US2849351A - Electroplating process - Google Patents
Electroplating process Download PDFInfo
- Publication number
- US2849351A US2849351A US442199A US44219954A US2849351A US 2849351 A US2849351 A US 2849351A US 442199 A US442199 A US 442199A US 44219954 A US44219954 A US 44219954A US 2849351 A US2849351 A US 2849351A
- Authority
- US
- United States
- Prior art keywords
- acid
- electroplating
- group
- lustrous
- sulfonic acids
- 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
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/41—Compounds containing sulfur bound to oxygen
- C08K5/42—Sulfonic acids; Derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
- C07D277/02—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings
- C07D277/20—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D277/32—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D277/58—Nitro radicals
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D7/00—Electroplating characterised by the article coated
- C25D7/02—Slide fasteners
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Engineering & Computer Science (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Electroplating And Plating Baths Therefor (AREA)
- Paints Or Removers (AREA)
- Electroplating Methods And Accessories (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
ELEcTRoPtA'riNG PROCESS No Drawing. Application July 8, 1954 Serial N 0. 442,199
Claims priority, application Germany September 19, 1953 14 Claims. 01. 204-44 This invention relates to an improvement in electroplating and more particularly to electroplating baths modified with an organic sulfonic acid addition agent which will produce a bright and lustrous electro deposit.
Electroplating baths have heretofore been modified by the inclusion of organic sulfonic acids or organic sulfation products of various compounds. While the prior art addition agents have usually effected some improvement in the characteristics of the electro deposit produced from such modified baths, the additives individually have not been sufficient to produce commercially desirable deposits and had to be used with another and sometimes with even two or more supplemental addition agents.
It is an object of the invention to provide electroplating compositions of improved character.
Another object of the invention is to provide an electroplating bath which will produce bright and lustrous electro deposits which in many instances may be used for their intended purpose without further polishing or buffing.
Still another object of the invention is to provide addition agents for electroplating baths which may advantageously be used as sole addition agents or with other addition agents to produce bright and lustrous deposits.
Still further objects and advantages will become apparent as the description of the invention proceeds.
We have found that bright, highly lustrous and welladhering electroplate deposits can be obtained by modifying electroplating baths containing the metal to be deposited primarily in the form of an acid solution of an inorganic salt of the metal with organic sulfonic acids or their salts having the general structural formula wherein G represents an organic radical which comprises a carbon atom bonded exclusively to hetero atoms and to the radical R SO H through a sulfur atom and R represents a bivalent aliphatic radical which may be unsubstituted or may carry other organic substituents, such as, for example, ethylene, propylene, alkyl propylene, hydroxy propylene, pentylene radicals.
In other words the brightening agents used in accordance with the present invention are organic sulfonic acids or salts thereof which have the general structural States Patent Patented Aug. 26, 1958 lCe CS--RSOsH Y and their salts, wherein X and Y are selected from the group consisting of nitrogen, sulfur and oxygen atoms.
Typical sulfonic acids or their salts which can a dvantageously be used, either individually or in combination with each other, as brightening agents in electroplating baths in accordance with the present invention are the following:
1(1) Sulfonic acids derived from thiourea and, if the cation chain is closed, from Z-thioimidazoles or Z-benzene imidazoles, having the following structural formula:
C-SR.SO3H
(2) Sulfonic acids derived from Z-mercaptothiazoles or 2-mercapt0benzene thiazoles and from thiocyanates, having the following structural formula:
t3s-R.sOiH
(3) Sulfonic acids derived from 2-thiobenzoxazoles and 2-thiocumazoles (2-thiobenzene-metoxazine), having the following structural formula:
(4) Sulfonic acids derived from dithiocarbamic acids, having the following structural formula:
(5) Sulfonic acids derived from thioxanthic acid or trithiocarbonic acid, having the following structural formula:
O-SR.SOsH
(6) Sulfonic acids derived from xanthic acid, having the following structural formula:
0 s-R.s0tH
(7) Sulfonic acids derived from carbaminothiol acids, having the following structural formula:
CSR.SO3H
In all of the above representative examples of sulfonic 1 acids suitable for use as brightening additives for the specific salts of sulfonic acids of the above general classes acid-n-propylestenet-sodium N-butyl-dithiocarbamic acid-n-butylester-w-sodium sulfonate;
N-p-tolyl-dithiocarbamic acid-n-propylester-w-potassium sulfonate;
Dithiocarbamic acid-n-propylester-ammonium sulfonate; S-phenyl-trithiocarbonic acid-n-propylester-w-sodium sulfonate;
Trithiocarbonic acid-bis-propylester-w-sodium sulfonate; Isopropyl-xanthic acid-n-butylester-w-sulfonate of sodium; n-butyl-xanthic acid-n-propylester-w-sodium sulfonate; Carbamino-thiol acid-n-propylester-potassium sulfonate; and the like.
The specific sulfonic acid salts listed above for the purpose of illustrating the invention, but not of limiting the invention thereof, can be used as brightening agents in all types of electroplating baths, and particularly in electroplating baths for electrodepositing nickel, copper, zinc, silver, bronze and brass. They are capable of producing bright and lustrous deposits either individually or in conjunction with other well-known brightening agents, salts which improve the conductivity of the electroplating bath, wetting agents, or agents which tend to reduce the porosity of the deposit. above brightening agents are suitable for use in conjunction with those additives disclosed in German Patents No. 863,159 and No. 871,392.
It is well known in the art that the amount of brightening agent added to an electroplating bath in order to produce a bright and lustrous deposit lies between certain limits within which the desired results will be obtained. These limits are different for each individual agent. It is also known that the range of current densities which will produce a bright and lustrous deposit lies between certain limits and those limits depend large- 1y upon the type and amount of agent used and the temperature of the electroplating bath. We have found that the addition of organic sulfonic acids in accordance with the invention as brightening agents for electroplating baths will increase the range of current densities over which deposits of satisfactory character can be produced. The amounts in which compounds of the invention are added to electroplating baths to produce bright and lustrous deposits vary between 0.01 and gm. per liter of bath. The current density limit within which the above amounts will produce bright and lustrous deposits lies between 0.5 and 12 amp./drn. at a temperature below 60 C. By employing a mixture of the brighten ing agents disclosed herein, it is possible to further widen the range of current densities which will produce satisfactory bright and lustrous deposits.
Non-precious metals to be electroplated, such as, for example, iron, steel or zinc, to mention only a few, are usually first provided with a base coating of copper in a potassium cyanide bath before being finally electroplated with the desired metal. The brightening agents of this invention are suitable for use in electroplating objects pro-coated in this manner as well as in electroplating objects not so pre-coated.
In particular, the
Metal electro deposits produced from baths modified with the sulfonic acid additives of this invention are bright, highly lustrous and adhere very firmly to the base. In most cases the luster of the electro deposit so produced is so high that the electroplated object requires no further polishing or buffing after rinsing, whereby this additional time-consuming and costly step can be omitted in the production of electroplated articles. Moreover, the sulfonic acid brightening agents of this invention have the additional advantage that they are chemically resistant to acid conditions, so that electroplating baths modified with such additives can remain in use virtually continuously, even at high temperatures, without losing their intended effectiveness.
The following examples will enable persons skilled in the art to understand our invention more completely. It. is understood, however, that these examples are merely representative of the general inventive concept and that we do not intend to limit our invention to their exact conditions.
Example I 0.5 to 1 gm. of N,N-diethyl-dithiocarbarnic acid-npropylester-w-sodium sulfonate was added to each liter of an acid copper sulfate bath which contains 60 gm. sulfuric acid and gm. crystallized copper sulfate per liter of solution. Sheet steel provided with a preliminary copper coating in the presence of potassium cyanide was electroplated in the above bath. Within a current density range of from 1 to 10 amp./dm. at room temperature, both flat and highly profiled sheet steel objects were provided with a highly lustrous and well-adhering copper plate which did not require any further polishing or buffing treatment after rinsing.
Example II 0.5 to 1.5 gm. 2-rnercaptobenzenethiazole-S-propanew-sodium sulfonate are added to each liter of the electroplating bath of Example I. An object electroplated in this solution at room temperature within current density limits of 7.5 to 10 amp./dm. was provided with a copper coating which was highly lustrous and did not need any further polishing treatment.
Example III 1 gm. of betaine salt of isothiourea-S-propane-w-sulfonic acid was added to each liter of the electroplating bath of Examples I and II. An object electroplated in this solution at room temperature and current densities between 6 and 7.5 amp./dm. was provided with a highly lustrous copper coating which required no further polishing treatment after rinsing.
Example I V Example V The same effect as in Example IV was obtained by adding 1 gm. of n-butylxanthic acid-n-propylester-w-sodium sulfonate per liter of acid copper sulfate solution of Example IV to such a solution and electroplating at the same temperature, but with a current density of 4 to 6 amp./dm.
Example V1 0.5 to 1 gm. of the betaine salt of isothiourea-S-butanew-SlllfOHlC acid was dissolved in each liter of a nickelplating bath containing 60 gm. nickel chloride, 220 gm. crystallized nickel sulfate and 35 gm. boric acid per liter of solution. An object electroplated in such a solution at room temperature and current densities between 1 and amp./dm. was provided with a well-adhering and highly lustrous nickel coating which required no further polishing treatment.
Example VII Effects similar to those of Example VI were obtained by adding to the nickel-plating bath of that example 0.5-1 gm. N,N-pentamethylene-dithiocarbamic acid-n-propylesteem-sodium sulfonate and electroplating at room temperature and current densities between 4 and 8 amp./dm. 1
Example VIII The same highly lustrous nickel plate was obtained by substituting an equal amount of unsubstituted dithiocarbamic acid-n-propylester-w-sodium sulfonate for the sulfonate of Example VII, and electroplating at the same conditions of temperature and current densities as those stated in Example VII.
Example IX v 0.5 to 1 gm. of N,N-dimethyl-dithiocarbamic acid-npropylester-w-sodium sulfonate was dissolved in each liter of a zinc electroplating bath containing 200 gm. zinc sulfate and 1 gm. glacial acetic acid per liter of solution. Sheet steel electroplated in such a solution at room temperature and current densities between 4 and 9 amp./dm. was plated With a highly lustrous zince coating which did not need to be polished after rinsing. Without the addition of the above sulfonate, the zinc coating was dull and required polishing to give it luster.
Instead of the electroplating baths described above, other electroplating solutions for depositing chromium, tin, precious metals and the like may be used, and various other modifications and changes may be made from the above description without departing from the spirit of our invention or the scope of the following claims.
We claim:
1. An electroplating bath for producing deposits of metals selected from the group consisting of nickel, copper, zinc, silver, bronz and brass, comprising an acid solution of an inorganic salt of the metal to be deposited and a compound selected from the group consisting of organic sulfonic acids having the general structural formula and their salts, wherein G is an organic radical which includes a carbon atom bonded exclusively with three hetero atoms, one of which is a sulfur atom through which said organic radical G is linked to the radical R-SO H, the other two hetero atoms being selected from the group consisting of nitrogen, sulfur and oxygen atoms, and R is a bivalent aliphatic radical, said compound being added in a quantity sufficient to produce a bright metal deposit.
2. The process of producing bright and lustrous deposits of metals selected from the group consisting of nickel, copper, zinc, silver, bronze and brass which comprise electrodepositing said metal from a bath containing said metal principally in the form of an acid solution of an inorganic salt of the metal in the presence of a brightening agent selected from the group consisting of organic sulfonic acids having the general structural formula and their salts, wherein G represents a carbon atom group consisting of a carbon atom linked exclusively to three hetero atoms, one of which is a sulfur atom which links the carbon atom to the radical R, the other two hetero atoms being selected from the group consisting of nitrogen, sulfur and oxygen atoms, and R is a bivalent aliphatic radical, said compound being added in a quantity sufficient to produce a bright metal deposit.
3. An electroplating bath for producing deposits of and their salts, wherein X and Y each represent an atom selected from the group consisting of oxygen, nitrogen and sulfur, and R is a bivalent aliphatic radical.
4. The process of producing bright and lustrous electrodeposits of metals selected from the group consisting of nickel, copper, zinc, silver, bronze and brass which comprises electrodepositing said metal from a bath containing said metal in the form of an acid solution of an inorganic salt of the metal in the presence of about 0.01 to 20 gm. per liter of a brightening agent selected from the group consisting of organic sulfonic acids having the general structural formula selected from the group consisting of and their salts, wherein X and Y each represent an atunl selected from the group consisting of nitrogen, sulfur and oxygen, and R is a bivalent aliphatic radical.
5. An electroplating bath as in claim 1, said bivalent aliphatic radical being substituted.
6. An electroplating bath as in claim 1, said bivalent aliphatic radical being unsubstituted.
7. A process as in claim 2, said bivalent aliphatic radical being substituted.
8. A process as in claim 2, said bivalent aliphatic radical being unsubstituted.
9. An electroplating bath for producing deposits of metals selected from the group consisting of nickel, copper, zinc, silver, bronze and brass comprising an acid solution of an inorganic salt of the metal to be deposited and 0.01 to 20 gm. per liter of a compound selected from the group consisting of organic sulfonic acids having the general structural formula and their salts, wherein X and Y each represent an atom selected from the group consisting of nitrogen, oxygen and sulfur, and R is a bivalent aliphatic radical.
10. An electroplating bath as in claim 9, said bivalent aliphatic radical being substituted.
11. An electroplating bath as in claim 9, said bivalent aliphatic radical being unsubstituted.
12. The process of producing bright and lustrous deposits of metals selected from the group consisting of nickel, copper, zinc, silver, bronze and brass which comprises electrodepositing said metal from a bath containing said metal in the form of an acid solution of an inorganic salt of the metal in the presence of about 0.01 to 20 gm. per liter of a brightening agent selected from the group consisting of organic sulfonic acids having the general structural formula References Cited in the file of this patent UNITED STATES PATENTS 2,389,181 Brown Nov. 20, 1945 2,424,887 Henricks July 29, 1947 2,648,627 Donnelly Aug. 11, 1953 2,663,684 Pierce Dec. 22, 1953
Claims (1)
1. AN ELECTROPLATING BATH FOR PRODUCING DEPOSITS OF METALS SELECTED FROM THE GROUP CONSISTING OF NICKEL, COPPER, ZINC, SILVER, BRONZ AND BRASS, COMPRISING AN ACID SOLUTION OF AN INORGANIC SALT OF THE METAL TO BE DEPOSITED AND A COMPOUND SELECTED FROM THE GROUP CONSISTING OF ORGANIC SULFONIC ACIDS HAVING THE GENERAL STRUCTURAL FORMULA
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE327298X | 1953-09-19 | ||
DED19318A DE1207177B (en) | 1953-09-19 | 1954-12-13 | Process for the production of shiny galvanic metal coatings |
DE2907786X | 1955-01-05 |
Publications (1)
Publication Number | Publication Date |
---|---|
US2849351A true US2849351A (en) | 1958-08-26 |
Family
ID=32329406
Family Applications (3)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US442199A Expired - Lifetime US2849351A (en) | 1953-09-19 | 1954-07-08 | Electroplating process |
US552699A Expired - Lifetime US2837472A (en) | 1953-09-19 | 1955-12-13 | Brighteners for electroplating baths |
US557422A Expired - Lifetime US2907786A (en) | 1953-09-19 | 1956-01-04 | Sulfonic derivatives of dithiocarbamic acid and method of making the same |
Family Applications After (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US552699A Expired - Lifetime US2837472A (en) | 1953-09-19 | 1955-12-13 | Brighteners for electroplating baths |
US557422A Expired - Lifetime US2907786A (en) | 1953-09-19 | 1956-01-04 | Sulfonic derivatives of dithiocarbamic acid and method of making the same |
Country Status (7)
Country | Link |
---|---|
US (3) | US2849351A (en) |
BE (1) | BE543413A (en) |
CH (2) | CH327298A (en) |
DE (2) | DE923407C (en) |
FR (3) | FR1097123A (en) |
GB (1) | GB823152A (en) |
NL (4) | NL202744A (en) |
Cited By (28)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2986498A (en) * | 1954-03-13 | 1961-05-30 | Dehydag Gmbh | Process for the production of metal electrodeposits |
US3000800A (en) * | 1957-04-16 | 1961-09-19 | Dehydag Gmbh | Copper-electroplating baths |
US3017333A (en) * | 1959-04-06 | 1962-01-16 | Mcgean Chem Co Inc | Self-leveling bright nickel plating bath and process |
US3023150A (en) * | 1954-03-22 | 1962-02-27 | Dehydag Gmbh | Bath for the production of metal electroplates |
US3051634A (en) * | 1957-11-30 | 1962-08-28 | Dehydag Gmbh | Baths for the production of copper electroplates |
US3075899A (en) * | 1958-04-26 | 1963-01-29 | Dehydag Gmbh | Baths for the production of metal electroplates |
US3084163A (en) * | 1958-04-29 | 1963-04-02 | Dehydag Gmbh | Heterocyclic thioalkane sulfonic acids and methods for their production |
US3165456A (en) * | 1960-11-21 | 1965-01-12 | Minnesota Mining & Mfg | Developer |
US3188312A (en) * | 1960-02-27 | 1965-06-08 | Dehydag Gmbh | New process for the preparation of thiourea derivatives |
US3215611A (en) * | 1962-07-20 | 1965-11-02 | Dehydag Gmbh | Process for deposition of fine grained deposits in the refining and reduction electrolysis of metals |
US3276979A (en) * | 1961-08-31 | 1966-10-04 | Dehydag Gmbh | Baths and processes for the production of metal electroplates |
US3502551A (en) * | 1966-08-20 | 1970-03-24 | Schering Ag | Acid electrolyte for the deposition of bright,levelling copper coatings |
US3940320A (en) * | 1972-12-14 | 1976-02-24 | M & T Chemicals Inc. | Electrodeposition of copper |
US3956084A (en) * | 1972-12-14 | 1976-05-11 | M & T Chemicals Inc. | Electrodeposition of copper |
US3956120A (en) * | 1972-12-14 | 1976-05-11 | M & T Chemicals Inc. | Electrodeposition of copper |
US3956078A (en) * | 1972-12-14 | 1976-05-11 | M & T Chemicals Inc. | Electrodeposition of copper |
US3956079A (en) * | 1972-12-14 | 1976-05-11 | M & T Chemicals Inc. | Electrodeposition of copper |
US3966565A (en) * | 1972-12-14 | 1976-06-29 | M & T Chemicals Inc. | Electrodeposition of copper |
US4014760A (en) * | 1974-11-21 | 1977-03-29 | M & T Chemicals Inc. | Electrodeposition of copper |
US4036711A (en) * | 1975-12-18 | 1977-07-19 | M & T Chemicals Inc. | Electrodeposition of copper |
US4036710A (en) * | 1974-11-21 | 1977-07-19 | M & T Chemicals Inc. | Electrodeposition of copper |
US4134803A (en) * | 1977-12-21 | 1979-01-16 | R. O. Hull & Company, Inc. | Nitrogen and sulfur compositions and acid copper plating baths |
US4376685A (en) * | 1981-06-24 | 1983-03-15 | M&T Chemicals Inc. | Acid copper electroplating baths containing brightening and leveling additives |
US4502927A (en) * | 1981-11-18 | 1985-03-05 | International Business Machines Corporation | Electrodeposition of chromium and its alloys |
US4549942A (en) * | 1981-07-06 | 1985-10-29 | Omi International Corporation | Process for electrodepositing composite nickel layers |
US5656148A (en) * | 1995-03-02 | 1997-08-12 | Atotech Usa, Inc. | High current density zinc chloride electrogalvanizing process and composition |
US9017463B2 (en) * | 2012-05-22 | 2015-04-28 | Byd Company Limited | Copper plating solution and method for preparing the same |
DE202015003382U1 (en) | 2014-05-09 | 2015-06-16 | Dr. Hesse GmbH & Cie. KG | Electrolytic deposition of copper from water-based electrolytes |
Families Citing this family (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3156717A (en) * | 1960-12-28 | 1964-11-10 | Montedison Spa | Organic sulfur compounds having fungicidal activity |
US3180791A (en) * | 1960-12-28 | 1965-04-27 | Montedison Spa | Method of controlling fungi with organic sulfur ester compounds |
NL134137C (en) * | 1961-02-02 | |||
DE1177142B (en) * | 1961-07-08 | 1964-09-03 | Dehydag Gmbh | Process for the preparation of dithiocarbamic acid ester derivatives containing sulfonic acid groups |
NL281922A (en) * | 1961-08-10 | |||
US3151123A (en) * | 1962-06-19 | 1964-09-29 | Keystone Chemurgic Corp | Acid-soluble chlorophyllins and their production |
US3322657A (en) * | 1964-04-28 | 1967-05-30 | Langbein Pfanhauser Werke Ag | Electrodeposition of bright copper |
US3414493A (en) * | 1965-10-19 | 1968-12-03 | Lea Ronal Inc | Electrodeposition of copper |
US3787297A (en) * | 1971-10-26 | 1974-01-22 | Conversion Chem Corp | Zinc plating bath and method |
US3876513A (en) * | 1972-06-26 | 1975-04-08 | Oxy Metal Finishing Corp | Electrodeposition of bright cobalt plate |
US4786746A (en) * | 1987-09-18 | 1988-11-22 | Pennsylvania Research Corporation | Copper electroplating solutions and methods of making and using them |
US4948474A (en) * | 1987-09-18 | 1990-08-14 | Pennsylvania Research Corporation | Copper electroplating solutions and methods |
CN101128421A (en) * | 2004-12-22 | 2008-02-20 | 神经化学(国际)有限公司 | Methods and compositions for treating amyloid-related diseases |
US8748656B2 (en) | 2006-10-12 | 2014-06-10 | Bhi Limited Partnership | Methods, compounds, compositions and vehicles for delivering 3-amino-1-propanesulfonic acid |
CN111910222B (en) * | 2020-08-21 | 2022-08-23 | 九江德福科技股份有限公司 | Electrolytic copper foil additive with brightening and leveling functions and application thereof |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2389181A (en) * | 1941-05-15 | 1945-11-20 | Udylite Corp | Electrodeposition of metals |
US2424887A (en) * | 1941-10-11 | 1947-07-29 | Houdaille Hershey Corp | Method and electrolyte for the electrodeposition of metals |
US2648627A (en) * | 1950-05-24 | 1953-08-11 | Wagner Brothers Inc | Bright nickel plating composition and process |
US2663684A (en) * | 1952-06-02 | 1953-12-22 | Houdaille Hershey Corp | Method of and composition for plating copper |
Family Cites Families (10)
Publication number | Priority date | Publication date | Assignee | Title |
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US1972961A (en) * | 1931-05-26 | 1934-09-11 | Du Pont | Disinfectant |
FR753080A (en) * | 1932-11-02 | 1933-10-06 | Manufacturing process for whitening, wetting, spumescent, dispersing and impregnating products | |
US2127375A (en) * | 1935-07-17 | 1938-08-16 | Du Pont | Esters of dithiocarbamic acids |
US2313871A (en) * | 1938-09-15 | 1943-03-16 | Du Pont | Polythiourea |
GB628397A (en) * | 1945-10-05 | 1949-08-29 | Goodrich Co B F | Improvements in or relating to beta-dithiocarbamyl carboxylic compounds and method of preparing same |
US2491772A (en) * | 1945-12-29 | 1949-12-20 | Standard Oil Dev Co | Extreme pressure lubricants |
US2647866A (en) * | 1950-07-17 | 1953-08-04 | Udylite Corp | Electroplating of nickel |
US2673839A (en) * | 1951-04-28 | 1954-03-30 | Standard Oil Dev Co | Lubricating oil composition |
DE888493C (en) * | 1951-11-03 | 1953-09-03 | Hydrierwerke A G Deutsche | Process for the production of firmly adhering and shiny galvanic copper coatings |
DE924489C (en) * | 1953-04-28 | 1955-03-03 | Degussa | Bath for the galvanic deposition of metals |
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0
- NL NL298381D patent/NL298381A/xx unknown
- NL NL110737D patent/NL110737C/xx active
- NL NL109804D patent/NL109804C/xx active
- BE BE543413D patent/BE543413A/xx unknown
- NL NL202744D patent/NL202744A/xx unknown
-
1953
- 1953-10-20 DE DEO3231A patent/DE923407C/en not_active Expired
-
1954
- 1954-01-20 CH CH327298D patent/CH327298A/en unknown
- 1954-03-24 FR FR1097123D patent/FR1097123A/en not_active Expired
- 1954-07-08 US US442199A patent/US2849351A/en not_active Expired - Lifetime
- 1954-12-13 DE DED19318A patent/DE1207177B/en active Pending
-
1955
- 1955-08-18 FR FR68292D patent/FR68292E/en not_active Expired
- 1955-12-08 CH CH344715D patent/CH344715A/en unknown
- 1955-12-09 GB GB35340/55A patent/GB823152A/en not_active Expired
- 1955-12-12 FR FR69683D patent/FR69683E/en not_active Expired
- 1955-12-13 US US552699A patent/US2837472A/en not_active Expired - Lifetime
-
1956
- 1956-01-04 US US557422A patent/US2907786A/en not_active Expired - Lifetime
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
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US2389181A (en) * | 1941-05-15 | 1945-11-20 | Udylite Corp | Electrodeposition of metals |
US2424887A (en) * | 1941-10-11 | 1947-07-29 | Houdaille Hershey Corp | Method and electrolyte for the electrodeposition of metals |
US2648627A (en) * | 1950-05-24 | 1953-08-11 | Wagner Brothers Inc | Bright nickel plating composition and process |
US2663684A (en) * | 1952-06-02 | 1953-12-22 | Houdaille Hershey Corp | Method of and composition for plating copper |
Cited By (30)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2986498A (en) * | 1954-03-13 | 1961-05-30 | Dehydag Gmbh | Process for the production of metal electrodeposits |
US3030283A (en) * | 1954-03-13 | 1962-04-17 | Dehydag Gmbh | Process for the production of metal electrodeposits |
US3023150A (en) * | 1954-03-22 | 1962-02-27 | Dehydag Gmbh | Bath for the production of metal electroplates |
US3000800A (en) * | 1957-04-16 | 1961-09-19 | Dehydag Gmbh | Copper-electroplating baths |
US3051634A (en) * | 1957-11-30 | 1962-08-28 | Dehydag Gmbh | Baths for the production of copper electroplates |
US3075899A (en) * | 1958-04-26 | 1963-01-29 | Dehydag Gmbh | Baths for the production of metal electroplates |
US3084163A (en) * | 1958-04-29 | 1963-04-02 | Dehydag Gmbh | Heterocyclic thioalkane sulfonic acids and methods for their production |
US3017333A (en) * | 1959-04-06 | 1962-01-16 | Mcgean Chem Co Inc | Self-leveling bright nickel plating bath and process |
US3188312A (en) * | 1960-02-27 | 1965-06-08 | Dehydag Gmbh | New process for the preparation of thiourea derivatives |
US3165456A (en) * | 1960-11-21 | 1965-01-12 | Minnesota Mining & Mfg | Developer |
US3276979A (en) * | 1961-08-31 | 1966-10-04 | Dehydag Gmbh | Baths and processes for the production of metal electroplates |
US3215611A (en) * | 1962-07-20 | 1965-11-02 | Dehydag Gmbh | Process for deposition of fine grained deposits in the refining and reduction electrolysis of metals |
US3502551A (en) * | 1966-08-20 | 1970-03-24 | Schering Ag | Acid electrolyte for the deposition of bright,levelling copper coatings |
US3956084A (en) * | 1972-12-14 | 1976-05-11 | M & T Chemicals Inc. | Electrodeposition of copper |
US3940320A (en) * | 1972-12-14 | 1976-02-24 | M & T Chemicals Inc. | Electrodeposition of copper |
US3956120A (en) * | 1972-12-14 | 1976-05-11 | M & T Chemicals Inc. | Electrodeposition of copper |
US3956078A (en) * | 1972-12-14 | 1976-05-11 | M & T Chemicals Inc. | Electrodeposition of copper |
US3956079A (en) * | 1972-12-14 | 1976-05-11 | M & T Chemicals Inc. | Electrodeposition of copper |
US3966565A (en) * | 1972-12-14 | 1976-06-29 | M & T Chemicals Inc. | Electrodeposition of copper |
US4014760A (en) * | 1974-11-21 | 1977-03-29 | M & T Chemicals Inc. | Electrodeposition of copper |
US4036710A (en) * | 1974-11-21 | 1977-07-19 | M & T Chemicals Inc. | Electrodeposition of copper |
US4036711A (en) * | 1975-12-18 | 1977-07-19 | M & T Chemicals Inc. | Electrodeposition of copper |
US4134803A (en) * | 1977-12-21 | 1979-01-16 | R. O. Hull & Company, Inc. | Nitrogen and sulfur compositions and acid copper plating baths |
US4376685A (en) * | 1981-06-24 | 1983-03-15 | M&T Chemicals Inc. | Acid copper electroplating baths containing brightening and leveling additives |
US4549942A (en) * | 1981-07-06 | 1985-10-29 | Omi International Corporation | Process for electrodepositing composite nickel layers |
US4502927A (en) * | 1981-11-18 | 1985-03-05 | International Business Machines Corporation | Electrodeposition of chromium and its alloys |
US5656148A (en) * | 1995-03-02 | 1997-08-12 | Atotech Usa, Inc. | High current density zinc chloride electrogalvanizing process and composition |
US9017463B2 (en) * | 2012-05-22 | 2015-04-28 | Byd Company Limited | Copper plating solution and method for preparing the same |
DE202015003382U1 (en) | 2014-05-09 | 2015-06-16 | Dr. Hesse GmbH & Cie. KG | Electrolytic deposition of copper from water-based electrolytes |
DE102014208733A1 (en) | 2014-05-09 | 2015-11-12 | Dr. Hesse Gmbh & Cie Kg | Process for the electrolytic deposition of copper from water-based electrolytes |
Also Published As
Publication number | Publication date |
---|---|
FR69683E (en) | 1958-11-18 |
US2837472A (en) | 1958-06-03 |
NL298381A (en) | |
NL109804C (en) | |
FR68292E (en) | 1958-04-28 |
DE923407C (en) | 1955-02-10 |
GB823152A (en) | 1959-11-04 |
BE543413A (en) | |
CH327298A (en) | 1958-01-31 |
CH344715A (en) | 1960-02-29 |
NL110737C (en) | |
NL202744A (en) | |
US2907786A (en) | 1959-10-06 |
DE1207177B (en) | 1965-12-16 |
FR1097123A (en) | 1955-06-29 |
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