US3878067A - Electrolyte and method for electrodepositing of bright nickel-iron alloy deposits - Google Patents
Electrolyte and method for electrodepositing of bright nickel-iron alloy deposits Download PDFInfo
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- US3878067A US3878067A US414003A US41400373A US3878067A US 3878067 A US3878067 A US 3878067A US 414003 A US414003 A US 414003A US 41400373 A US41400373 A US 41400373A US 3878067 A US3878067 A US 3878067A
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- bath
- nickel
- complexing agent
- iron
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- 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
- C25D3/12—Electroplating: Baths therefor from solutions of nickel or cobalt
- C25D3/14—Electroplating: Baths therefor from solutions of nickel or cobalt from baths containing acetylenic or heterocyclic compounds
-
- 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
- C25D3/56—Electroplating: Baths therefor from solutions of alloys
- C25D3/562—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of iron or nickel or cobalt
Definitions
- Applicants invention is directed to the electrodeposition of a bright iron-nickel alloy deposit of from 5 to 50 percent by weight iron preferably about to about 35% by weight which can be used as the basis for subsequent electrodeposition of chromium in order to impart desirable decorative and/or corrosion resistant properties to substrates, such as metallic substrates.
- the bath and process of the present invention can also be used in the electrodeposition of nickeLiron alloy for plastics.
- plastic substrate such as, acrylonitrile-butadiene-styrene, polyethylene, polypropylene, polyvinyl chloride, phenol-formaldehyde polymers is pretreated by applying a conductive metallic deposit onto the plastic substrate such as, nickel or copper.
- the iron-nickel deposit may then be used as a subsequent coating onto the conductive metallic deposit.
- the bath that may be employed in the present invention utilizes one or more salts of nickel, one or more salts of iron, and a complexing agent.
- any bath soluble iron or nickel containing compound may be employed providing the corresponding anion is not detrimental to the bath.
- inorganic nickel salts may be employed, such as, nickel sulfate, nickel chloride, and the like as well as other nickel materials such as nickel sulfamate and the like.
- nickel sulfate salts When nickel sulfate salts are used they are normally present in amounts ranging from 40 to 300 grams/liter (calculated as nickel sulfate 6I-I O); nickel chloride may also be used and is present in an amount ranging from about to 250 grams/liter.
- the chloride or halide ions are employed in order to obtain satisfactory conductivity of the solution and at the same time to obtain satisfactory corrosion properties of the soluble anodes.
- the inorganic salts of iron are employed, such as, ferrous salts, such as, ferrous sulfate, ferrous chloride, and the like. These salts are present in an amount ranging from about 3 to 60 grams/liter.
- Other bath soluble iron salts may be employed, such as, soluble ferrous fluo'borate, or sulfamate, and the like. The bath 'should contain not less than about 10 g/l of nickel plus ferric and ferrous ions.
- the iron complexing agent that is employed in the present invention is one that is bath soluble and contains complexing groups independently selected from the group consisting of carboxy and hydroxy providing at least I of the complexing groups is a carboxy group and further providing that there are at least two complexing groups.
- the complexing agent that may be employed is present in amount ranging from about 10 to about grams/liter.
- Suitable complexing agents are hydroxy substituted lower aliphatic carboxylic acids having from 2 to 8 carbon atoms, from 1 to 6 hydroxy] groups and from 1 to 3 carboxyl groups such as, ascorbic acid, isoascorbic acid, citric acid, malic acid, gluteric acid, gluconic acid, muconic, glutamic, gluheptonate, glycollic acid, aspartic acid and the like as well as amine containing complexing agents, such as nitrilotriacetic acid, ethylene diamine tetra-acetic acid, as well as the water soluble salts thereof such as ammonium and the alkali metal salts such as potassium, sodium, lithium, and the like. It can also be appreciated that the iron may be introduced into the bath as a salt of the complexing agent.
- carboxy is meant the group-COOH. However, it is to be appreciated that in solution, the proton disassociates from the carboxy group and therefore this group is to be included in the meaning of carboxy.
- the purpose of the complexing agent is to keep the metal ions, in particular, the ferrous and ferric ions in solution. It has been found that as the pH of a normal Watts nickel plating bath increases above a pH of 3.0, ferric ions tend to precipitate as ferric hydroxide. The complexing agent will prevent the precipitation from taking place and therefore makes the iron and nickel ions available for electrodeposition from the complexing agent.
- the pH of the bath preferably ranges from about 2.5 to about 5.5 and even more preferably about 3 to about 3.5.
- the temperature of the bath may range from about F to about 180F preferably about F.
- the average cathode current density may range from about 10 to about 70 amps sq. ft. preferably about 45 amps sq. ft.
- the complexing agent concentration should be at least three times the total iron ion concentration in the bath.
- the complexing agent concentration ratio to total iron ion concentration may range from 3 to 50:1.
- the bath may also contain various buffers such as boric acid and sodium acetate and the like ranging in amounts from about 30 to 60 grams/ liter, preferably 40 grams/liter.
- the ratio of nickel ions to iron ions ranges from about 5 to about 50 to 1.
- While the bath may'be operated without agitation, various means of agitation may be employed such as mechanical agitation, air agitation, cathode rod movement and the like.
- Suitable additives are the sulfo oxygen compounds as are described as brighteners of the first class described in Modern Electroplating, published by John Wiley and Sons, second edition, page 272.
- the amount of sulfo-oxygen compounds employed in the present invention ranges from about 0.5 to about g/l. It has been found that saccharin may be used in amounts ranging from 0.5 to about 5 g/l resulting in a bright ductile deposit. When other sulfo-oxygen compounds are employed, such as, naphthlenetrisulfonic, sulfobenzaldehyde, dibenzenesulfonamide, good brightness is obtained but the ductility is not as good as with saccharin.
- the bath soluble sulfo-oxygen compounds that may be used in the present invention are those such as the unsaturated aliphatic sulfonic acids, mononuclear and binuclear aromatic sulfonic acids, mononuclear aromatic sulfinic acids, mononuclear aromatic sulfonamides and sulfonimides, and the like.
- acetylenic nickel brighteners may also be used in amounts ranging from about 10 to about 500 mg/l. Suitable compounds are the acetylenic sulfo-oxygen compounds mentioned in U.S. Pat. No. 2,800,440. These nickel brighteners are the oxygen containing acetylenic sulfo-oxygen compounds. Other acetylenic nickel brighteners are those described in U.S. Pat. No.
- 3,366,557 such as the polyethers resulting from the condensation reaction of acetylenic alcohols and diols such as, propargyl alcohol, butyndiol, and the like and lower alkylene oxides such as, epichlorohydrin, ethylene oxide, propylene oxide and the like.
- nitrogen heterocyclic quaternary or betaine nickel brighteners may also be used in amounts ranging from about I to about 50 mg/l. Suitable compounds are those nickel brighteners described in U.S. Pat. No. 2,647,866 and the nitrogen heterocyclic sulfonates described in U.S. Pat. No. 3,023,151. Preferred compounds described therein are the pyridine quaternaries or betaines or the pyridine sulfobetaines.
- Suitable quaternaries that may be employed are quinaldine propane sultone, quinaldine dimethyl sulfate, quinaldine allyl bromide, pyridine allyl bromide, isoquinaldine propane sultone, isoquinaldine dimethyl sulfate, isoquinaldine allyl bromide, and the like.
- R l R -N C-S-R where R is hydrogen or a carbon atom of an organic radical, R is nitrogen or a carbon atom of an organic radical and R is a carbon atom of an organic radical. R and R or R may be linked together through a single organic radical.
- bath soluble organic sulfide compounds used are 2-amino thiazoles and isothioureas having the formulae:
- halogens it is intended to include chlorine, bromine, fluorine and iodine, although chlorine is generally preferred.
- lower alkyl or alkoxy groups it is intended to include groups containing from about 1 to 6 carbon atoms in a straight or branched chain, with from about 1 to 4 carbon atoms being preferred.
- sulfonic or carboxy acids and their salts it is intended to include those sulfonic and carboxy acids which have halogen substituents on their alkyl, alkoxy or aryl groups and wherein TABLE I (3) HC-N a N (CH -S0 Na (6) I-lzC-N Compound (1), 2-aminothiazole and compound (2), 2-aminobezothiazole can be reacted with bromoethane sulfonate, propane sultone, benzyl chloride, dimethylsulfate, diethyl sulfate, methyl bromide, propargyl bromide, ethylene dibromide, allyl bromide, methyl chloro acetate, sulfophenoxyethylene bromide, the latter, for example, can be reacted with compound (1) to give compound (3), etc., to form compounds that give even improved results over compounds (1) and (2).
- substituted 2-aminothiazoles and 2- amionbenzothiazoles such as 2-amino-5- chlorothiazole, 2-amino-4-methylthiazole, etc.
- 2-amino-5- chlorothiazole 2-amino-4-methylthiazole, etc.
- thiourea can be reacted with propiolactone, butyrolactone, chloroacetic acid, chloropropionic acid, propane sultone, dimethyl sulfate, etc.
- phenyl thiourea, methyl thiourea, allyl thiourea and other similar substituted thiourea may be used in the reactions to form compounds similar to types (5) and (6).
- nickel brighteners must be soluble in the electroplating bath and may be introduced into the bath, when an acid is involved, as the acid itself or as a salt having bath soluble cations,
- Concentration Range such as ammonium ions or the alkali metal ion, such as, lithium, potassium, sodium, and the like.
- relatively thin coatings of bright nickel iron having less than about 0.5 mil thickness (such as 0.1 mil thickness) with an alloy content of about 20 to 45% iron function more effectively than an equivalent bright nickel coating when copper or brass undercoats are employed.
- the iron content is about 35% or more, the alloy deposits corrode more preferentially to copper or brass undercoats than does bright nickel. This action delays penetration to the basis metal.
- These bright nickel iron coatings also function well as the thin top coat on semi-bright sulfur free nickel deposits.
- the bright nickel iron is very effective in such a composite electroplate when overplated with micro discontinuous chromium coatings such as that described in U.S. Pat. Nos. 3,563,864 and 3,151,971-3.
- the microdiscontinuous chromium coatings may be achieved by thin nickel deposits which induce microporosity or micro-cracking in the chromium or by plating the chromium deposit from a specific solution which deposits a microcracked chromium.
- nickel salts may be substituted with minor amounts up to 50% of the nickel salts with cobalt salts in order to achieve different corrosion behavior.
- a suitable composition that may be employed in the present invention is as follows:
- soluble iron anodes or nickel-iron alloy anodes should be employed.
- the ratio of nickel to iron in the anode area should be maintained at approximately 4 to l.
- dual (nickel and iron) anodes are used and the iron anodes should be insulated from a direct contact to the anode rail and connected subsequently to the anode rail through a highly electrically resistant device such as a nickel-chrome wire or controlled by a separate rheostate to maintain a total current to the iron anodes of about 8 to 30% preferably about 10 to 25% of the total anode current.
- Anode bags, filter bags, hoses, tank linings etc. should be those which are generally employed in other bright nickel processes.
- a bright iron nickel bath was formulated as follows:
- Nickel sulfate hexahydrate I g/l Nickel chloride hexahydrate l g/l Ferrous sulfate heptahydrate 26 g/l Ammonium hydrogen citrate 60 g/l Boric acid Temp. l50F Agitation Rod 4.5 g/l Saccharin 3.75 g/l Allyl sulfonate 200 mg/l Butyne diol ethylene oxide (ratio 1.8 moles oxide: l mole diol) mg/l Quinaldine propane sultone Rolled steel panels were plated at 45 ASF and gave full bright lustrous ductile deposits containing 15-20% iron.
- Example No. l but containing; 7.5 g/l glycine instead of citrate resulted in the formation of an insoluble complex. No acceptable nickel-iron deposit was obtained.
- the iron content of the plated deposit was approximately 20-25%.
- a nickel-iron plating bath having a high iron concentration was tested in a pilot plating laboratory.
- the composition of the bath was as follows:
- the iron included in these deposits was approximately 38-47%.
- a bath was formulated as follows:
- Two nickel-iron plating solutions were prepared having the following compositions.
- a plurality of complexing agents may be used to obtain desirable results. It has also been determined that the gluconate complexing agent tends after long periods of electrolysis to form insoluble materials such as nickel salt of a gluconate degradation product. To continue to obtain desirable results a combination of complexing agents may be employed, such as, citrate and gluconate.
- An aqueous bath suitable for the electrodeposition of a bright iron-nickel electrodeposit onto a substrate susceptible to corrosion comprising not less than about 10 grams per liter nickel plus ferric and ferrous ions, the ratio of nickel ions to ferric and ferrous ions being from about 5 to about 50 to l, 0.5 to 10 g/l of a bath soluble organic primary nickel brightener of the first class containing a sulfo-oxygen group, an amount of a bath soluble complexing agent effective to keep substantially all of the ferric and ferrous ions in solution and containing at least two complexing groups, said groups being independently selected from the group consisting of carboxy and hydroxy, provided at least one group is a carboxy group; the bath having a pH from about 2.5 and about 5.5 and 0.5 to 40 mg/l of an organic sulfide of the formula:
- R is selected from H, lower alkyl sulfonic acid groups, aryl sulfonic acid groups, lower alkoxy aryl sulfonic acid groups and the salts thereof:
- R and R are selected from H, halogen, lower alkyl groups and the bivalent radical in which R is H, halogen or lower alkyl groups and n is 0 or 1, the R groups being selected from H, halogen and lower alkyl groups, R is selected from lower alkyl sulfonic acid groups and lower alkyl carboxy acid groups and the salts thereof; and R and R are selected from H, halogen, lower alkyl groups and the bivalent radical in which the R and R, groups are selected from H, halogen and lower alkyl groups, n is O or 1, and providing that when n O, the bivalent radicals form a six membered ring when R and R are joined and a five membered ring when R and R are joined.
- the complexing agent is an aliphatic carboxylic acid having from 1 to 3 carboxyl groups, 2 to 8 carbon atoms, and l to 6 hydroxyl groups.
- R is lower alkyl carboxy acid and salts thereof.
- the bath of claim 1 wherein the total iron ions are present in an amount ranging from about 5 to 40 g/l, calculated as FeSO .7H O; nickel sulfate present in an amount ranging from about 40 to 300 g/l, calculated as nickel sulfate.6H O; nickel chloride hexahydrate present in an amount from about 80 to 250 g/l and the complexing agent is present in an amount from about 10 to 100 g/l.
- the bath of claim 1 further comprising an acety- 12 lenic nickel brightener present in an amount ranging from about 10 to 500 mg/l.
- the bath of claim 1 further comprising a quaternary nitrogen heterocyclic nickel brightener present in an amount ranging from about 1 to about 50 mg/l.
- a process for producing a bright iron nickel alloy electrodeposit comprising passing a current through the bath of claim 1 and electrodepositing an iron nickel alloy containing about from 5 to about 50% iron onto a cathodic surface.
- R is selected from H, lower alkyl sulfonic acid groups, aryl sulfonic acid groups, lower alkoxy aryl sulfonic acid groups and the salts thereof;
- R and R are selected from H, halogen, lower alkyl groups and the bivalent radical F10 C I in which R, is H, halogen or lower alkyl groups and n is O or 1, the R groups being selected from H, halogen and lower alkyl groups, R is selected from lower alkyl sulfonic acid groups and lower alkyl carboxy acid groups and the salts thereof; and R and R are selected from H, halogen, lower alkyl groups and the bivalent radical in which the R and R groups are selected from H, halogen and lower alkyl groups, n is 0 or 1, and providing that when n O, the bivalent radicals form a six membered ring when R, and R are joined and a five membered ring when R and R are joined.
- the complexing agent is an aliphatic carboxylic acid having from 1 to 3 carboxyl groups, 2 to 8 carbon atoms, and l to 6 hydroxyl groups.
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Abstract
Description
Claims (40)
Priority Applications (9)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US414003A US3878067A (en) | 1972-07-03 | 1973-11-08 | Electrolyte and method for electrodepositing of bright nickel-iron alloy deposits |
AR25646774A AR224853A1 (en) | 1973-11-08 | 1974-10-08 | A SUITABLE AQUEOUS BATHROOM FOR THE ELECTRO-DEPOSITION OF A GLOSSY IRON-NICKEL ALLOY ON A SUBSTRATE SUSCEPTIBLE TO CORROSION AND ELECTRO-DEPOSITION PROCEDURE FROM SUCH A BATH |
CA213,100A CA1028649A (en) | 1973-11-08 | 1974-11-04 | Organic sulfides useful for the electrodeposition of bright nickel iron deposits |
DE19742452831 DE2452831A1 (en) | 1973-11-08 | 1974-11-07 | BATH AND METHOD FOR GALVANIC DEPOSITION OF GLOSSY NICKEL IRON |
BR937574A BR7409375A (en) | 1973-11-08 | 1974-11-07 | BATH AND PROCESS TO PRODUCE A BRIGHT IRON-NICKEL ALLOY ELECTRODEPOSIT |
JP12883474A JPS5635753B2 (en) | 1973-11-08 | 1974-11-08 | |
FR7437049A FR2250834A1 (en) | 1973-11-08 | 1974-11-08 | Electrodepositing bright nickel-iron alloy deposits - from aq. bath contg. complexing agent and sulphide brightener |
IT5393774A IT1023186B (en) | 1973-11-08 | 1974-11-08 | ACOUSE BATH FOR THE ELECTRODEPOSITION OF IRON NICKEL AND PROCEDURE TO PRODUCE |
NL7414615A NL7414615A (en) | 1973-11-08 | 1974-11-08 | PROCESS FOR ELECTROLYTIC DEPOSITION OF GLOSSY NICKEL IRON COATINGS. |
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US26835272A | 1972-07-03 | 1972-07-03 | |
US414003A US3878067A (en) | 1972-07-03 | 1973-11-08 | Electrolyte and method for electrodepositing of bright nickel-iron alloy deposits |
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US3878067A true US3878067A (en) | 1975-04-15 |
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US414003A Expired - Lifetime US3878067A (en) | 1972-07-03 | 1973-11-08 | Electrolyte and method for electrodepositing of bright nickel-iron alloy deposits |
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Cited By (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3974044A (en) * | 1975-03-31 | 1976-08-10 | Oxy Metal Industries Corporation | Bath and method for the electrodeposition of bright nickel-iron deposits |
US3994694A (en) * | 1975-03-03 | 1976-11-30 | Oxy Metal Industries Corporation | Composite nickel-iron electroplated article |
US4014759A (en) * | 1975-07-09 | 1977-03-29 | M & T Chemicals Inc. | Electroplating iron alloys containing nickel, cobalt or nickel and cobalt |
US4053373A (en) * | 1975-07-09 | 1977-10-11 | M & T Chemicals Inc. | Electroplating of nickel, cobalt, nickel-cobalt, nickel-iron, cobalt-iron and nickel-iron-cobalt deposits |
US4089754A (en) * | 1977-07-18 | 1978-05-16 | Oxy Metal Industries Corporation | Electrodeposition of nickel-iron alloys |
US4179343A (en) * | 1979-02-12 | 1979-12-18 | Oxy Metal Industries Corporation | Electroplating bath and process for producing bright, high-leveling nickel iron electrodeposits |
US4375849A (en) * | 1981-05-15 | 1983-03-08 | Sage Products, Inc. | Syringe needle removal and disposal device |
US4450051A (en) * | 1981-01-13 | 1984-05-22 | Omi International Corporation | Bright nickel-iron alloy electroplating bath and process |
US4874103A (en) * | 1986-10-01 | 1989-10-17 | Winfield Corporation | Receptacle for receiving infectious waste material |
US5683568A (en) * | 1996-03-29 | 1997-11-04 | University Of Tulsa | Electroplating bath for nickel-iron alloys and method |
US20100167087A1 (en) * | 2007-07-13 | 2010-07-01 | Hille & Muller Gmbh | Method of providing a metallic coating layer and substrate provided with said coating layer |
US20130071738A1 (en) * | 2010-02-10 | 2013-03-21 | Qiming Wang | Soft package lithium battery tab material and its method of plating and application |
US8637165B2 (en) | 2011-09-30 | 2014-01-28 | Apple Inc. | Connector with multi-layer Ni underplated contacts |
US9004960B2 (en) | 2012-08-10 | 2015-04-14 | Apple Inc. | Connector with gold-palladium plated contacts |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2892760A (en) * | 1954-10-28 | 1959-06-30 | Dehydag Gmbh | Production of metal electrodeposits |
US2978391A (en) * | 1958-08-25 | 1961-04-04 | Harshaw Chem Corp | Nickel plating process and solution |
US3276979A (en) * | 1961-08-31 | 1966-10-04 | Dehydag Gmbh | Baths and processes for the production of metal electroplates |
-
1973
- 1973-11-08 US US414003A patent/US3878067A/en not_active Expired - Lifetime
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2892760A (en) * | 1954-10-28 | 1959-06-30 | Dehydag Gmbh | Production of metal electrodeposits |
US2978391A (en) * | 1958-08-25 | 1961-04-04 | Harshaw Chem Corp | Nickel plating process and solution |
US3276979A (en) * | 1961-08-31 | 1966-10-04 | Dehydag Gmbh | Baths and processes for the production of metal electroplates |
Cited By (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3994694A (en) * | 1975-03-03 | 1976-11-30 | Oxy Metal Industries Corporation | Composite nickel-iron electroplated article |
US3974044A (en) * | 1975-03-31 | 1976-08-10 | Oxy Metal Industries Corporation | Bath and method for the electrodeposition of bright nickel-iron deposits |
US4014759A (en) * | 1975-07-09 | 1977-03-29 | M & T Chemicals Inc. | Electroplating iron alloys containing nickel, cobalt or nickel and cobalt |
US4053373A (en) * | 1975-07-09 | 1977-10-11 | M & T Chemicals Inc. | Electroplating of nickel, cobalt, nickel-cobalt, nickel-iron, cobalt-iron and nickel-iron-cobalt deposits |
US4089754A (en) * | 1977-07-18 | 1978-05-16 | Oxy Metal Industries Corporation | Electrodeposition of nickel-iron alloys |
US4179343A (en) * | 1979-02-12 | 1979-12-18 | Oxy Metal Industries Corporation | Electroplating bath and process for producing bright, high-leveling nickel iron electrodeposits |
FR2448584A1 (en) * | 1979-02-12 | 1980-09-05 | Oxy Metal Industries Corp | PROCESS FOR PRODUCING NICKEL-IRON ELECTROLYTIC DEPOSITS AND BATHS USED FOR THIS PURPOSE, INCLUDING IN PARTICULAR A TARTRATE AND A REDUCING MONO OR DISACCHARIDE |
US4450051A (en) * | 1981-01-13 | 1984-05-22 | Omi International Corporation | Bright nickel-iron alloy electroplating bath and process |
US4375849A (en) * | 1981-05-15 | 1983-03-08 | Sage Products, Inc. | Syringe needle removal and disposal device |
US4874103A (en) * | 1986-10-01 | 1989-10-17 | Winfield Corporation | Receptacle for receiving infectious waste material |
US5683568A (en) * | 1996-03-29 | 1997-11-04 | University Of Tulsa | Electroplating bath for nickel-iron alloys and method |
US5932082A (en) * | 1996-03-29 | 1999-08-03 | The University Of Tulsa | Electroplating bath for nickel-iron alloys and method |
US20100167087A1 (en) * | 2007-07-13 | 2010-07-01 | Hille & Muller Gmbh | Method of providing a metallic coating layer and substrate provided with said coating layer |
US8551316B2 (en) * | 2007-07-13 | 2013-10-08 | Hille & Muller Gmbh | Method of electrodepositing a metallic coating layer containing nickel and molybdenum |
US20130071738A1 (en) * | 2010-02-10 | 2013-03-21 | Qiming Wang | Soft package lithium battery tab material and its method of plating and application |
US8637165B2 (en) | 2011-09-30 | 2014-01-28 | Apple Inc. | Connector with multi-layer Ni underplated contacts |
US9004960B2 (en) | 2012-08-10 | 2015-04-14 | Apple Inc. | Connector with gold-palladium plated contacts |
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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 |
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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 |