US3898137A - Method of electroplating gold and gold plating baths containing an amido-polyphosphate - Google Patents
Method of electroplating gold and gold plating baths containing an amido-polyphosphate Download PDFInfo
- Publication number
- US3898137A US3898137A US462268A US46226874A US3898137A US 3898137 A US3898137 A US 3898137A US 462268 A US462268 A US 462268A US 46226874 A US46226874 A US 46226874A US 3898137 A US3898137 A US 3898137A
- Authority
- US
- United States
- Prior art keywords
- bath
- gold
- amido
- polyphosphate
- polyphosphate compound
- 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
- 239000010931 gold Substances 0.000 title claims abstract description 47
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 229910052737 gold Inorganic materials 0.000 title claims abstract description 43
- 229920000388 Polyphosphate Polymers 0.000 title claims abstract description 36
- 239000001205 polyphosphate Substances 0.000 title claims abstract description 36
- 238000007747 plating Methods 0.000 title claims abstract description 29
- 238000000034 method Methods 0.000 title claims abstract description 6
- 238000009713 electroplating Methods 0.000 title claims description 9
- 150000001875 compounds Chemical class 0.000 claims abstract description 40
- 239000010941 cobalt Substances 0.000 claims abstract description 25
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 25
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 20
- 235000011176 polyphosphates Nutrition 0.000 claims abstract description 16
- IZLAVFWQHMDDGK-UHFFFAOYSA-N gold(1+);cyanide Chemical compound [Au+].N#[C-] IZLAVFWQHMDDGK-UHFFFAOYSA-N 0.000 claims abstract description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 20
- 229910017052 cobalt Inorganic materials 0.000 claims description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 10
- 229910052698 phosphorus Inorganic materials 0.000 claims description 10
- 239000011574 phosphorus Substances 0.000 claims description 10
- 230000000694 effects Effects 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 claims description 9
- 229910052759 nickel Inorganic materials 0.000 claims description 8
- 150000003863 ammonium salts Chemical class 0.000 claims description 7
- 150000001408 amides Chemical class 0.000 claims description 6
- 229910021529 ammonia Inorganic materials 0.000 claims description 4
- SRCZENKQCOSNAI-UHFFFAOYSA-H gold(3+);trisulfite Chemical class [Au+3].[Au+3].[O-]S([O-])=O.[O-]S([O-])=O.[O-]S([O-])=O SRCZENKQCOSNAI-UHFFFAOYSA-H 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 230000005494 condensation Effects 0.000 claims description 3
- 238000009833 condensation Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 230000007935 neutral effect Effects 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 239000011541 reaction mixture Substances 0.000 claims description 3
- 229910000069 nitrogen hydride Inorganic materials 0.000 claims 3
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical group [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 claims 1
- 230000000007 visual effect Effects 0.000 abstract description 8
- 229910001429 cobalt ion Inorganic materials 0.000 abstract description 5
- 229910001453 nickel ion Inorganic materials 0.000 abstract description 5
- 239000000203 mixture Substances 0.000 abstract description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 8
- -1 selenium ions Chemical class 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 4
- 229910019142 PO4 Inorganic materials 0.000 description 4
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 4
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical compound [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 description 4
- 235000011180 diphosphates Nutrition 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
- 229940048084 pyrophosphate Drugs 0.000 description 4
- 229910001369 Brass Inorganic materials 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 239000010951 brass Substances 0.000 description 3
- 238000005282 brightening Methods 0.000 description 3
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000004070 electrodeposition Methods 0.000 description 2
- 230000001747 exhibiting effect Effects 0.000 description 2
- 230000000737 periodic effect Effects 0.000 description 2
- 125000004437 phosphorous atom Chemical group 0.000 description 2
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 1
- 241000080590 Niso Species 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 150000004885 piperazines Chemical class 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 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 1
- 229940048086 sodium pyrophosphate Drugs 0.000 description 1
- 235000019832 sodium triphosphate Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229940066771 systemic antihistamines piperazine derivative Drugs 0.000 description 1
- 235000019818 tetrasodium diphosphate Nutrition 0.000 description 1
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 1
- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/48—Electroplating: Baths therefor from solutions of gold
Definitions
- the visual quality of the deposits improves further by the additional inclusion of a polyphosphate compound. Still further improvements may be obtained by the inclusion in a bath containing a gold cyanide complex of a small quantity of cobalt or nickel ion. In addition to improved brightness, the latter bath also exhibits improved hardness, an important characteristic for many applications.
- the gold cyanide baths are adjusted to a pH of 3.5 or greater.
- the sulfite baths are adjusted to a pH of from 5.5 to 10.5 and often rely on the presence of an amine compound in order to maintain stability at the lower pl-ls.
- an aqueous gold plating bath containing gold in the form of a complex is provided with a quantity of an amido-polyphosphate compound sufficient to improve the brightness of the deposits obtained by electroplating therewith.
- the aqueous plating solution additionally contains at least 1 g/l of a polyphosphate com pound.
- a further improvement in brightness and an improvement of hardness in the deposit can be obtained by further including at least 0.01 g/l of cobalt or nickel ion.
- gold plating solutions commonly contain between 1 and 100 g/l gold in the form of a complex. In order to minimize losses due to dragout, the concentration of gold is preferably maintained between 1 and g/l.
- the gold is normally provided as an ammonium, amine, or alkali metal gold sulfite.
- the gold is normally provided in the form of an ammonium or alkali metal gold cyanide.
- the potassium salts are the most preferred. Common alloying metals may also be present in the solution.
- the essential component of the plating baths of the present invention is an amido-polyphosphatc compound.
- This compound differs from the normal polyphosphate compounds in that one or more 'of the oxygen linkages between phosphorus atoms has been replaced by an NH- linkage.
- the amido-polyphosphates may be added either as the ammonium or alkali salts.
- Compounds of this type may be made in various ways, for example, by the reaction of dry ammonia with a phosphoric anhydride compound as described in U.S. Pat. No. 2,122,122.
- These compounds may be made by reacting anhydrous ammonia with phosphorus pentoxide and heating the reaction mixture in the presence of excess anhydrous ammonia at a temperature of at least about 150C. for a sufficient period of time to effect a molecular condensation with loss of ammonia from the product, forming a substantially neutral product in which the atomic ratio of nitrogen to phosphorus is less than 1.5 to 1.
- the amido-polyphosphates have a P 0 equivalent phosphorus content of from 65 to percent by weight and an NI-l equivalent amide nitrogen content of from about 5 to 12 percent by weight. Where the ammonium salt is employed, the NI-l equivalent ammonium nitrogen content should be from about 8 to 22 percent by weight.
- One commercially available ammonium salt of an amide-polyphosphate is sold by the Stauffer Chemical Company under the trademark Victamide.
- the product contains approximately 76 percent P 0 equivalent phosphorus, 7 percent Nl-I equivalent amide nitrogen, and 15.4 percent NI-I equivalent ammonium.
- the compound exhibits an average phosphorus content of about 4 to 5 atoms per molecule.
- the precise concentration of the amidopolyphosphate compound in the gold plating solution depends to some extent on the nature and concentrations of the other components present. It appears, however, that at least 1 g/l is necessary to obtain any appreciable effect and a quantity in excess of g/l does not provide any further improvement in brightness. In general, sufficient brightening effect can be obtained by employing quantities between 5 and 40 g/l.
- a polyphosphate compound in the solution in a preferred embodiment of this invention, it has been found desirable to include a polyphosphate compound in the solution as well.
- the amidopolyphosphate and the polyphosphate apparently coact in some matter to further enhance the brightness of the deposit.
- at least 1 g/l should be included in order to obtain beneficial effects.
- suitable compounds include the ammonium and alkali metal salts of the pyrophosphate, tripolyphosphate, and tetrarnetapolyphosphate anions. Quantities in excess of 20 g/l are preferred.
- a still further preferred embodiment is the inclusion of a small quantity of cobalt or nickel in depositable form. While addition of the amido-polyphosphate and the polyphosphate compound improve the brightness of the deposit, the final inclusion of cobalt and nickel ion brings the deposit to full brightness. The inclusion of cobalt or nickel is thus preferred wherever brightness is of extreme importance as in the case of jewelry manufacture. As demonstrated in the examples, the inclusion of cobalt and nickel has the additional advantage of improving the hardness of the gold deposit.
- the precise concentration of cobalt and nickel ions required in order to obtain the foreoging advantages depends upon the concentration of the other components of the solution. Since it is desirable to minimize the amount of cobalt or nickel in the final deposit, it is, of course, desirable to include no more cobalt in the solution than is necessary to obtain the desired brightness.
- the minimum cobalt concentration required appears to vary in proportion to the concentration of the amidopolyphosphate compound in the solution. Cobalt concentrations of 100 mg/l and less have been found effective, whereas amounts as high as l.] g/l have also been found effective without increasing the cobalt content of the deposit beyond 0.5 percent.
- Plating on cathodic brass panels was performed at approximately 120F. and 3 ASP with periodic replenishment for a period of 6- /2 hours.
- Deposits obtained exhibited an average visual rating of 2. Where the same bath was employed without the amido-polyphosphatc, the visual rating of the deposit was 4.
- Plating was performed on cathodic brass panels at approximately lOOF. and 10 ASP.
- the deposit exhibited a visual rating of 1 compound to a rating of 4 without the cobalt.
- the concentration of cobalt required to produce a 1 rating gradually increased.
- the cobalt concentration required to obtain a 1 rating was in excess of 0.5 g/l, although lesser quantities did improve the brightness to some extent.
- An analysis of the deposits obtained indicated a cobalt content not exceeding 0.5 percent. Similar results were obtained when nickel as NiSO -6H O was used in place of the cobalt.
- EXAMPLE V A bath was prepared in Example 4 but containing 25 g/l amido-polyphosphate and 0.35 g/l cobalt. Plating was performed under the conditions of the prior example and deposits exhibiting a visual rating of l and containing from 0.2 to 0.3 percent cobalt were obtained. The Knoop hardness of these deposits was in the range of 147-159. Without the inclusion of cobalt, hardness values ranged from to 90.
- an aqueous gold electroplating bath containing gold in an electrodepositable form adjusted to a pH suitable for plating the improvement comprising in cluding an amido-polyphosphate compound differing from a normal polyphosphate compound in that one or more of the oxygen linkages between phosphorous atoms is replaced by an -Nl-l-linkage in a sufficient quantity to effect a brighter deposit.
- amidopolyphosphatc compound has a P 0 equivalent phosphorus content of from about 65 to weight percent
- the bath of claim 1 additionally containing at least 1 g/l of normal polyphosphate compound.
- amidopolyphosphate compound is present in a concentration of from 1 to 100 g/l.
- the bath of claim 1 wherein said gold is present in the form of a gold cyanide complex, the pH of the bath is maintained at a value of at least 3.5, and the bath contains at least 0.01 g/l of a metal selected from the group consisting of cobalt and nickel in eo-depositable form.
- a method of electroplating a gold layer on a metallic article comprising electrolyzing the solution of claim 1 with said article as cathode.
- an aqueous gold electroplating bath containing gold in an elcctrodcpositable form adjusted to a pH suitable for plating comprising including an amidopolyphosphatc compound obtained by reacting anhydrous ammonia with phosphorus pentamidooxide and heating the reaction mixture in the presence of excess anhydrous ammonia at a temperature of at least about 150C. for a sufficient period of time to effeet a molecular condensation with loss of ammonia from the product, forming a substantially neutral product in which the atomic ratio of nitrogen to phosphorus is less than 1.5 to l in a quantity sufficient to effect a brighter deposit.
- amidopolyphosphate compound has a P 0 equivalent phosphorus content of from about 65 to weight percent, and a NH equivalent amide nitrogen content of from about 5 to 12 weight percent.
- amidopolyphosphate is an ammonium salt.
- the bath of claim 10 additionally containing at least 1 g/l of a normal polyphosphate compound.
- amidopolyphosphate compound is present in a concentration of from 1 to g/l.
- the bath of claim 10 wherein said gold is present in the form of a gold cyanide complex, the pH of the bath is maintained at a value of at least 3.5, and the bath contains at least 0.01 g/l of a metal selected from the group consisting of cobalt and nickel in codepositable form.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electroplating And Plating Baths Therefor (AREA)
Priority Applications (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US462268A US3898137A (en) | 1974-04-19 | 1974-04-19 | Method of electroplating gold and gold plating baths containing an amido-polyphosphate |
| CH461375A CH606504A5 (enrdf_load_stackoverflow) | 1974-04-19 | 1975-04-11 | |
| DE2516252A DE2516252C3 (de) | 1974-04-19 | 1975-04-14 | Elektrolyt für die galvanische Goldabscheidung |
| FR7511864A FR2268093B1 (enrdf_load_stackoverflow) | 1974-04-19 | 1975-04-16 | |
| GB16105/75A GB1506496A (en) | 1974-04-19 | 1975-04-18 | Gold plating baths |
| CA224,943A CA1043734A (en) | 1974-04-19 | 1975-04-18 | Method of electroplating gold and gold plating baths containing amido-polyphosphate |
| JP4807975A JPS5510672B2 (enrdf_load_stackoverflow) | 1974-04-19 | 1975-04-19 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US462268A US3898137A (en) | 1974-04-19 | 1974-04-19 | Method of electroplating gold and gold plating baths containing an amido-polyphosphate |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3898137A true US3898137A (en) | 1975-08-05 |
Family
ID=23835821
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US462268A Expired - Lifetime US3898137A (en) | 1974-04-19 | 1974-04-19 | Method of electroplating gold and gold plating baths containing an amido-polyphosphate |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US3898137A (enrdf_load_stackoverflow) |
| JP (1) | JPS5510672B2 (enrdf_load_stackoverflow) |
| CA (1) | CA1043734A (enrdf_load_stackoverflow) |
| CH (1) | CH606504A5 (enrdf_load_stackoverflow) |
| DE (1) | DE2516252C3 (enrdf_load_stackoverflow) |
| FR (1) | FR2268093B1 (enrdf_load_stackoverflow) |
| GB (1) | GB1506496A (enrdf_load_stackoverflow) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4207149A (en) * | 1974-12-04 | 1980-06-10 | Engelhard Minerals & Chemicals Corporation | Gold electroplating solutions and processes |
| US5277790A (en) * | 1992-07-10 | 1994-01-11 | Technic Incorporated | Non-cyanide electroplating solution for gold or alloys thereof |
| US5454876A (en) * | 1994-08-02 | 1995-10-03 | 21St Century Companies, Inc. | Process for reducing lead leachate in brass plumbing components |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04107279U (ja) * | 1991-02-25 | 1992-09-16 | 株式会社学習研究社 | カード学習器 |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2122122A (en) * | 1935-11-25 | 1938-06-28 | Victor Chemical Works | Water softener |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4953543A (enrdf_load_stackoverflow) * | 1972-09-28 | 1974-05-24 |
-
1974
- 1974-04-19 US US462268A patent/US3898137A/en not_active Expired - Lifetime
-
1975
- 1975-04-11 CH CH461375A patent/CH606504A5/xx not_active IP Right Cessation
- 1975-04-14 DE DE2516252A patent/DE2516252C3/de not_active Expired
- 1975-04-16 FR FR7511864A patent/FR2268093B1/fr not_active Expired
- 1975-04-18 CA CA224,943A patent/CA1043734A/en not_active Expired
- 1975-04-18 GB GB16105/75A patent/GB1506496A/en not_active Expired
- 1975-04-19 JP JP4807975A patent/JPS5510672B2/ja not_active Expired
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2122122A (en) * | 1935-11-25 | 1938-06-28 | Victor Chemical Works | Water softener |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4207149A (en) * | 1974-12-04 | 1980-06-10 | Engelhard Minerals & Chemicals Corporation | Gold electroplating solutions and processes |
| US5277790A (en) * | 1992-07-10 | 1994-01-11 | Technic Incorporated | Non-cyanide electroplating solution for gold or alloys thereof |
| US5454876A (en) * | 1994-08-02 | 1995-10-03 | 21St Century Companies, Inc. | Process for reducing lead leachate in brass plumbing components |
Also Published As
| Publication number | Publication date |
|---|---|
| FR2268093B1 (enrdf_load_stackoverflow) | 1978-06-30 |
| DE2516252C3 (de) | 1980-01-10 |
| GB1506496A (en) | 1978-04-05 |
| JPS50143734A (enrdf_load_stackoverflow) | 1975-11-19 |
| DE2516252B2 (de) | 1979-05-17 |
| JPS5510672B2 (enrdf_load_stackoverflow) | 1980-03-18 |
| FR2268093A1 (enrdf_load_stackoverflow) | 1975-11-14 |
| CH606504A5 (enrdf_load_stackoverflow) | 1978-10-31 |
| DE2516252A1 (de) | 1975-11-20 |
| CA1043734A (en) | 1978-12-05 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| AS | Assignment |
Owner name: HOOKER CHEMICALS & PLASTICS CORP. Free format text: MERGER;ASSIGNOR:OXY METAL INDUSTRIES CORPORATION;REEL/FRAME:004075/0885 Effective date: 19801222 |
|
| AS | Assignment |
Owner name: OCCIDENTAL CHEMICAL CORPORATION Free format text: CHANGE OF NAME;ASSIGNOR:HOOKER CHEMICAS & PLASTICS CORP.;REEL/FRAME:004126/0054 Effective date: 19820330 |
|
| AS | Assignment |
Owner name: OMI INTERNATIONAL CORPORATION, 21441 HOOVER ROAD, Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNOR:OCCIDENTAL CHEMICAL CORPORATION;REEL/FRAME:004190/0827 Effective date: 19830915 |
|
| AS | Assignment |
Owner name: MANUFACTURERS HANOVER TRUST COMPANY, A CORP OF NY Free format text: SECURITY INTEREST;ASSIGNOR:INTERNATIONAL CORPORATION, A CORP OF DE;REEL/FRAME:004201/0733 Effective date: 19830930 |