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DE882505C - Bath and process for the electrolytic deposition of tin and tin alloys - Google Patents

Bath and process for the electrolytic deposition of tin and tin alloys

Info

Publication number
DE882505C
DE882505C DE1939P0002358 DEP0002358D DE882505C DE 882505 C DE882505 C DE 882505C DE 1939P0002358 DE1939P0002358 DE 1939P0002358 DE P0002358 D DEP0002358 D DE P0002358D DE 882505 C DE882505 C DE 882505C
Authority
DE
Germany
Prior art keywords
tin
baths
bath
stannite
polyvinyl
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
Application number
DE1939P0002358
Other languages
German (de)
Inventor
Harold J Barett
C J Wernlund
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
EIDP Inc
Original Assignee
EI Du Pont de Nemours and Co
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by EI Du Pont de Nemours and Co filed Critical EI Du Pont de Nemours and Co
Application granted granted Critical
Publication of DE882505C publication Critical patent/DE882505C/en
Expired legal-status Critical Current

Links

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
    • C25D3/22—Electroplating: Baths therefor from solutions of zinc
    • C25D3/24—Electroplating: Baths therefor from solutions of zinc from cyanide baths
    • 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
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/26—Electroplating: Baths therefor from solutions of cadmium
    • C25D3/28—Electroplating: Baths therefor from solutions of cadmium from cyanide baths
    • 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
    • C25D3/30—Electroplating: Baths therefor from solutions of tin
    • C25D3/32—Electroplating: Baths therefor from solutions of tin characterised by the organic bath constituents used
    • 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
    • C25D3/60—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of tin

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • Electroplating And Plating Baths Therefor (AREA)

Description

Durch das Patent 687136 sind Bäder für die elektrolytische Abscheidung von Zinn und Legierungen des Zinns auf anderen Metallen geschützt, welche dadurch gekennzeichnet sind, daß sie außer einer Zinnverbindung Polyvinylalkohol oder ein anderes hydrophiles Derivat desselben in geringen Mengen enthalten.By the patent 687136 are baths for the electrolytic Deposition of tin and alloys of tin on other metals protected, which thereby are characterized in that, in addition to a tin compound, they are polyvinyl alcohol or another hydrophilic Derivative of the same contained in small amounts.

Bei der Elektroplattierung von Metallen mit Zinn hat man bisher fast ausschließlich Bäder verwendet, welche das Zinn in vierwertiger Form enthalten. Die aus solchen Stannatbädern erzielten Niederschläge zeigen eine sehr feinkörnige Struktur. Durch Anwesenheit von Zusatzmitteln, wie Maltose, Malzzucker, Stärke od. dgl., kann dabei eine weitere Kornverfeinerung erzielt werden. Die Streufähigkeit dieser Bäder ist ausgezeichnet, und die Stromausbeuten betragen etwa 90%, bezogen auf den Niederschlag von Sn++++-Ionen.In the electroplating of metals with tin, baths which contain the tin in tetravalent form have hitherto been used almost exclusively. The precipitates obtained from such stannate baths show a very fine-grain structure. Through the presence of additives such as maltose, malt sugar, starch or the like, further grain refinement can be achieved. The throwing power of these baths is excellent, and the current yields are about 90%, based on the precipitation of Sn + +++ - ions.

Beim Arbeiten mit Stannatbädern besteht aber der Nachteil, daß gewöhnlich ein geringer Anteil des Stannats zu Stannit reduziert wird. Schon das Vorhandensein nur geringer Mengen von zweiwertigemWhen working with stannate baths, however, there is the disadvantage that usually a small proportion of the Stannate is reduced to stannite. Even the presence of only small amounts of bivalent

Zinn kann bereits Veranlassung zur Bildung eines porösen oder schwammigen Niederschlags geben. Um dieser Schwierigkeit Herr zu werden, hat man dem Bad von Zeit zu Zeit Wasserstoffsuperoxyd oder andere oxydierende Mittel zugesetzt, um gebildetes Stannit zu oxydieren. Die verhältnismäßig geringe Geschwindigkeit der Zinnabscheidung und die mit dem Zusatz von Oxydationsmitteln, wie Wasserstoffsuperoxyd, entstehenden zusätzlichen Kosten sind ίο bei der Herstellung dünner Zinnüberzüge nicht von erheblicher Bedeutung; sie fallen aber erheblich ins Gewicht, wenn es sich darum handelt, dicke Zinn-• niederschlage zu erzeugen.Tin can already give rise to the formation of a porous or spongy precipitate. Around To cope with this difficulty, one has hydrogen peroxide or hydrogen peroxide in the bath from time to time other oxidizing agents added in order to oxidize formed stannite. The relatively small one Speed of tin deposition and that with the addition of oxidizing agents such as hydrogen peroxide, The additional costs incurred are ίο not from the production of thin tin coatings considerable importance; but they are of considerable importance when it comes to thick tin- • to generate precipitation.

Es wurde nun gefunden, daß die elektrolytische 1-5 Abscheidung von Zinn gemäß Hauptpatent auch dann unter Erzielung ausgezeichneter Ergebnisse gelingt, wenn die Zinnverbindung ganz oder zum Teil in zweiwertiger Form, vorzugsweise als Alkalistannit vorliegt. Man erhält bei Verwendung solcher Bäder unporöse Zinniederschläge von ausgezeichneter Weiße und hübschem mattem Lüster. Es können hierbei bei Einhaltung bestimmter Arbeitsbedingungen innerhalb bestimmter Zeit Niederschläge erzielt werden, welche doppelt so dick sind wie bei Verwendung eines Stannatbades. Zusätze von Wasserstoffsuperoxyd oder anderen Oxydationsmitteln sind bei dieser Arbeitsweise unnötig.It has now been found that the electrolytic 1-5 deposition of tin according to the main patent also then succeed with achieving excellent results if the tin compound wholly or for Part is present in divalent form, preferably as alkali stannite. One obtains when using such Baths of non-porous tin deposits of excellent whiteness and a pretty matt luster. It can in this case, if certain working conditions are observed, precipitation is achieved within a certain period of time which are twice as thick as when using a stannate bath. Additions of hydrogen peroxide or other oxidizing agents are unnecessary in this procedure.

Die Erfindung eignet sich für die Erzeugung von Zinniederschlägen aus Bädern, welche Stannit und Stannat in irgendwelchen Mengenverhältnissen enthalten. Hierbei kann man die Eigenschaft der zu erzeugenden Niederschläge durch das Verhältnis von Stannat zu Stannit in dem Bad in gewissem Ausmaß beeinflussen. Die Erfindung ist auch nicht beschränkt auf Bäder von besonderer Zusammensetzung; sie ist vielmehr anwendbar auf alle für Zinnplattierungen geeigneten Bäder, welche zweiwertige Zinnionen in kleineren oder größeren Mengen enthalten. Die Erfindung hat sich insbesondere bewährt bei Verwendung von Bädern, welche einen Gehalt an alkalischen Stoffen, z. B. Alkalihydroxyd, aufweisen. So können z. B-. Bäder, welche vorwiegend aus Alkalimetallstannit bestehen, z. B. 13 bis 104 g/l Natriumstannit enthalten und außerdem etwa 10 bis 65 g 1 Natriumhydroxyd und etwa 0,1 bis 1 g/l Polyvinylalkohol aufweisen, verwendet werden. Es können aber auch äquivalente Mengen anderer hydrophiler Polyvinylverbindungen im Bad vorhanden sein.The invention is suitable for the production of tin precipitates from baths, which stannite and Contains stannate in any proportions. Here one can use the property of the to generating precipitates due to the ratio of stannate to stannite in the bath to some extent influence. The invention is also not restricted to baths of particular composition; she is rather applicable to all baths suitable for tin plating which contain divalent tin ions in contain smaller or larger amounts. The invention has proven particularly useful when used of baths which contain alkaline substances, e.g. B. alkali hydroxide. So can z. B-. Baths consisting primarily of alkali metal stannite, e.g. B. 13 to 104 g / l sodium stannite and also about 10 to 65 g 1 sodium hydroxide and about 0.1 to 1 g / L polyvinyl alcohol can be used. But it can also equivalent amounts of other hydrophilic polyvinyl compounds should be present in the bath.

Claims (3)

PATENTANSPRÜCHE:PATENT CLAIMS: Die Erfindung ist auch anwendbar auf Bäder, welche außer Zinn noch andere Metalle enthalten, wie solche z. B. zur Niederschlagung von Zinnlegierungen Verwendung finden. Man kann z. B. mit Vorteil Stannitbäder verwenden, die untergeordnete Mengen von anderen Metallen aufweisen und ebenso Stannit-Stannatbäder, welche andere Metalle enthalten. The invention is also applicable to baths which contain other metals besides tin, such as B. used to suppress tin alloys. You can z. B. with It is advantageous to use stannite baths that contain minor amounts of other metals and likewise Stannite-stannate baths which contain other metals. Natriumstannitbäder können z. B. durch Zusatz von Zinnchloridlösung zu Ätznatronlösung bei 20 ° nicht übersteigenden Temperaturen und unter gründlichem Rühren gewonnen werden, wobei etwa entstehende geringfügige Niederschläge durch Abfiltrieren beseitigt werden können.Sodium stannite baths can e.g. B. by adding tin chloride solution to caustic soda solution at 20 ° Temperatures not exceeding and with thorough stirring can be obtained, with any resulting minor precipitates can be removed by filtering off. Die Menge der dem Bad einzuverleibenden Polyvinylverbindungen richtet sich nach der Zusammensetzung des Bades und den gewünschten Eigenschaften, z. B. dem Weißgrad des Zinniederschlags. Im allgemeinen bringen bereits sehr geringe Zusatzmengen die gewünschten Wirkungen hervor. Zusätze von Polyvinylverbindungen, welche mehr als 1 g 1 betragen, bewirken im allgemeinen keine Wirkungs-Steigerungen mehr. Man kann aber auch größere Zusätze verwenden. Häufig ist die obere Grenze des Zusatzes durch die Löslichkeit der Poly vinylverbindung gegeben. Zusätze, die zur Ausfällung führen, sind im allgemeinen zu vermeiden.The amount of polyvinyl compounds to be incorporated into the bath depends on the composition of the bath and the desired properties, e.g. B. the whiteness of the tin precipitate. In general, even very small amounts add the desired effects. Additions of polyvinyl compounds, which amount to more than 1 g 1, generally no longer cause any increases in effectiveness. But you can also do bigger ones Use additives. Often the upper limit of the addition is due to the solubility of the polyvinyl compound given. Additives that lead to precipitation should generally be avoided. ι. Bad für die elektrolytische Abscheidung von Zinn, welches neben einer Zinnverbindung geringe Mengen von Polyvinylalkohol oder von anderen wasserlöslichen Polyvinylverbindungen enthält, nach Patent 687136, dadurch gekennzeichnet, daß die Zinnverbindung ganz oder teüwdse in zweiwertiger Form, vorzugsweise als Alkalistannit vorliegt.ι. Bath for the electrolytic deposition of tin, which is low in addition to a tin compound Contains quantities of polyvinyl alcohol or other water-soluble polyvinyl compounds, according to patent 687136, characterized in, that the tin compound is wholly or partially in divalent form, preferably present as alkali stannite. 2. Bad nach Anspruch 1, gekennzeichnet durch einen Gehalt an alkalischen Stoffen, z, B. Alkalihydroxyd. 2. Bath according to claim 1, characterized by a content of alkaline substances, e.g. alkali hydroxide. 3. Verfahren zur Herstellung von Bädern nach go Ansprüchen 1 und 2, dadurch gekennzeichnet, daß SnCl2-H2O, Alkalihydroxyd und eine hydrophile Polyviny!verbindung in Wasser gelöst werden.3. Process for the production of baths according to claims 1 and 2, characterized in that SnCl 2 -H 2 O, alkali hydroxide and a hydrophilic polyvinyl compound are dissolved in water. Angezogene Druckschriften: Französische Patentschrift Nr. 824277.References: French Patent No. 824277. © 5258 6.53© 5258 6.53
DE1939P0002358 1936-07-13 1939-11-21 Bath and process for the electrolytic deposition of tin and tin alloys Expired DE882505C (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US90382A US2171842A (en) 1936-07-13 1936-07-13 Electroplating
US242042A US2211251A (en) 1936-07-13 1938-11-23 Tin plating

Publications (1)

Publication Number Publication Date
DE882505C true DE882505C (en) 1953-07-09

Family

ID=21797082

Family Applications (2)

Application Number Title Priority Date Filing Date
DE1937P0075487 Expired DE687136C (en) 1936-07-13 1937-07-06 Baeder and process for the electrodeposition of metals
DE1939P0002358 Expired DE882505C (en) 1936-07-13 1939-11-21 Bath and process for the electrolytic deposition of tin and tin alloys

Family Applications Before (1)

Application Number Title Priority Date Filing Date
DE1937P0075487 Expired DE687136C (en) 1936-07-13 1937-07-06 Baeder and process for the electrodeposition of metals

Country Status (6)

Country Link
US (2) US2171842A (en)
BE (1) BE422634A (en)
CH (1) CH201630A (en)
DE (2) DE687136C (en)
FR (2) FR824277A (en)
NL (1) NL48191C (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0570033A1 (en) * 1992-04-15 1993-11-18 Recherche et Développement GROUPE COCKERILL SAMBRE Process for electroplating tin or tin alloy on a metal workpiece

Families Citing this family (28)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2171842A (en) * 1936-07-13 1939-09-05 Du Pont Electroplating
US2288318A (en) * 1937-12-29 1942-06-30 Du Pont Electroplating process
US2545566A (en) * 1943-03-11 1951-03-20 Mallory & Co Inc P R Electrodeposition of metals and alloys
US2461507A (en) * 1943-07-07 1949-02-15 Du Pont Electrodepositing composition and process
BE495952A (en) * 1943-07-07
US2451426A (en) * 1943-11-25 1948-10-12 Du Pont Bright zinc plating
US2523191A (en) * 1945-07-07 1950-09-19 Udylite Corp Electrodeposition of nickel from an acid bath
FR955898A (en) * 1945-07-07 1950-01-20
US2524619A (en) * 1945-07-09 1950-10-03 Udylite Corp Electrodeposition of nickel
US2466677A (en) * 1945-08-27 1949-04-12 Udylite Corp Electrodeposition of nickel from an acid bath
US2740754A (en) * 1952-11-07 1956-04-03 Allied Res Products Inc Zinc plating brightener
DE1061526B (en) * 1952-11-21 1959-07-16 Mond Nickel Co Ltd Process and bath for the electrolytic deposition of nickel
US2769775A (en) * 1953-12-01 1956-11-06 Canadian Copper Refiners Ltd Electrolyte for copper refining, including polyvinyl alcohol
NL202898A (en) * 1954-12-16
US2729557A (en) * 1955-02-02 1956-01-03 American Cyanamid Co Method of preventing deposition of alkaline earth metal salts in cyanidation of precious metal ores
US2849353A (en) * 1955-02-08 1958-08-26 Hanson Van Winkle Munning Co Bright nickel plating
DE1112638B (en) * 1955-09-15 1961-08-10 Dow Chemical Co Bath and process for the electrolytic extraction of metals, especially zinc, from aqueous solutions
US2860089A (en) * 1956-08-09 1958-11-11 R O Hull & Company Inc Method of electro depositing zinc
US2893933A (en) * 1956-10-01 1959-07-07 Incar Inc Nickel plating compositions and method
US2928800A (en) * 1957-03-12 1960-03-15 Du Pont Zinc plating
US2966448A (en) * 1958-06-04 1960-12-27 Gen Electric Methods of electroplating aluminum and alloys thereof
US3296105A (en) * 1964-04-03 1967-01-03 Du Pont Zinc cyanide electroplating bath and process
US3411996A (en) * 1965-12-02 1968-11-19 Du Pont Process for brightening zinc and cadmium electroplate using an inner salt of a quaternized pyridine carboxylic acid and compositions containing the same
US3505184A (en) * 1966-02-07 1970-04-07 Enthone Acid zinc electrodepositing
US3386898A (en) * 1967-07-17 1968-06-04 Du Pont Alkaline, cyanide zinc electroplating bath process, and additive therefor
US10793956B2 (en) * 2015-08-29 2020-10-06 Mitsubishi Materials Corporation Additive for high-purity copper electrolytic refining and method of producing high-purity copper
JP6733313B2 (en) * 2015-08-29 2020-07-29 三菱マテリアル株式会社 High-purity copper electrolytic refining additive and high-purity copper manufacturing method
TWI705159B (en) * 2015-09-30 2020-09-21 日商三菱綜合材料股份有限公司 Additive for high-purity copper electrolytic refining, method of producing high-purity copper, and high-purity electrolytic copper

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR824277A (en) * 1936-07-13 1938-02-04 Du Pont Baths and process for the electrolytic precipitation of metals

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR824277A (en) * 1936-07-13 1938-02-04 Du Pont Baths and process for the electrolytic precipitation of metals

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0570033A1 (en) * 1992-04-15 1993-11-18 Recherche et Développement GROUPE COCKERILL SAMBRE Process for electroplating tin or tin alloy on a metal workpiece
BE1005730A4 (en) * 1992-04-15 1993-12-28 Rech S Et Dev Du Groupe Cocker Tin electroplating process and / or alloys tin on a metal support.

Also Published As

Publication number Publication date
US2171842A (en) 1939-09-05
BE422634A (en) 1937-08-31
DE687136C (en) 1940-01-23
CH201630A (en) 1938-12-15
NL48191C (en) 1940-04-15
FR824277A (en) 1938-02-04
FR863403A (en) 1941-04-01
US2211251A (en) 1940-08-13

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