US3130072A - Silver-palladium immersion plating composition and process - Google Patents
Silver-palladium immersion plating composition and process Download PDFInfo
- Publication number
- US3130072A US3130072A US139858A US13985861A US3130072A US 3130072 A US3130072 A US 3130072A US 139858 A US139858 A US 139858A US 13985861 A US13985861 A US 13985861A US 3130072 A US3130072 A US 3130072A
- Authority
- US
- United States
- Prior art keywords
- silver
- palladous
- salt
- palladium
- bath
- 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 claims description 9
- 238000000034 method Methods 0.000 title description 10
- 238000007654 immersion Methods 0.000 title description 4
- 238000007747 plating Methods 0.000 title description 3
- SWELZOZIOHGSPA-UHFFFAOYSA-N palladium silver Chemical compound [Pd].[Ag] SWELZOZIOHGSPA-UHFFFAOYSA-N 0.000 title description 2
- 150000003839 salts Chemical class 0.000 claims description 17
- 238000000151 deposition Methods 0.000 claims description 13
- 229910052709 silver Inorganic materials 0.000 claims description 13
- 239000004332 silver Substances 0.000 claims description 13
- 239000007864 aqueous solution Substances 0.000 claims description 6
- LFAGQMCIGQNPJG-UHFFFAOYSA-N silver cyanide Chemical compound [Ag+].N#[C-] LFAGQMCIGQNPJG-UHFFFAOYSA-N 0.000 claims description 6
- 229940098221 silver cyanide Drugs 0.000 claims description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 19
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical group [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 12
- 229910052763 palladium Inorganic materials 0.000 description 7
- 230000008021 deposition Effects 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- KPZGRMZPZLOPBS-UHFFFAOYSA-N 1,3-dichloro-2,2-bis(chloromethyl)propane Chemical compound ClCC(CCl)(CCl)CCl KPZGRMZPZLOPBS-UHFFFAOYSA-N 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- QXNVGIXVLWOKEQ-UHFFFAOYSA-N Disodium Chemical compound [Na][Na] QXNVGIXVLWOKEQ-UHFFFAOYSA-N 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 3
- 229910052737 gold Inorganic materials 0.000 description 3
- 239000010931 gold Substances 0.000 description 3
- 150000001447 alkali salts Chemical class 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 2
- HKSGQTYSSZOJOA-UHFFFAOYSA-N potassium argentocyanide Chemical compound [K+].[Ag+].N#[C-].N#[C-] HKSGQTYSSZOJOA-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 229910001369 Brass Inorganic materials 0.000 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 description 1
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 101150003085 Pdcl gene Proteins 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- -1 acetic Chemical class 0.000 description 1
- WTHXTWHYLIZJBH-UHFFFAOYSA-N acetic acid;azane Chemical compound N.CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O WTHXTWHYLIZJBH-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 239000010951 brass Substances 0.000 description 1
- 150000001860 citric acid derivatives Chemical class 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000000615 nonconductor Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical class O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical class OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 150000007519 polyprotic acids Polymers 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- YWYZEGXAUVWDED-UHFFFAOYSA-N triammonium citrate Chemical compound [NH4+].[NH4+].[NH4+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O YWYZEGXAUVWDED-UHFFFAOYSA-N 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
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
- C23C18/42—Coating with noble metals
- C23C18/44—Coating with noble metals using reducing agents
Definitions
- the electroless or chemical method for depositing metals permits the deposition of heavy coatings as opposed to simple replacement or immersion technique because the electrons necessary for reduction of the metal are supplied by a reducing agent which is in turn oxidized.
- a reducing agent which is in turn oxidized.
- hypophosphites are widely used as reducing agents in chemical plating processes.
- Among the objects of the invention is to provide an electroless method of depositing silver.
- This invention is based on the discovery that an entirely difierent system from any in common usage is effective to deposit silver from an aqueous solution thereof.
- an entirely difierent system from any in common usage is effective to deposit silver from an aqueous solution thereof.
- the bath of this invention therefore, comprises a potassium silver cyanide solution to which is added 0.1-30 g./l. of a soluble palladous salt (calculated as Pd).
- a soluble palladous salt (calculated as Pd).
- Suitable palladous salts include palladium P salt, (NH Pd(NO disodium palladium tetrachloride, Na PdCl palladous chloride and sulfate.
- Soluble silver cyanide 8 0. H0 Alkali salt of weak acid- 25 up to 200 Weak Acid 12 up to 100 Soluble palladous salt. 2 0. 01-30 Ammonium hydroxide pH 10 pH 8-10 Temperature 80 0. 50100 G.
- the weak acid salts as well as the acids, which, of course, exist in the bath as salts at the pH specified, are optional.
- Effective salts include, the organic acids such as acetic, propionic, citric, tartaric, etc., as well as the inorganic phosphorous acids.
- hydroxy polybasic acids salts such as citrates and the salts of polybasic amino acids such as ethylene di- Patented Apr. 21, 1964 amine tetraacetic acid are particularly desirable, apparently because of their complexing ability.
- a bath was made up as follows:
- a bath was made up similar to the bath in Example 1, except that disodium palladium tetrachloride was substituted for the diamino-dinitro palladium salt.
- a bath was made up to contain G./l. KAg(CN) 2 8.0 Palladium P salt 2.0
- a gold plated brass panel immersed in this bath received a deposit of 1.7 microns in 15 minutes at C.
- composition for chemically depositing silver an aqueous solution having a pH of 8-10 and comprising 0.530 g./1. of a soluble silver cyanide and 0.01 to 30 g./l. of a soluble palladous salt.
- composition for chemically depositing silver an aqueous solution containing G./l. Alkali silver cyanide (calc. as Ag) 0.5-30 Alkali salt of a weak acid Up to 300 Weak acid Up to Palladous salt (calc. as Pd) 0.01-30 Ammonia, sufiicient to provide a pH of 8 to 10.
- an aqueous solution containing G./l. Potassium silver cyanide About 4 Trialkali citrate About 25 Citric acid About 12 Palladous salt About 2 Ammonia, sufiicient to provide a pH of about 10.
- composition as claimed in claim 2 in which the palladous salt is (NH Pd(NO 5.
- the composition as claimed in claim 2 in which the palladous salt is disodium palladium tetrachloride.
- a process for depositing silver on a workpiece having a surface layer of metal comprising immersing the workpiece in an aqueous solution at a temperature of 50 to 100 C. containing 0.5-30 g./l. of a soluble silver cyanide in the presence of 0.01 to 30 g./l. of palladous ions until the desired amount of silver is deposited.
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)
- Chemically Coating (AREA)
Description
United States Patent 3,130,072 SILVER-PALLADIUM IMMERSION PLATING COMPOSITION AND PROCESS Robert Duva, Paramus, Donald Gardner Foulke, Watchung, Plainfield, and Richard Brenneman, Nutley, N.J., assignors to Sel-Rex Corporation, Nutley, N.J., a corporation of New Jersey No Drawing. Filed Sept. 22, 1961, Ser. No. 139,858 9 Claims. (Cl. 117-130) This invention is concerned with the deposition of silver and specifically with the deposition of silver without the use of applied electric current.
The electroless or chemical method for depositing metals permits the deposition of heavy coatings as opposed to simple replacement or immersion technique because the electrons necessary for reduction of the metal are supplied by a reducing agent which is in turn oxidized. For example, hypophosphites are widely used as reducing agents in chemical plating processes.
Among the objects of the invention is to provide an electroless method of depositing silver.
This invention is based on the discovery that an entirely difierent system from any in common usage is effective to deposit silver from an aqueous solution thereof. Thus, it has been discovered that when palladous ions are added to a bath containing a soluble silver cyanide at a suitable temperature, silver rapidly deposits on metals or suitably activated non-conductors.
The bath of this invention, therefore, comprises a potassium silver cyanide solution to which is added 0.1-30 g./l. of a soluble palladous salt (calculated as Pd). Suitable palladous salts include palladium P salt, (NH Pd(NO disodium palladium tetrachloride, Na PdCl palladous chloride and sulfate.
The mechanism of this reduction is not fully understood, but it is known that silver can be deposited to considerable thickness, i.e., much thicker than immersion deposits which are limited to A; to A of a micron. Furthermore, the rate of deposition depends upon the base metal being plated. Deposition of silver on gold is of the order of microns per 6.45 cm. /per hour, on copper 6 microns/6.45 cm. /hour at 80 C.
In practicing this invention, a bath of the compositions shown in Table I may be used.
TABLE I Constituent Optimum, Range,
g./l. g./l.
Soluble silver cyanide 8 0. H0 Alkali salt of weak acid- 25 up to 200 Weak Acid 12 up to 100 Soluble palladous salt. 2 0. 01-30 Ammonium hydroxide pH 10 pH 8-10 Temperature 80 0. 50100 G.
1 G. 1.:grams per liter.
The weak acid salts as well as the acids, which, of course, exist in the bath as salts at the pH specified, are optional. Effective salts include, the organic acids such as acetic, propionic, citric, tartaric, etc., as well as the inorganic phosphorous acids.
The hydroxy polybasic acids salts such as citrates and the salts of polybasic amino acids such as ethylene di- Patented Apr. 21, 1964 amine tetraacetic acid are particularly desirable, apparently because of their complexing ability.
Example No. 1
A bath was made up as follows:
G./l. )2 8 Palladium P salt 2 Ammonium citrate 15.0 Disodium EDTA 37.5
NH OH, to pH 10.0.
Example N0. 2
A bath was made up similar to the bath in Example 1, except that disodium palladium tetrachloride was substituted for the diamino-dinitro palladium salt.
The results were similar to those obtained in Example 1.
Example N0. 3
A bath was made up to contain G./l. KAg(CN) 2 8.0 Palladium P salt 2.0
NH CH, to pH 10.0.
A gold plated brass panel immersed in this bath received a deposit of 1.7 microns in 15 minutes at C.
When K HPO was added to this bath in the amount of 20 g./l., the rate of deposition on gold was 1% microns per 6.45 cm. per 15 minutes at 80 C.
We claim:
1. As a composition for chemically depositing silver an aqueous solution having a pH of 8-10 and comprising 0.530 g./1. of a soluble silver cyanide and 0.01 to 30 g./l. of a soluble palladous salt.
2. As a composition for chemically depositing silver, an aqueous solution containing G./l. Alkali silver cyanide (calc. as Ag) 0.5-30 Alkali salt of a weak acid Up to 300 Weak acid Up to Palladous salt (calc. as Pd) 0.01-30 Ammonia, sufiicient to provide a pH of 8 to 10.
3. As a composition for chemically depositing silver, an aqueous solution containing G./l. Potassium silver cyanide About 4 Trialkali citrate About 25 Citric acid About 12 Palladous salt About 2 Ammonia, sufiicient to provide a pH of about 10.
4. The composition as claimed in claim 2 in which the palladous salt is (NH Pd(NO 5. The composition as claimed in claim 2 in which the palladous salt is disodium palladium tetrachloride.
6. A process for depositing silver on a workpiece having a surface layer of metal comprising immersing the workpiece in an aqueous solution at a temperature of 50 to 100 C. containing 0.5-30 g./l. of a soluble silver cyanide in the presence of 0.01 to 30 g./l. of palladous ions until the desired amount of silver is deposited.
7. A process according to claim 6 wherein the palladous ions are obtained from (NH Pd(NO 8. A process according to claim 6 wherein the palladous ions are obtained from disodium palladium tetrachloride.
9. A process according to claim 6 wherein the palladous ions are obtained from palladous chloride.
References Cited in the file of this patent UNITED STATES PATENTS
Claims (1)
1. AS A COMPOSITION FOR CHEMICALLY DEPOSITING SILVER AN AQUEOUS SOLUTION HAVING A PH OF 8-10 AND COMPRISING 0.5-30 G./L. OF A SOLUBLE SILVER CYANIDE AND 0.01 TO 30 G./L. OF A SOLUBLE PALLADOUS SALT.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US139858A US3130072A (en) | 1961-09-22 | 1961-09-22 | Silver-palladium immersion plating composition and process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US139858A US3130072A (en) | 1961-09-22 | 1961-09-22 | Silver-palladium immersion plating composition and process |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3130072A true US3130072A (en) | 1964-04-21 |
Family
ID=22488613
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US139858A Expired - Lifetime US3130072A (en) | 1961-09-22 | 1961-09-22 | Silver-palladium immersion plating composition and process |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US3130072A (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3337350A (en) * | 1963-01-11 | 1967-08-22 | Mitsubishi Electric Corp | Electroless silver plating |
| US3468676A (en) * | 1963-09-09 | 1969-09-23 | Photocircuits Corp | Electroless gold plating |
| US3530050A (en) * | 1964-06-12 | 1970-09-22 | Johnson Matthey Co Ltd | Electrodeposition of palladium |
| US4424241A (en) | 1982-09-27 | 1984-01-03 | Bell Telephone Laboratories, Incorporated | Electroless palladium process |
| US20020150692A1 (en) * | 1994-12-09 | 2002-10-17 | Soutar Andrew Mcintosh | Printed circuit board manufacture |
| USRE45175E1 (en) | 1994-12-09 | 2014-10-07 | Fry's Metals, Inc. | Process for silver plating in printed circuit board manufacture |
| USRE45297E1 (en) | 1996-03-22 | 2014-12-23 | Ronald Redline | Method for enhancing the solderability of a surface |
| USRE45842E1 (en) | 1999-02-17 | 2016-01-12 | Ronald Redline | Method for enhancing the solderability of a surface |
| USRE45881E1 (en) | 1996-03-22 | 2016-02-09 | Ronald Redline | Method for enhancing the solderability of a surface |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US1208507A (en) * | 1916-07-22 | 1916-12-12 | Agnes Dalby | Preparation for silvering or gilding metal articles. |
| US2430581A (en) * | 1944-11-29 | 1947-11-11 | Rca Corp | Metallizing nonmetallic bodies |
| US2719821A (en) * | 1951-07-19 | 1955-10-04 | Charles R Campana | Gold alloy plating bath |
| US2915406A (en) * | 1958-03-03 | 1959-12-01 | Int Nickel Co | Palladium plating by chemical reduction |
| US2958610A (en) * | 1957-10-07 | 1960-11-01 | Reynolds Metals Co | Pre-plating treatment of aluminous surfaces |
| US3011920A (en) * | 1959-06-08 | 1961-12-05 | Shipley Co | Method of electroless deposition on a substrate and catalyst solution therefor |
| US3053741A (en) * | 1961-04-06 | 1962-09-11 | Leesona Corp | Deposition of metals |
-
1961
- 1961-09-22 US US139858A patent/US3130072A/en not_active Expired - Lifetime
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US1208507A (en) * | 1916-07-22 | 1916-12-12 | Agnes Dalby | Preparation for silvering or gilding metal articles. |
| US2430581A (en) * | 1944-11-29 | 1947-11-11 | Rca Corp | Metallizing nonmetallic bodies |
| US2719821A (en) * | 1951-07-19 | 1955-10-04 | Charles R Campana | Gold alloy plating bath |
| US2958610A (en) * | 1957-10-07 | 1960-11-01 | Reynolds Metals Co | Pre-plating treatment of aluminous surfaces |
| US2915406A (en) * | 1958-03-03 | 1959-12-01 | Int Nickel Co | Palladium plating by chemical reduction |
| US3011920A (en) * | 1959-06-08 | 1961-12-05 | Shipley Co | Method of electroless deposition on a substrate and catalyst solution therefor |
| US3053741A (en) * | 1961-04-06 | 1962-09-11 | Leesona Corp | Deposition of metals |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3337350A (en) * | 1963-01-11 | 1967-08-22 | Mitsubishi Electric Corp | Electroless silver plating |
| US3468676A (en) * | 1963-09-09 | 1969-09-23 | Photocircuits Corp | Electroless gold plating |
| US3530050A (en) * | 1964-06-12 | 1970-09-22 | Johnson Matthey Co Ltd | Electrodeposition of palladium |
| US4424241A (en) | 1982-09-27 | 1984-01-03 | Bell Telephone Laboratories, Incorporated | Electroless palladium process |
| US20020150692A1 (en) * | 1994-12-09 | 2002-10-17 | Soutar Andrew Mcintosh | Printed circuit board manufacture |
| US20110192638A1 (en) * | 1994-12-09 | 2011-08-11 | Enthone Inc. | Silver immersion plated printed circuit board |
| USRE45175E1 (en) | 1994-12-09 | 2014-10-07 | Fry's Metals, Inc. | Process for silver plating in printed circuit board manufacture |
| USRE45279E1 (en) | 1994-12-09 | 2014-12-09 | Fry's Metals, Inc. | Process for silver plating in printed circuit board manufacture |
| US9072203B2 (en) | 1994-12-09 | 2015-06-30 | Enthone Inc. | Solderability enhancement by silver immersion printed circuit board manufacture |
| USRE45297E1 (en) | 1996-03-22 | 2014-12-23 | Ronald Redline | Method for enhancing the solderability of a surface |
| USRE45881E1 (en) | 1996-03-22 | 2016-02-09 | Ronald Redline | Method for enhancing the solderability of a surface |
| USRE45842E1 (en) | 1999-02-17 | 2016-01-12 | Ronald Redline | Method for enhancing the solderability of a surface |
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| Date | Code | Title | Description |
|---|---|---|---|
| AS | Assignment |
Owner name: OXY METAL INDUSTRIES CORPORATION Free format text: CHANGE OF NAME;ASSIGNOR:OXY METAL FINISHING CORPORATION;REEL/FRAME:003967/0084 Effective date: 19741220 |
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| AS | Assignment |
Owner name: HOOKER CHEMICALS & PLASTICS CORP. Free format text: MERGER;ASSIGNOR:OXY METAL INDUSTRIES CORPORATION;REEL/FRAME:004075/0885 Effective date: 19801222 |
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| 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 |