US3677827A - Composition and method for blackening metal articles - Google Patents
Composition and method for blackening metal articles Download PDFInfo
- Publication number
- US3677827A US3677827A US856481A US3677827DA US3677827A US 3677827 A US3677827 A US 3677827A US 856481 A US856481 A US 856481A US 3677827D A US3677827D A US 3677827DA US 3677827 A US3677827 A US 3677827A
- Authority
- US
- United States
- Prior art keywords
- sodium
- iron
- triethanolamine
- composition
- sequestrant
- 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
- 239000000203 mixture Substances 0.000 title abstract description 38
- 229910052751 metal Inorganic materials 0.000 title abstract description 15
- 239000002184 metal Substances 0.000 title abstract description 15
- 238000000034 method Methods 0.000 title description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 64
- 239000003352 sequestering agent Substances 0.000 abstract description 33
- 229910052742 iron Inorganic materials 0.000 abstract description 32
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 abstract description 27
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 abstract description 23
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 abstract description 20
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 abstract description 20
- -1 FERROUS METALS Chemical class 0.000 abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 12
- 235000011121 sodium hydroxide Nutrition 0.000 abstract description 10
- 235000010344 sodium nitrate Nutrition 0.000 abstract description 10
- 239000004317 sodium nitrate Substances 0.000 abstract description 10
- 235000010288 sodium nitrite Nutrition 0.000 abstract description 10
- 239000007788 liquid Substances 0.000 abstract description 8
- 239000000176 sodium gluconate Substances 0.000 description 12
- 235000012207 sodium gluconate Nutrition 0.000 description 12
- 229940005574 sodium gluconate Drugs 0.000 description 12
- AEQDJSLRWYMAQI-UHFFFAOYSA-N 2,3,9,10-tetramethoxy-6,8,13,13a-tetrahydro-5H-isoquinolino[2,1-b]isoquinoline Chemical compound C1CN2CC(C(=C(OC)C=C3)OC)=C3CC2C2=C1C=C(OC)C(OC)=C2 AEQDJSLRWYMAQI-UHFFFAOYSA-N 0.000 description 10
- NDFUILURRSPQPF-CWONUKFKSA-G [Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O.OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O.OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O.OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O.OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O.OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O.OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O.OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O.OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O.OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O.OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O.OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O.OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O NDFUILURRSPQPF-CWONUKFKSA-G 0.000 description 10
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 9
- 239000000600 sorbitol Substances 0.000 description 9
- 238000007792 addition Methods 0.000 description 8
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 7
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 6
- 239000000654 additive Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 5
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 5
- 229910052783 alkali metal Inorganic materials 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- ZAWGLAXBGYSUHN-UHFFFAOYSA-M sodium;2-[bis(carboxymethyl)amino]acetate Chemical compound [Na+].OC(=O)CN(CC(O)=O)CC([O-])=O ZAWGLAXBGYSUHN-UHFFFAOYSA-M 0.000 description 4
- 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 3
- 230000000996 additive effect Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- OCUCCJIRFHNWBP-IYEMJOQQSA-L Copper gluconate Chemical class [Cu+2].OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O.OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O OCUCCJIRFHNWBP-IYEMJOQQSA-L 0.000 description 2
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 2
- 229910001963 alkali metal nitrate Inorganic materials 0.000 description 2
- 239000012670 alkaline solution Substances 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
- HJMZMZRCABDKKV-UHFFFAOYSA-N carbonocyanidic acid Chemical class OC(=O)C#N HJMZMZRCABDKKV-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 230000009919 sequestration Effects 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- CKJGHPBOPQNPHM-UHFFFAOYSA-N 2-[bis(2-hydroxyethyl)amino]ethanol;sodium Chemical compound [Na].OCCN(CCO)CCO CKJGHPBOPQNPHM-UHFFFAOYSA-N 0.000 description 1
- 229910000640 Fe alloy Inorganic materials 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical class [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 150000002826 nitrites Chemical class 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 235000011118 potassium hydroxide Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- MSXHSNHNTORCAW-GGLLEASOSA-M sodium;(2s,3s,4s,5r,6s)-3,4,5,6-tetrahydroxyoxane-2-carboxylate Chemical compound [Na+].O[C@H]1O[C@H](C([O-])=O)[C@@H](O)[C@H](O)[C@H]1O MSXHSNHNTORCAW-GGLLEASOSA-M 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
- C23C22/62—Treatment of iron or alloys based thereon
Definitions
- This invention relates to improved chemical compositions and their use for production of black oxide coatings on ferrous metals.
- a principal object of this invention is to provide compositions which give oxide coatings superior in depth of color and corrosion resistance.
- Another object of the invention is to provide blackening compositions which can be stored in either dry or liquid form, the latter form obviating the mixing of highly alkaline powder with water, and the attendant risk of boil-over or danger.
- a further object of the invention is to provide blackening compositions as liquid baths having a greatly extended service life as compared to prior art baths.
- Still another object of the invention is to provide blackening compositions which are operable and produce good results over a much wider temperature range and with which blackening times are relatively shorter than with prior art baths.
- a still further object of the invention is to provide blackening compositions which are useful in baths operable at lower temperatures than are prior art baths, in the range, for example, of 245 F. to 290 F., or 20 F. to 60 F. lower than operable temperature ranges for prior art baths.
- compositions consisting essentially of sodium hydroxide, sodium nitrate, and sodium nitrite, to which triethanolamine or other specified additives have been added, which compositions may be stored as dry mixtures or as solutions made up with water.
- iron sequestrants suitable in the present invention are triethanolamine, sodium gluconate, sodium heptagluconate, sorbitol, diethanolamine, monoethanolamine, sodium nitriloacetate, etc. Of these, triethanolamine is superior and the preferred sequestrant because of bath stability, lack of foaming, and superior sequestration of iron. Cations other than sodium are equally effective; and bath alkalinity can be achieved with sodium or potassium hydroxides. Superiority of the black oxide coating which results is in both appearance and corrosion resistance. Superiority lies also in lower temperature operations and in greater diversity of iron alloys that can be processed successfully.
- compositions of the present invention in liquid form is an advance over the prior art because of the advantages of a composition approximating that of a working bath so that additions can be made at optimum bath temperature without risk of boil-over or danger.
- the latter consideration is important because of the fact that the bath is operated at high temperatures.
- iron sequestrant additive Up to 10% of iron sequestrant additive may be used, alone or in mixtures of two or more. With triethanolamine, sodium gluconate, or sodium heptagluconate, a concentration of 0.05 to 2% sufiices. For the other iron sequestrant additives, the concentration should range between 1 and 10%.
- Baths 4, 5 Total of triethanolamine, sorbitol, sodium gluconate or sodium heptagluconate (alone or mixtures).
- Baths 6, 7 Total of diethanolamine, monoethanolamine and sodium nitriloaeetate (alone or as mixtures).
- compositions defined immediately above using triethanolamine as the sequestrant represents preferred embodiments of the invention.
- a mixture of the dry ingredients (sodium hydroxide, sodium nitrite, and sodium nitrate) is formed, and can then be stored as a separate product, or may be made up with the required amount of water to achieve the desired bath concentration.
- the triethanolamine or other sequestrant is added up to the limit of its solubility and then may be added in increments as the bath is used.
- compositions of the invention As indicated hereinabove the preparation and storing of these compositions in liquid form represents a distinct advantage, sparing the users having to dissolve strong alkali in high concentration. Using liquid forms of the compositions of the invention, thus, the user need merely pump the liquid into the tank and heat to boiling before immersing articles to be blackened.
- the blackening bath is used in the usual way, that is to say, once the components have been brought together, the bath is heated to almost the boiling point and then the articles to be blackened are immersed in the heated composition and are held therein until the desired depth of blackening has been achieved. On removal from the bath the articles are permitted to dry in air and subsequently rinsed to remove any salt residue.
- a blackening composition for ferrous articles consisting essentially of the following in percent by weight:
- Iron sequestrant 0.05-l0 balance to make Water; said iron sequestrant being stable in highly alkaline solutions at temperatures above 245 F. and capable of sequestering iron introduced into said solution and being selected from the group consisting of alcohol amines, sorbitol and derivatives, metal gluconates and derivatives, metal nitriloacetates and derivatives and combinations thereof.
- composition of claim 1 in which the sequestrant is selected from the group consisting of:
- composition of claim 1 wherein the alkali metal salts are sodium salts.
- composition of claim 3 wherein the proportions are Percent Sodium hydroxide 34-38 Sodium nitrite 4.5-6
- Sodium nitrate 2.2-4.0 'Iron sequestrant l-10 5 The composition of claim 1 wherein the iron sequestrant is a member of the group consisting of sodium gluconate, sodium heptagluconate, and triethanolamine; and its proportion is 0.05-2%.
- a method of extending the useful life of a blackening bath which has lost its ability to blacken ferrous metal objects and which consisted essentially of sodium hydroxide, sodium nitrite and sodium nitrate dissolved in water, which comprises adding up to 10% by weight of an iron sequestrant selected from the group consisting of sodium gluconate, sorbitol, monoethanolamine, diethanolamine, sodium nitriloacetate, sodium heptagluconate, and triethanolamine to said bath.
- a method of extending the useful life of a blackening bath which has lost its ability to blacken ferrous metal objects and which consisted essentially of sodium hydroxide, sodium nitrite and sodium nitrate dissolved in water, which comprises adding up to 10% by weight of an iron sequestrant selected from the group consisting of sodium gluconate, sodium heptagluconate, and triethanolamine.
- a blackening composition for ferrous articles consisting essentially of the following in parts by weight:
- composition of claim 1 in which the percentage by weight of iron sequestrant is 0.05-0.35% and the iron sequestrant is selected from the group consisting of sodium gluconate, sodium heptagluconate, t-riethanolamine and combinations thereof.
- composition of claim 1 in which the percentage by weight of iron sequestrant is 0.350.70% and the iron sequestrant is selected from a group consisting of sodium gluconate, sodium heptagluconate, triethanolamine and combinations thereof.
- composition of claim 1 in which the percentage by weight of the iron sequestrant is 0.7010.0% and the iron sequestrant is selected from the group consisting of triethanolamine, sodium gluconate, sorbitol, mon0- ethanolamine, diethanolamine, sodium nitriloacetate, sodium heptagluconate and combinations thereof.
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)
- Detergent Compositions (AREA)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US85648169A | 1969-09-09 | 1969-09-09 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3677827A true US3677827A (en) | 1972-07-18 |
Family
ID=25323740
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US856481A Expired - Lifetime US3677827A (en) | 1969-09-09 | 1969-09-09 | Composition and method for blackening metal articles |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US3677827A (fr) |
| BE (1) | BE780002A (fr) |
| CA (1) | CA919063A (fr) |
| GB (1) | GB1318297A (fr) |
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3905838A (en) * | 1974-04-10 | 1975-09-16 | Hikaru Ito | Bath for treating aluminum and aluminum alloys to form oxide film nonelectrolytically thereon and method for the treatment |
| US3920486A (en) * | 1973-05-10 | 1975-11-18 | Oxy Metal Industries Corp | Method of blackening ferrous metal surfaces |
| US3929514A (en) * | 1974-03-05 | 1975-12-30 | Heatbath Corp | Composition and method for forming a protective coating on a zinc metal surface |
| US4045253A (en) * | 1976-03-15 | 1977-08-30 | Halliburton Company | Passivating metal surfaces |
| US4226646A (en) * | 1979-03-26 | 1980-10-07 | E. I. Du Pont De Nemours And Company | Process of coating a ferrous metal substrate with an aqueous fluoropolymer coating |
| US4325749A (en) * | 1980-11-04 | 1982-04-20 | Barlet Loren E | Method of treating welding rod for corrosion resistance |
| US4512818A (en) * | 1983-05-23 | 1985-04-23 | Shipley Company Inc. | Solution for formation of black oxide |
| US6309476B1 (en) * | 1999-05-24 | 2001-10-30 | Birchwood Laboratories, Inc. | Composition and method for metal coloring process |
| US20030034095A1 (en) * | 2001-08-03 | 2003-02-20 | Heimann Robert L. | Electrolytic and electroless process for treating metallic surfaces and products formed thereby |
| US6695931B1 (en) | 1999-05-24 | 2004-02-24 | Birchwood Laboratories, Inc. | Composition and method for metal coloring process |
| US20040250748A1 (en) * | 1999-05-24 | 2004-12-16 | Ravenscroft Keith N. | Composition and method for metal coloring process |
| US20060014042A1 (en) * | 2004-07-15 | 2006-01-19 | Block William V | Hybrid metal oxide/organometallic conversion coating for ferrous metals |
| US7964044B1 (en) | 2003-10-29 | 2011-06-21 | Birchwood Laboratories, Inc. | Ferrous metal magnetite coating processes and reagents |
| US20200246921A1 (en) * | 2019-02-04 | 2020-08-06 | Lincoln Global, Inc. | Coated welding wire |
| US10845309B2 (en) | 2017-12-21 | 2020-11-24 | Ecolab Usa Inc. | Blackened optical component without fluorescence |
| US12497684B2 (en) | 2021-07-28 | 2025-12-16 | Birchwood Laboratories Llc | Methods and compositions for forming magnetite coatings on ferrous metals |
-
1969
- 1969-09-09 US US856481A patent/US3677827A/en not_active Expired - Lifetime
-
1970
- 1970-08-07 CA CA090254A patent/CA919063A/en not_active Expired
- 1970-08-21 GB GB4032470A patent/GB1318297A/en not_active Expired
-
1972
- 1972-02-29 BE BE780002A patent/BE780002A/fr unknown
Cited By (23)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3920486A (en) * | 1973-05-10 | 1975-11-18 | Oxy Metal Industries Corp | Method of blackening ferrous metal surfaces |
| US3929514A (en) * | 1974-03-05 | 1975-12-30 | Heatbath Corp | Composition and method for forming a protective coating on a zinc metal surface |
| US3905838A (en) * | 1974-04-10 | 1975-09-16 | Hikaru Ito | Bath for treating aluminum and aluminum alloys to form oxide film nonelectrolytically thereon and method for the treatment |
| US4045253A (en) * | 1976-03-15 | 1977-08-30 | Halliburton Company | Passivating metal surfaces |
| US4226646A (en) * | 1979-03-26 | 1980-10-07 | E. I. Du Pont De Nemours And Company | Process of coating a ferrous metal substrate with an aqueous fluoropolymer coating |
| US4325749A (en) * | 1980-11-04 | 1982-04-20 | Barlet Loren E | Method of treating welding rod for corrosion resistance |
| US4512818A (en) * | 1983-05-23 | 1985-04-23 | Shipley Company Inc. | Solution for formation of black oxide |
| US6695931B1 (en) | 1999-05-24 | 2004-02-24 | Birchwood Laboratories, Inc. | Composition and method for metal coloring process |
| US20040250748A1 (en) * | 1999-05-24 | 2004-12-16 | Ravenscroft Keith N. | Composition and method for metal coloring process |
| US6899769B2 (en) * | 1999-05-24 | 2005-05-31 | Birchwood Laboratories, Inc. | Composition and method for metal coloring process |
| US6309476B1 (en) * | 1999-05-24 | 2001-10-30 | Birchwood Laboratories, Inc. | Composition and method for metal coloring process |
| US6753039B2 (en) | 2001-08-03 | 2004-06-22 | Elisha Holding Llc | Electrolytic and electroless process for treating metallic surfaces and products formed thereby |
| US20040217334A1 (en) * | 2001-08-03 | 2004-11-04 | Heimann Robert L. | Electrolytic and electroless process for treating metallic surfaces and products formed thereby |
| US20030034095A1 (en) * | 2001-08-03 | 2003-02-20 | Heimann Robert L. | Electrolytic and electroless process for treating metallic surfaces and products formed thereby |
| WO2003035942A3 (fr) * | 2001-08-03 | 2004-01-29 | Elisha Holding Llc | Procede electrolytique et autocatalytique de traitement de surfaces metalliques et produits traites selon ce procede |
| US7964044B1 (en) | 2003-10-29 | 2011-06-21 | Birchwood Laboratories, Inc. | Ferrous metal magnetite coating processes and reagents |
| US20060014042A1 (en) * | 2004-07-15 | 2006-01-19 | Block William V | Hybrid metal oxide/organometallic conversion coating for ferrous metals |
| US7144599B2 (en) | 2004-07-15 | 2006-12-05 | Birchwood Laboratories, Inc. | Hybrid metal oxide/organometallic conversion coating for ferrous metals |
| US7481872B1 (en) | 2004-07-15 | 2009-01-27 | Birchwood Laboratories, Inc. | Process for making bath composition for converting surface of ferrous metal to mixed oxides and organometallic compounds of aluminum and iron |
| US7625439B1 (en) | 2004-07-15 | 2009-12-01 | Birchwood Laboratories, Inc. | Bath composition for converting surface of ferrous metal to mixed oxides and organometallic compounds of aluminum and iron |
| US10845309B2 (en) | 2017-12-21 | 2020-11-24 | Ecolab Usa Inc. | Blackened optical component without fluorescence |
| US20200246921A1 (en) * | 2019-02-04 | 2020-08-06 | Lincoln Global, Inc. | Coated welding wire |
| US12497684B2 (en) | 2021-07-28 | 2025-12-16 | Birchwood Laboratories Llc | Methods and compositions for forming magnetite coatings on ferrous metals |
Also Published As
| Publication number | Publication date |
|---|---|
| BE780002A (fr) | 1972-06-16 |
| GB1318297A (en) | 1973-05-23 |
| CA919063A (en) | 1973-01-16 |
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