 Feb. 8, 1949 H'EED PROCESS AND COMPOSITION FOR COLOR- ING COPPER AND COPPER ALLOY SUB- FACES Walter E. Meyer, Hamden, Conn.,. assignor, by
mesne assignments, to- Enthone, Inc.,
New
Haven, Conn., a corporation of Connecticut No Drawing. Application November 4, 1944, Serial No. 562,053
'1 Claims. (01. 148-614) This invention relates to the coloring of copper and copper alloy surfaces.
It is frequently desirable in the finishing of articles such as metal buttons and buckles, costume and cosmetic accessories, lamp bases and stands, urns, screens, tacks, particularly upholstery tacks, builders hardware and architectural items, and the like, fabricated from copper and copper alloys, such as brass, to treat the surfaces of the article to impart thereto a color not characteristic of the untreated metal. Various shades of brown including tan, greenish-brown, brownish-gold, etc., are considered particularly desirable. I
In accordance with the present invention, .I, produce these and other colors on copper and copper alloy surfaces by a process which comprises contacting the surface with an aqueous solution containing an alkali or alkaline earth metal chlorite, e. g. sodium, potassium, and calcium chlorites, and an alkaline salt. The alkali and alkaline earth metal chlorites are salts of chlorous acid and when chemically pure are essentially neutral in reaction. In the preferred mode of executing the process the surface to be cc]- ored is immersed in the salt solution.
Among the many alkaline salts which may be employed in the process of my invention may be mentioned: sodium carbonate, sodium metasilicate, sodium tetraborate, trisodium phosphate, tetrasodium pyrophosphate, sodium sesquisilicate, sodium orthosilicate, and the corresponding potassium and alkaline earth compounds where they are water-soluble. If desired, the process may be executed using a plurality of alkaline salts and/r chlorites. The presence of substantial amounts of a strong alkali such as sodium or potassium hydroxide in the coloring solution is without harmful efiect, in fact maybe advantageous particularly where it is desired to accomplish the coloring as rapidly as possible or to impart colors other than shades of brown, for example, a bluish, purplish, or greenish color.
It will be understood that the words color and coloring are used herein andv in the appended claims in the strict sense and do not include black or blackening. I
The exact color produced on the surface treated depends upon various factors including the composition of the surface, the particular salts being employed, the concentration of the salts, the temperature at which the solution is maintained, and the contact or treating time. tions necessary to achieve a particular color can be readily determined by simple experiments well 2 within the skill of those experienced in the metal coloring art.
I have found that in most cases the solution with proper adjustment of other conditions may be effectively operated at any temperature between 70 F. and its boiling point. However, I
" prefer to operate the solution at temperatures tains the chlorite and alkaline salt in a ratio The condiby weight within the range 1:1 to 122.5. Using such ratios of chlorite and alkaline salts, I have been able in many cases to obtain equivalent results from saturated solutions and solutions containing as little as a total of 4'. grams per liter of-the salts. The less concentrated solutions, however, must usually be operated at a higher temperature in order to accomplish the coloring in the same length of time. In operating at high concentrations, I have noticed that no adverse effect results from the presence of substantial amounts of undissolved salts in the solution. In general, I prefer to employ a solution in which the concentrations of the salts are within the following limits: chlorite- 10 g./l., alkaline salt-20 g./l. to chlorite g./l., alkaline saltg./l. I usually employ sodium chlorite in the practice of the invention because of its solubility and because it is readily available commercially.
Some combinations of the salts used in the execution of the invention give various colors while other combinations appear capable of imparting only a relatively few colors or of giving only a single color. I have found that the solution as prepared with sodium chlorite and either sodium carbonate or trisodium phosphate will give the greatest number of colors of the various chloritealkaline salt mixtures. When prepared with borax or sodium metasilicate in lieu of sodium carbonate or trisodium phosphate, the solution is relatively limited in coloring range. A very attractive brownish-gold color may be achieved, however, with a solution containing about 66 grams per liter of borax and an equal amount of sodium chlorite. This solution is best operated at the boiling point. If sodium metasilicate is used instead of borax, a greenish to brown color results depending upon the temperature of operation and the length of the treating period.
I prefer to carry out my process in a container formed of low carbon steel. The container or tank should be welded, not soldered,
ecause the solution will quickly dissolve solder. Inameled ware and ceramic vessels are not recommended for use with solutions which also coniin caustic because such solutions will gradually ttaclr the enamel or ceramic and frequently the Jlution may be poisoned by components of the camel.
In making up the solution, the tank is usually lied about three-quarters full of water after hich the pre-inixed salts are added with stirng until they are completely dissolved. The mk is then filled to the operatinglevel with iditional water.
I have found that unlike pure chlorlte a mixire of a chlorlte and an alkaline salt containing cm 1 to 2.5 parts of the alkaline salt for each tll". of chlorlte is not explosive upon percussion the presence of organic matter and does not arkedly increase the infiammability of ordinary brics when permitted to remain in contact lerewith. Also, the mixture or composition is as reactive with sulfur and when brought into ntact with acid is less prone to give oif danger-' LS amounts of chlorine dioxide. This last charteristic of my composition is particularly derable from the standpoint of safety since many etal surface treatments involve the use of acid iutions which are sometimes rather carelessly .ndled. Thus, when'accidentally spilled about plating room in which acid solutions are being ed, my composition does not involve the risk of lorine dioxide liberation that would be involved the chloritehandled separately were so spilled. consider the composition resulting from intiitely mixing an alkali or alkaline earth metal lorite with an alkaline salt a part ofmy inven- ,n. Where it is desired to practice the process ing a highly alkaline solution, the composition ty include substantial amounts, i.e. up to 50%, sodium or potassium hydroxide.
in commercial practice the composition conning 2 parts alkaline salt per part chlorlte is ded to water to form the coloring solution in a proportion of about 1 lb. for each gallon of ter.
During the coloring operation, water should-be led from time to time to replace that lost by lporation; otherwise, the solution may become l concentrated. No precise analytical control the solution is required. The need for more 50 ts is indicated by a slowing up of the coloring e. When the coloring rate has dropped about t, I usually add about 4 ounces of the original zture for each gallon of water present in the consider it highly important to thoroughly m the copper. or copper alloy surface. Cleancan he done with alkaline cleaners, vapor or or-solvent de-greasers, or by emulsion clean- The cleaning is not as critical as that for ting, but it is recommended to the end of ining uniform coloring that the surface be med to the extent that water when placed on surface remains thereon as a continuous film at least one minute without separating into plets i. e.. no water-break. n the case of highly buifed surfaces, it is ecially desirable to clean the surface to no lter-break." However, the work is preferably roughly rinsed after cleaning and then dipped :odiu'm cyanide solution as in the instance of itroplated copper.
have found that I can usually produce'the [red color on pure copper and high copper iys in from 1 to 10 minutes. In some cases 4 less than 30 seconds is suilicient. Low copper alloys may require as long as 20 minutes. After coloring, the work should be thoroughly rinsed in running cold water and then in hot water if it 5 is to be dried.
I In the immersion treatment, small parts can be supported in steel baskets or cylinders, and large objects on steel or iron racks, hooks, or wires. Where baskets are used, it is advisable to shake the work occasionally so that all surfaces will be exposed to the solution.
Following the coloring operation, the work may be subjected to various after-treatments such as tumbling in saw-dust, corn cob drying meal, or
paraffin coated ground cork." Where the work must withstand severe outdoor weathering, it is advisable to augment the protective effect of the finish with either lacquer, oil, or wax.
The herein described process is suitable for coloring all copper alloys containing as little as 60% of copper. Thus 60:40, 65:35, 70:30, 80:20, and 90:10 brasses are readily colored, as well as tin bronzes, silicon bronzes, beryllium coppers, and phosphor bronzes. Pure copper whether cast,
rolled, or electro-plated, is quickly given a deep finish. The process is also applicable to the coloring of electrolytically deposited brass alloys where the nominal copper content or the alloy is 60% or more.
I claim:
1. A solid composition in finely divided form adapted for use in aqueous solution to color copper surfaces or surfaces of copper alloys con taining not less than 60% copper which consists of about 1 part by weight of an alkali metal chlorlte and from about 1 to about 2.5 parts by weight of an alkaline salt having an alkalinity equal to or greater than that of tetrasodium pyrophosphate but less than that of caustic soda 40 or potash.
. 2. A solid composition in finely divided form' adapted for use in aqueous solution to color copper surfaces or surfaces of copper alloys comprising not less than 60% copper which consists of about 1 part by weight of sodium chlorlte and about 2 parts by weight of an alkaline salt having an alkalinity equal to or greater than that of tetrasodiumpyrophosphate but less than that of caustic sodayor potash.
.3. A process for coloring copper surfaces and surfaces of copper alloys containing not less than 60% copper which comprises contacting the surface with an aqueous solution consisting essentially of water. a chlorlte of the group consisting of alkali and alkaline earth metal chlo-.
rites, an alkaline salt having an alkalinity equal to,"or greater than, that of tetrasodium pyrophosphate but less than that of caustic soda or caustic potash, in proportions by weight within the range of 1 to 2.5 parts of the alkaline salt per part of the chlorlte, and 0 to 50%, based on the total weight of the chlorlte and alkaline salt, of a caustic alkali, the concentration of the salts in the solution being within the range of 4 grams per liter to saturation.
4. A process for coloring copper surfaces and A surfaces of copper alloys containing not less than V 60% copper whichcomprises immersing the surface in a hot aqueous solution consisting essentially of water, an alkali metal salt of chlorous acid, an alkaline salt having'an alkalinity equal to, or greater than, that of tetrasodium pyrophosphate but less, than that of caustic soda or caustic potash, in proportions by weight within the range of 1 to 2.5 parts of the alkaline salt per part of the chlorite, the concentration of the salts in the solution being within the range of 4 grams per liter to saturation.
5. A process for coloring copper surfaces and surfaces of copper alloys containing not less than 60% copper which comprises immersing the surface in a hot aqueous solution consisting essentially of water, sodium chlorite and an alkaline salt having an alkalinity equal to, or greater than, that of tetrasodium pyrophosphate but less than that of caustic soda or caustic potash, in proportions by weight of about 1 to 2, the concentration of the chlorlte in the solution being within the range of 10 grams per liter to 80 grams per liter.
6. A solid composition in finely divided form adapted for use in aqueous solutions to color copper surfaces and surfaces of copper alloys containing not less than 60% copper, the composition consisting essentially of a chlorite of the group consisting of the alkali and alkaline earth metal chlorites, an alkaline salt having an alkalinity equal to, or greater than, that of tetrasodium pyrophosphate, but less than that 01 caustic soda or caustic potash, in proportions by weight within the range of 1 to 2.5 parts of the alkaline salt per part of the chlorite, and 0 to 50% based on the total weight 01' the chlorite and alkaline salt of a caustic alkali.
7. A solid composition in finely divided form for use in aqueous solution to color copper surfaces or surfaces of copper alloys containing not less than 60% copper, the composition consisting essentially of an alkali metal chlorite, an alkaline salt having an alkalinity equal to, or greater than, that of tetrasodlum pyrophosphate but less than that of caustic soda or caustic potash, in proportions by weight within the range of 1 to 2.5 parts of the alkaline salt per part of the chlorite, and 0 to 50% based on the total weight of the chlorite and alkaline salt of a caustic alkali.
WALTER R. MEYER.
REFERENCES CITED The following references'are of record in the file of this patent:
UNITED STATES PATENTS Meyer Dec. 12, 1944
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US562053A US2460898A (en) | 1944-11-04 | 1944-11-04 | Process and composition for coloring copper and copper alloy surfaces |
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US562053A US2460898A (en) | 1944-11-04 | 1944-11-04 | Process and composition for coloring copper and copper alloy surfaces |
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Cited By (16)
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US2852421A (en) * | 1954-06-08 | 1958-09-16 | Johnson & Johnson | Adhesive coated metallic sheet and its method of manufacturing |
US3150016A (en) * | 1960-12-27 | 1964-09-22 | Gen Motors Corp | Antifriction bearing |
US3216866A (en) * | 1961-03-06 | 1965-11-09 | Allied Decals Inc | Treatment of anodized aluminum |
FR2549088A1 (en) * | 1983-05-23 | 1985-01-18 | Shipley Co | |
US4512818A (en) * | 1983-05-23 | 1985-04-23 | Shipley Company Inc. | Solution for formation of black oxide |
US4702793A (en) * | 1986-03-12 | 1987-10-27 | Etd Technology Inc. | Method for manufacturing a laminated layered printed wiring board using a sulfuroxy acid and an oxiding treatment of the metallic wiring patterns to insure the integrity of the laminate product |
US4816086A (en) * | 1988-04-25 | 1989-03-28 | Armstrong World Industries, Inc. | Compositions useful in copper oxidation, and a method to prepare copper oxidation solutions |
US5288377A (en) * | 1991-06-05 | 1994-02-22 | Macdermid, Incorporated | Process for the manufacture of printed circuits using electrophoretically deposited organic resists |
US5976228A (en) * | 1997-09-15 | 1999-11-02 | The Dexter Corporation | Reducing agent for forming an acid resistant barrier |
US6506314B1 (en) | 2000-07-27 | 2003-01-14 | Atotech Deutschland Gmbh | Adhesion of polymeric materials to metal surfaces |
US20080000552A1 (en) * | 2006-06-30 | 2008-01-03 | Letize Raymond A | Process for increasing the adhesion of a metal surface to a polymer |
US9345149B2 (en) | 2010-07-06 | 2016-05-17 | Esionic Corp. | Methods of treating copper surfaces for enhancing adhesion to organic substrates for use in printed circuit boards |
EP3091104A1 (en) * | 2015-05-08 | 2016-11-09 | Ernst Strassacker GmbH & Co. KG Kunstgiesserei | Method and device for patinating components |
US9763336B2 (en) | 2010-07-06 | 2017-09-12 | Atotech Deutschland Gmbh | Methods of treating metal surfaces and devices formed thereby |
US9942982B2 (en) | 1997-08-04 | 2018-04-10 | Continental Circuits, Llc | Electrical device with teeth joining layers and method for making the same |
US20210388505A1 (en) * | 2018-09-06 | 2021-12-16 | Ykk Corporation | Fastener Member |
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Cited By (18)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2852421A (en) * | 1954-06-08 | 1958-09-16 | Johnson & Johnson | Adhesive coated metallic sheet and its method of manufacturing |
US3150016A (en) * | 1960-12-27 | 1964-09-22 | Gen Motors Corp | Antifriction bearing |
US3216866A (en) * | 1961-03-06 | 1965-11-09 | Allied Decals Inc | Treatment of anodized aluminum |
FR2549088A1 (en) * | 1983-05-23 | 1985-01-18 | Shipley Co | |
US4512818A (en) * | 1983-05-23 | 1985-04-23 | Shipley Company Inc. | Solution for formation of black oxide |
US4702793A (en) * | 1986-03-12 | 1987-10-27 | Etd Technology Inc. | Method for manufacturing a laminated layered printed wiring board using a sulfuroxy acid and an oxiding treatment of the metallic wiring patterns to insure the integrity of the laminate product |
US4816086A (en) * | 1988-04-25 | 1989-03-28 | Armstrong World Industries, Inc. | Compositions useful in copper oxidation, and a method to prepare copper oxidation solutions |
US5288377A (en) * | 1991-06-05 | 1994-02-22 | Macdermid, Incorporated | Process for the manufacture of printed circuits using electrophoretically deposited organic resists |
US9942982B2 (en) | 1997-08-04 | 2018-04-10 | Continental Circuits, Llc | Electrical device with teeth joining layers and method for making the same |
US5976228A (en) * | 1997-09-15 | 1999-11-02 | The Dexter Corporation | Reducing agent for forming an acid resistant barrier |
US6506314B1 (en) | 2000-07-27 | 2003-01-14 | Atotech Deutschland Gmbh | Adhesion of polymeric materials to metal surfaces |
US20080000552A1 (en) * | 2006-06-30 | 2008-01-03 | Letize Raymond A | Process for increasing the adhesion of a metal surface to a polymer |
US10375835B2 (en) | 2009-07-06 | 2019-08-06 | Atotech Deutchland Gmbh | Methods of treating metal surfaces and devices formed thereby |
US9345149B2 (en) | 2010-07-06 | 2016-05-17 | Esionic Corp. | Methods of treating copper surfaces for enhancing adhesion to organic substrates for use in printed circuit boards |
US9763336B2 (en) | 2010-07-06 | 2017-09-12 | Atotech Deutschland Gmbh | Methods of treating metal surfaces and devices formed thereby |
US9795040B2 (en) | 2010-07-06 | 2017-10-17 | Namics Corporation | Methods of treating copper surfaces for enhancing adhesion to organic substrates for use in printed circuit boards |
EP3091104A1 (en) * | 2015-05-08 | 2016-11-09 | Ernst Strassacker GmbH & Co. KG Kunstgiesserei | Method and device for patinating components |
US20210388505A1 (en) * | 2018-09-06 | 2021-12-16 | Ykk Corporation | Fastener Member |
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