US3272662A - Process for after-treating metal surfaces coated with crystalline anticorrosion layers - Google Patents
Process for after-treating metal surfaces coated with crystalline anticorrosion layers Download PDFInfo
- Publication number
- US3272662A US3272662A US168261A US16826162A US3272662A US 3272662 A US3272662 A US 3272662A US 168261 A US168261 A US 168261A US 16826162 A US16826162 A US 16826162A US 3272662 A US3272662 A US 3272662A
- Authority
- US
- United States
- Prior art keywords
- metal surfaces
- crystalline
- treatment
- water
- plates
- 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
- 229910052751 metal Inorganic materials 0.000 title claims description 18
- 239000002184 metal Substances 0.000 title claims description 18
- 238000000034 method Methods 0.000 title claims description 12
- 239000000243 solution Substances 0.000 claims description 26
- 230000007797 corrosion Effects 0.000 claims description 11
- 238000005260 corrosion Methods 0.000 claims description 11
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims description 4
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 1
- 229920006395 saturated elastomer Polymers 0.000 claims 1
- 239000010410 layer Substances 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 239000000203 mixture Substances 0.000 description 11
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 10
- 125000004432 carbon atom Chemical group C* 0.000 description 9
- -1 aliphatic phosphonic acids Chemical class 0.000 description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 229910000831 Steel Inorganic materials 0.000 description 6
- 239000010959 steel Substances 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 229910019142 PO4 Inorganic materials 0.000 description 4
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 4
- GJWAEWLHSDGBGG-UHFFFAOYSA-N hexylphosphonic acid Chemical compound CCCCCCP(O)(O)=O GJWAEWLHSDGBGG-UHFFFAOYSA-N 0.000 description 4
- 239000004922 lacquer Substances 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 4
- 239000010452 phosphate Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 239000012141 concentrate Substances 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical class [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 2
- NJGCRMAPOWGWMW-UHFFFAOYSA-N octylphosphonic acid Chemical compound CCCCCCCCP(O)(O)=O NJGCRMAPOWGWMW-UHFFFAOYSA-N 0.000 description 2
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 description 2
- 150000003009 phosphonic acids Chemical class 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 241000251468 Actinopterygii Species 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 150000001845 chromium compounds Chemical class 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- DZQISOJKASMITI-UHFFFAOYSA-N decyl-dioxido-oxo-$l^{5}-phosphane;hydron Chemical compound CCCCCCCCCCP(O)(O)=O DZQISOJKASMITI-UHFFFAOYSA-N 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- XLYOFNOQVPJJNP-DYCDLGHISA-N deuterium hydrogen oxide Chemical compound [2H]O XLYOFNOQVPJJNP-DYCDLGHISA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229940057952 methanol Drugs 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 1
- 229910000165 zinc phosphate Inorganic materials 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
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
- C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
- C23F11/167—Phosphorus-containing compounds
- C23F11/1676—Phosphonic acids
-
- 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
- C23C22/82—After-treatment
- C23C22/83—Chemical after-treatment
Definitions
- the present invention provides a process and a composition for the after-treatment of metal surfaces coated with crystalline anticorrosion layers in order to improve the protection against corrosion.
- the invention is particularly directed to the after-treatment of said metal surfaces by treating them with a solution containing aliphatic phosphonic acids having more than 5 carbon atoms.
- an inorganic covering layer for example a phosphate layer. Due to their porosity crystalline layers of this kind alone do not ensure an effective protection against corrosion. It is known that iron and steel surfaces are well protected against corrosion only when the free area of the pores of the coating covers less than 0.01% of the total surface.
- a dense protection layer is, for example, the natural oxide film on aluminiurn and chromium.
- phosphate layers have a pore area which is about 50 times larger, namely about 0.5%. Consequently, it is necessary to subject protecting layers of this kind to an after-treatment.
- the anticorrosion layers on metal surfaces are Often oiled. This is only possible, however, when the metal parts are not to be lacquered.
- the layers are passivated with dilute solutions of hexavalent chromium compounds. The use of such compounds is, however, disadvantageous in that the waste water must be freed from the toxic chromium compounds.
- metals especially such as zinc, aluminium, iron and steel can be well protected against corrosion by inorganic crystalline covering layers, preferably phosphate layers, when the metal parts provided with the crystalline layers are after-treated with solutions containing aliphatic phosphonic acids having more than 5 carbon atoms, and subsequently dried.
- the solutions for the after-treatment suitably contain the aliphatic phosphonic acids in an amount in the range of to 10 mol per liter and preferably 10* to 10 mol per liter.
- the short-chain aliphatic phosphonic acids are suitably applied in the form of aqueous solutions. Since, however, the solubility of these compounds in water decreases as the chain length increases and products having a long chain are practically insoluble in water it is of advantage to dissolve said substances in mixtures of water with organic solvents, especially aliphatic ketones or aliphatic alcohols having 1-5 carbon atoms. Especially suitable organic solvents are acetone and isopropanol.
- the present invention furthermore provides a composition for the preparation of the after-treatment solutions which composition consists of a concentrate of the ali- "ice phatic phosphonic acids having more than 5 carbon atoms, water and/ or organic solvents, for example alcohols having 1-5 carbon atoms, or ketones.
- composition for preparing the after-treatment solutions in the form of a concentrate it is possible from the beginning to maintain a suitable mixing ratio so that when introducing the concentrate into water a bath is obtained which contains a sufiicient amount of compounds required for a successful treatment.
- the process of the present invention is carried out in a manner such that the degreased metal parts, which have subsequently been provided with an anticorrosion layer, are after-treated for a short period of time, for example, a few seconds up to some minutes, with the described solutions in usual manner, for example by spraying, immersing and flooding, and then dried.
- An upper limitation of the treatment time is only important when such crystalline layers are after-treated and are attacked to a substantial degree, i.e. dissolved, by the aliphatic, long-chain phosphonic acids used according to the invention.
- the low concentrations used in the process of the invention dissolve the crystalline coating layers in most cases to a very small degree only and at a treatment time of less than about 15 minutes by the immersion or spraying process a dissolution of the crystalline layer cannot be detected.
- the lower limit of the treatment time is practically given by a complete wetting of the after-treated surface with the solutions according to the invention.
- the temperature of the after-treatment solution used according to the invention is not critical and only limited by the boiling and freezing point of said solution.
- Example 1 Steel plates for motor car bodies were degreased at boiling temperature with a commercial, strongly alkaline cleansing agent rinsed with water and treated for ten minutes at a bath temperature of 60 C. in a phosphatization bath containing an oxidizing accelerator and having 35 points (the total acidity, as determined by standard titration procedures, wherein a 10 ml. sample of the solution is titra-ted with 0.1 normal sodium hydroxide to a phenolphthalein end point, is represented by the number of milliliters of base used, this number being referred to as points).
- the steel plates were thus provided with a firmly adhering layer of zinc phosphate.
- phosphatized plates One part of the phosphatized plates was immersed for 15 seconds in a 2.7 10- molar solution of eicosanephosphonic acid (C H PO I-I in a water/isopropanol mixture (proportion by weight 1:1) and then dried in warm air. The other part of the phosphatized plates was treated for 45 seconds with a commercial after-passivation solution containing about 0.03% of chromic acid in addition to small amounts of phosphoric acid.
- C H PO I-I eicosanephosphonic acid
- a commercial after-passivation solution containing about 0.03% of chromic acid in addition to small amounts of phosphoric acid.
- the plates treated with the solution of the invention as well as the plates treated with chromic acid were then provided with an alkyd resin baking lacquer and the plates were subjected to the usual standardized corrosion and lacquer adherence tests.
- the plates treated by the process of the invention showed an excellent protection against corrosion which was superior to that produced on the comparative plates with chromic acid.
- the values obtained for the lacquer adherence were about equal for either type of plates.
- Example 2 Steel plates for motor car bodies were degreased and phosphatized as described in Example 1.
- the plates leaving the phosphatization bath were rinsed with water and immersed in a solution of 3X10 mol per liter of hexane-phosphonic acid in isopropanol.
- the drying of the plates with hot air took a much shorter time than the drying of the plates treated with aqueous solutions according to Example 1.
- the plates treated in this manner showed the same protection against corrosion and the same good lacquer adherence as the plates of Example 1.
- a process for the after-treatment of phosphatizcd ferrous surfaces in order to improve the corrosion protection which comprises treating said coated metal surfaces with an aqueous solution containing about 10 mol per liter solution to about 10- mol per liter solution of a saturated aliphatic phosphonic acid containing more than 5 carbon atoms, and subsequently drying said metal surfaces.
- said solution contains as an additional solvent 21 member from the group consisting of water aliphatic alcohols containing 1 to 5 carbon atoms, and aliphatic ketones containing less than 5 carbon atoms.
- a process for the after-treatment of phosphatized surfaces of a metal selected from the group consisting of zinc, aluminum, iron and steel in order to improve the corrosion protection which comprises treating said coated metal surfaces with an aqueous solution containing about 10- mol per liter solution to about 10- mol per liter solution of a saturated aliphatic phosphonic acid containing more than 5 carbon atoms, and subsequently drying said metal surface.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Chemical Treatment Of Metals (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Laminated Bodies (AREA)
- Chemically Coating (AREA)
- Paints Or Removers (AREA)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEF33161A DE1207759B (de) | 1961-02-08 | 1961-02-08 | Verfahren zur Nachbehandlung von mit kristallinen Schutzschichten versehenen Metalloberflaechen |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3272662A true US3272662A (en) | 1966-09-13 |
Family
ID=7094973
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US168261A Expired - Lifetime US3272662A (en) | 1961-02-08 | 1962-01-23 | Process for after-treating metal surfaces coated with crystalline anticorrosion layers |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US3272662A (enrdf_load_stackoverflow) |
| BE (1) | BE613686A (enrdf_load_stackoverflow) |
| CH (1) | CH423408A (enrdf_load_stackoverflow) |
| DE (1) | DE1207759B (enrdf_load_stackoverflow) |
| GB (1) | GB950377A (enrdf_load_stackoverflow) |
| LU (1) | LU41110A1 (enrdf_load_stackoverflow) |
| NL (2) | NL274316A (enrdf_load_stackoverflow) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3630790A (en) * | 1969-05-13 | 1971-12-28 | Dow Chemical Co | Method of protection of metal surfaces from corrosion |
| US3900370A (en) * | 1972-03-10 | 1975-08-19 | Henkel & Cie Gmbh | Process for treating aluminum surfaces |
| US20050268991A1 (en) * | 2004-06-03 | 2005-12-08 | Enthone Inc. | Corrosion resistance enhancement of tin surfaces |
| US20080261025A1 (en) * | 2007-04-18 | 2008-10-23 | Enthone Inc. | Metallic surface enhancement |
| US20080314283A1 (en) * | 2007-06-21 | 2008-12-25 | Enthone Inc. | Corrosion protection of bronzes |
| US20090121192A1 (en) * | 2007-11-08 | 2009-05-14 | Enthone Inc. | Self assembled molecules on immersion silver coatings |
| US20100291303A1 (en) * | 2007-11-21 | 2010-11-18 | Enthone Inc. | Anti-tarnish coatings |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2885312A (en) * | 1956-03-05 | 1959-05-05 | Kelite Corp | Metal coating compositions |
| US3003965A (en) * | 1953-09-29 | 1961-10-10 | Philips Corp | Method of preparing a magnetic sound carrier |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR1174045A (fr) * | 1957-03-26 | 1959-03-05 | Pechiney | Protection des métaux |
-
0
- NL NL129791D patent/NL129791C/xx active
- NL NL274316D patent/NL274316A/xx unknown
-
1961
- 1961-02-08 DE DEF33161A patent/DE1207759B/de active Pending
-
1962
- 1962-01-17 LU LU41110D patent/LU41110A1/xx unknown
- 1962-01-23 US US168261A patent/US3272662A/en not_active Expired - Lifetime
- 1962-02-06 CH CH145162A patent/CH423408A/de unknown
- 1962-02-08 GB GB4978/62A patent/GB950377A/en not_active Expired
- 1962-02-08 BE BE613686A patent/BE613686A/fr unknown
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3003965A (en) * | 1953-09-29 | 1961-10-10 | Philips Corp | Method of preparing a magnetic sound carrier |
| US2885312A (en) * | 1956-03-05 | 1959-05-05 | Kelite Corp | Metal coating compositions |
Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3630790A (en) * | 1969-05-13 | 1971-12-28 | Dow Chemical Co | Method of protection of metal surfaces from corrosion |
| US3900370A (en) * | 1972-03-10 | 1975-08-19 | Henkel & Cie Gmbh | Process for treating aluminum surfaces |
| US20050268991A1 (en) * | 2004-06-03 | 2005-12-08 | Enthone Inc. | Corrosion resistance enhancement of tin surfaces |
| WO2005121405A1 (en) * | 2004-06-03 | 2005-12-22 | Enthone Inc. | Corrosion resistance enhancement of tin surfaces |
| TWI409362B (zh) * | 2004-06-03 | 2013-09-21 | Enthone | 錫表面抗蝕性的增強 |
| CN101001980B (zh) * | 2004-06-03 | 2011-06-15 | 恩索恩公司 | 锡表面的耐腐蚀性改进 |
| US20080261025A1 (en) * | 2007-04-18 | 2008-10-23 | Enthone Inc. | Metallic surface enhancement |
| US20100151263A1 (en) * | 2007-04-18 | 2010-06-17 | Enthone Inc. | Metallic surface enhancement |
| US7883738B2 (en) | 2007-04-18 | 2011-02-08 | Enthone Inc. | Metallic surface enhancement |
| US8741390B2 (en) | 2007-04-18 | 2014-06-03 | Enthone Inc. | Metallic surface enhancement |
| US20100319572A1 (en) * | 2007-06-21 | 2010-12-23 | Enthone Inc. | Corrosion protection of bronzes |
| US20080314283A1 (en) * | 2007-06-21 | 2008-12-25 | Enthone Inc. | Corrosion protection of bronzes |
| US10017863B2 (en) | 2007-06-21 | 2018-07-10 | Joseph A. Abys | Corrosion protection of bronzes |
| US20090121192A1 (en) * | 2007-11-08 | 2009-05-14 | Enthone Inc. | Self assembled molecules on immersion silver coatings |
| US8216645B2 (en) | 2007-11-08 | 2012-07-10 | Enthone Inc. | Self assembled molecules on immersion silver coatings |
| US8323741B2 (en) | 2007-11-08 | 2012-12-04 | Abys Joseph A | Self assembled molecules on immersion silver coatings |
| US20100291303A1 (en) * | 2007-11-21 | 2010-11-18 | Enthone Inc. | Anti-tarnish coatings |
| US7972655B2 (en) | 2007-11-21 | 2011-07-05 | Enthone Inc. | Anti-tarnish coatings |
Also Published As
| Publication number | Publication date |
|---|---|
| NL274316A (enrdf_load_stackoverflow) | |
| DE1207759B (de) | 1965-12-23 |
| GB950377A (en) | 1964-02-26 |
| BE613686A (fr) | 1962-08-08 |
| NL129791C (enrdf_load_stackoverflow) | |
| CH423408A (de) | 1966-10-31 |
| LU41110A1 (enrdf_load_stackoverflow) | 1962-03-17 |
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