EP0346740A1 - Alcaline aqueous bath for the galvanic deposition of zinc-iron alloys - Google Patents

Alcaline aqueous bath for the galvanic deposition of zinc-iron alloys Download PDF

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Publication number
EP0346740A1
EP0346740A1 EP89110247A EP89110247A EP0346740A1 EP 0346740 A1 EP0346740 A1 EP 0346740A1 EP 89110247 A EP89110247 A EP 89110247A EP 89110247 A EP89110247 A EP 89110247A EP 0346740 A1 EP0346740 A1 EP 0346740A1
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Prior art keywords
iron
zinc
liter
aqueous bath
compound
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EP89110247A
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German (de)
French (fr)
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EP0346740B1 (en
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Günter Voss
Martin Dr. Kurpjoweit
Wolfgang Richter
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Atotech Deutschland GmbH and Co KG
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Schering AG
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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
    • C25D3/56—Electroplating: Baths therefor from solutions of alloys
    • C25D3/565—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of zinc

Definitions

  • the invention relates to an alkaline aqueous bath for the galvanic deposition of zinc-iron alloys containing as essential components a zincate and an iron compound.
  • Electrolytes for the deposition of zinc alloys have long been known. Their technical usability is limited, not least because of their alloy composition, which is very dependent on the current density, above all to coil galvanization.
  • iron salts are used in this bath, which lead to an accumulation of unwanted foreign anions.
  • the object of the invention is to create a bath of the type described above, which enables deposition of highly corrosion-resistant zinc-iron alloys independently of the current density, while avoiding disruptive foreign anions.
  • the bath according to the invention enables the deposition of almost constant zinc-iron alloy coatings with exceptionally high corrosion resistance in an outstanding manner.
  • the sodium zincate can be used with particular advantage, but if desired the other alkali zincates can also be used.
  • mixtures of alkali hydroxides with alkali carbonates can also be obtained in the bath.
  • bonds with iron can be those with polyhydroxy aldehydes, such as monosaccharides, disaccharides, trisaccharides and starch degradation products.
  • the iron saccharate to be used according to the invention is known per se and can be prepared by processes known per se, for example by reacting iron (II) chloride, soda, sucrose and sodium hydroxide solution.
  • the bath according to the invention is used in a manner known per se under the following process conditions: Temperature: 25 ° C Current density: 1 - 4 A / dm2 pH:> 13
  • Iron-steel are particularly suitable as substrates for the zinc-iron alloy coatings to be deposited.
  • the basic composition of the bath according to the invention is as follows: 120 g / liter alkali hydroxide 10 g / liter zinc oxide 30 g / liter alkali carbonate
  • the alloy coatings deposited from the bath according to the invention can be provided with chromate cover layers in a manner known per se by means of suitable chrome sorting solutions.
  • the following table shows the alloy composition (proportion Fe) at different current densities, depending on the zinc and iron concentration in the bath.
  • table % -Fe in the coating Bath (g / liter) Current densities (A / dm2) Zn Fe 1 2nd 3rd 4th 7.6 0.05 0.24 0.24 0.24 0.26 8.0 0.2 0.7 0.7 0.7 0.74 % Fe in the coating 8.9 0.5 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1
  • the baths used had the following composition: 120 g / liter NaOH 30 g / liter Na2CO3 10 g / liter Sodium zincate 8 g / liter Additive
  • Example II 8 ⁇ m thick Zn-Fe coatings were deposited from a bath of the composition given in Example I in the table. These contained 0.5% Fe.

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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)
  • Electroplating And Plating Baths Therefor (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)
  • Cosmetics (AREA)

Abstract

The invention relates to an alkaline aqueous bath for the electrodeposition of zinc-iron alloys containing a zincate as essential constituent and an iron compound, characterised in that the iron compound is present in the form of a compound of iron with a polyhydroxyaldehyde.

Description

Die Erfindung betrifft ein alkalisches wässriges Bad zur galvanischen Abschei­dung von Zink-Eisen-Legierungen enthaltend als wesentliche Bestandteile ein Zinkat und eine Eisenverbindung.The invention relates to an alkaline aqueous bath for the galvanic deposition of zinc-iron alloys containing as essential components a zincate and an iron compound.

Elektrolyte zur Abscheidung von Zinklegierungen sind seit längerem bekannt. Ihre technische Verwendbarkeit beschränkt sich, nicht zuletzt wegen ihrer sehr stromdichteabhängigen Legierungszusammensetzung, vor allem auf die Bandgalvani­sierung.Electrolytes for the deposition of zinc alloys have long been known. Their technical usability is limited, not least because of their alloy composition, which is very dependent on the current density, above all to coil galvanization.

In letzter Zeit wurde versucht saure Elektrolyte auf dem Markt einzuführen, aus denen korrosionsbeständige Legierungen von Zink mit Nickel, Kobalt, Eisen oder Chrom abgeschieden werden. Trotz relativ guter bis sehr guter Korrosionsdaten blieb das Anwendungsspektrum solcher Elektrolyte auffallend eng begrenzt. Die Gründe hierfür sind insbesondere die Instabilität der Elektrolyte, infolge der hohen Salzkonzentrationen und die problematische, weil stromdichteabhängige Legierungszusammensetzung. Das gleiche gilt auch für bisher bekannte Zinkei­senbäder, die den Nachteil haben, daß Zink-Eisen als Endoberfläche nicht ein­setzbar wäre, da durch den Eisenanteil sich sehr schnell sowohl Rotrost als auch Weißrost bildet.Recently, attempts have been made to introduce acidic electrolytes from which corrosion-resistant alloys of zinc with nickel, cobalt, iron or chromium are deposited. Despite relatively good to very good corrosion data, the range of applications for such electrolytes remained remarkably limited. The reasons for this are in particular the instability of the electrolytes due to the high salt concentrations and the problematic alloy composition, which is dependent on the current density. The same also applies to previously known zinc iron baths, which have the disadvantage that zinc iron could not be used as the end surface, since both red rust and white rust form very quickly due to the iron content.

Ein Grund für dieses unzureichende Korrosionsverhalten der bisherigen Zink- Ei­sen-Überzüge mag darin liegen, daß sie aus Bädern abgeschieden wurden, die unterschiedliche, aber insgesamt ungünstige Chelatbildner enthielten. So werden i. d. DE-DS 3 506 709 unter anderem folgende Chelatbilder genannt:
Hydroxycarbonsäuren, Amninoalkohol, Polyamin, Aminocarbonsäure und andereOne reason for this inadequate corrosion behavior of the previous zinc-iron coatings may be that they were deposited from baths which contained different, but generally unfavorable chelating agents. For example, the following chelated images are mentioned in DE-DS 3 506 709:
Hydroxycarboxylic acids, amino alcohol, polyamine, aminocarboxylic acid and others

Außerdem werden in diesem Bad Eisensalze verwendet, die zu einer Anreicherung unerwünschter Fremdanionen führen.In addition, iron salts are used in this bath, which lead to an accumulation of unwanted foreign anions.

Aufgabe der Erfindung ist die Schaffung eines Bades der oben bezeichneten Gat­tung, welches eine von der Stromdichte unabhängige Abscheidung von Hochkorro­sionsbeständigen Zink-Eisen-Legierungen unter Vermeidung von störenden Fremd­anionen ermöglicht.The object of the invention is to create a bath of the type described above, which enables deposition of highly corrosion-resistant zinc-iron alloys independently of the current density, while avoiding disruptive foreign anions.

Diese Aufgabe wird erfindungsgemäß durch ein alkalisches wässriges Bad gemäß dem kennzeichnenden Teil des Patentanspruchs gelöst.This object is achieved by an alkaline aqueous bath according to the characterizing part of the patent claim.

Weitere Ausgestaltungen der Erfindung sind den Kennzeichnungsteilen der Unter­ansprüche zu entnehmen.Further refinements of the invention can be found in the characterizing parts of the subclaims.

Das erfindungsgemäße Bad ermöglicht in herausragender Weise die Abscheidung nahezu konstant zusammengesetzter Zink-Eisen-Legierungsüberzüge mit außerge­wöhnlich hoher Korrosionsbeständigkeit.The bath according to the invention enables the deposition of almost constant zinc-iron alloy coatings with exceptionally high corrosion resistance in an outstanding manner.

Die Stromdichte-Unabhängigkeit ist hierbei besonders überraschend und von großer technischer Bedeutung für die Verfahrensdurchführung.The current density independence is particularly surprising and of great technical importance for the implementation of the process.

Als weitere Vorteile sind insbesondere die Abwesenheit von störenden Fremdionen sowie weiterer Komplex- bzw. Chelatbildner zu nennen.The absence of interfering foreign ions and other complexing agents or chelating agents are further advantages.

Von den Zinkaten läßt sich mit besonderem Vorteil das Natriumzinkat verwenden, jedoch können gewünschtenfalls auch die anderen Alkalizinkate zur Anwendung kommen.Of the zincates, the sodium zincate can be used with particular advantage, but if desired the other alkali zincates can also be used.

Außer Alkalihydroxid können auch Mischungen von Alkalihydroxiden mit Alkali­carbonaten im Bad erhalten sein.In addition to alkali hydroxide, mixtures of alkali hydroxides with alkali carbonates can also be obtained in the bath.

Als Bindungen des Eisens können erfahrensgemäß solche mit Polyhydroxidalde­hyden, wie Monosacchariden, Disacchariden, Trisacchariden sowie Stärkeabbau­produkte verwendet werden.According to the process, bonds with iron can be those with polyhydroxy aldehydes, such as monosaccharides, disaccharides, trisaccharides and starch degradation products.

Das erfindungsgemäß zu verwendende Eisensaccharat ist an sich bekannt und kann durch an sich bekannte Verfahren hergestellt werden, zum Beispiel durch Umset­zung von Eisen-II-Chlorid, Soda, Saccharose und Natronlauge.The iron saccharate to be used according to the invention is known per se and can be prepared by processes known per se, for example by reacting iron (II) chloride, soda, sucrose and sodium hydroxide solution.

Es ist besonders vorteilhaft, die Zucker bzw. Saccharide im Bad im Überschuß einzusetzen.It is particularly advantageous to use the sugar or saccharides in excess in the bath.

Die Anwedung des erfindungsgemäßen Bades erfolgt in an sich bekannter Weise unter den folgenden Verfahrensbedingungen:
Temperatur : 25 °C
Stromdichte : 1 - 4 A/dm²
pH-Wert : > 13The bath according to the invention is used in a manner known per se under the following process conditions:
Temperature: 25 ° C
Current density: 1 - 4 A / dm²
pH:> 13

Als Substrate für die abzuscheidenden Zink-Eisen-Legierungsüberzüge sind insbesondere Eisen-Stahl geeignet.Iron-steel are particularly suitable as substrates for the zinc-iron alloy coatings to be deposited.

Die Grundzusammensetzung des erfindungsgemäßen Bades ist wie folgt:
120 g/Liter Alkalihydroxid
10 g/Liter Zinkoxid
30 g/Liter AlkalicarbonatThe basic composition of the bath according to the invention is as follows:
120 g / liter alkali hydroxide
10 g / liter zinc oxide
30 g / liter alkali carbonate

Die aus dem erfindungsgemäßen Bad abgeschiedenen Legierungsüberzüge können in an sich bekannter Weise mittels geeigneter Chromartierlösungen mit Chromat­deckschichten versehen werden.The alloy coatings deposited from the bath according to the invention can be provided with chromate cover layers in a manner known per se by means of suitable chrome sorting solutions.

Die folgenden Beispiele dienen zur Erläuterung der Erfindung.The following examples serve to illustrate the invention.

Beispiel 1example 1

Die folgende Tabelle zeigt die Legierungszusammensetzung (Anteil Fe) bei unterschiedlichen Stromdichten, in Abhängigkeit von der Zink- und Eisenkon­zentration im Bad. Tabelle %-Fe im Überzug Bad (g/Liter) Stromdichten (A/dm²) Zn Fe 1 2 3 4 7,6 0,05 0,24 0,24 0,24 0,26 8,0 0,2 0,7 0,7 0,7 0,74 % Fe im Überzug 8,9 0,5 1,1 1,1 1,1 1,1 The following table shows the alloy composition (proportion Fe) at different current densities, depending on the zinc and iron concentration in the bath. table % -Fe in the coating Bath (g / liter) Current densities (A / dm²) Zn Fe 1 2nd 3rd 4th 7.6 0.05 0.24 0.24 0.24 0.26 8.0 0.2 0.7 0.7 0.7 0.74 % Fe in the coating 8.9 0.5 1.1 1.1 1.1 1.1

Die verwendeten Bäder hatten neben den in der Tabelle aufgeführten Bestandtei­len folgende Zusammensetzung: 120 g/Liter NaOH 30 g/Liter Na₂CO₃ 10 g/Liter Natriumzinkat 8 g/Liter Glanzzusatz In addition to the components listed in the table, the baths used had the following composition: 120 g / liter NaOH 30 g / liter Na₂CO₃ 10 g / liter Sodium zincate 8 g / liter Additive

Die Befunde zeigten den ungewöhnlichen Standard der erfindungsgemäßen Bäder, nämlich relativ niedrige Eisenkonzentration im Elektrolyten und den dennoch ungewöhnlich gleichmäßigen Eisengehalt im Überzug bei unterschiedlichen Strom­dichten.The results showed the unusual standard of the baths according to the invention, namely relatively low iron concentration in the electrolyte and the nevertheless unusually uniform iron content in the coating at different current densities.

Zum Vergleich seien die entsprechenden Daten eines kommerziellen alkalischen Zink-Eisen-Bades angeführt: Bad (g/Liter) Stromdichten (A/dm²) Zn Fe 1 2 3 4 19 0,33 0,26 0,47 0,61 --- % Fe im Überzug For comparison, the corresponding data of a commercial alkaline zinc-iron bath are given: Bath (g / liter) Current densities (A / dm²) Zn Fe 1 2nd 3rd 4th 19th 0.33 0.26 0.47 0.61 --- % Fe in the coating

Beispiel 2Example 2

Aus einem Bad der im Beispiel I in der Tabelle genannten Zusammensetzung wurden 8 µm dicke Zn-Fe-Überzüge abgeschieden. Diese enthielten 0,5 % Fe.8 µm thick Zn-Fe coatings were deposited from a bath of the composition given in Example I in the table. These contained 0.5% Fe.

Diese Überzüge wurden durch Tauchen in eine übliche Chromatierlösung passiviert:These coatings were passivated by immersing them in a conventional chromating solution:

Ein Teil der Proben wurde nach dem Chromatieren 1h bei 120 °C getempert (Son­derforderung der Autoindustrie), der Rest wurde bei 60 - 80 °C ca. 15 min. lang getrocknet.Some of the samples were tempered for 1 hour at 120 ° C after chromating (special requirement of the automotive industry), the rest were at 60 - 80 ° C for approx. 15 min. dried long.

Nach einer Lagerzeit von mind. 1 Woche wurden die Proben im Salzsprühtest gem. DIN 50021 55 getestet,

  • a) bis zu deutlich beginnender Oberflächenkorrosion (Weißrost);
  • b) bis zum Auftreten von Rotrost.
After a storage period of at least 1 week, the samples were subjected to the salt spray test in accordance with DIN 50021 55 tested,
  • a) up to clearly beginning surface corrosion (white rust);
  • b) until the appearance of red rust.

Parallel dazu werden unter optimalen Bedingungen hergestellte Proben aus alka­lischen Zinkelektrolyten zum Vergleich getestet. Die Ergebnisse sind in der folgenden Tabelle aufgeführt. Tabelle Korrosion im Salzsprühtest Überzugssysteme getempert 120 °C x 1h Stunden Salzsprühtest bis zu Weißrost Rotrost Zn-chromatiert nein 360/420 720 Zn-chromatiert ja 48/144 --- Zn-Fe-chromatiert nein >984/>984 >1000 Zn-Fe-chromatiert ja 504/528 --- In parallel, samples from alkaline zinc electrolytes produced under optimal conditions are tested for comparison. The results are shown in the table below. table Corrosion in the salt spray test Coating systems annealed 120 ° C x 1h Hours of salt spray test up to White rust Red rust Zn chromated No 360/420 720 Zn chromated Yes 48/144 --- Zn-Fe chromated No > 984 /> 984 > 1000 Zn-Fe chromated Yes 504/528 ---

Bei diesem Vergleich muß beachtet werden, daß die zum Vergleich eingesetzten chromatierten Zinkmuster bereits einen ungewöhnlich hohen Standard darstellen. Dennoch verhielten sich selbst die getemperten Zn-Fe-Chromatüberzüge bestän­diger.In this comparison it must be noted that the chromated zinc samples used for the comparison already represent an unusually high standard. Nevertheless, even the annealed Zn-Fe chromate coatings behaved more consistently.

Der mit den ungetemperten Proben erreichte Korrosionsschutz von ca. 1000 Stun­den Salzsprühtest für Zn-Fe-chromatiert beweist, daß mit dem erfindungsgerech­ten Bad Korrosionsschutzwerte erreicht werden, wie sie bisher nur mit einem speziellen Zink-Nickel-Verfahren aus sauren Bädern erzielbar waren, was jedoch die aus der Tabelle ersichtlichen Nachteile besitzt. Tabelle Unterschiede zwischen Zn-Ni (sauer) und Zn-Fe, (alkalisch auf Zucker-Basis) Merkmal Zn-Fe Zn-Ni a) Bad alkalisch sauer keine Abwasserprobleme hochammonialkalisch (>200g/l) deshalb Abwasserschädlich b) Anoden unlösliche Eisenanoden, Zink wird chemisch nach gelöst. getrennte Zn- u. Ni-Anoden doppelter Stromkreis erforderlich Innenanoden zur Qualitätsverbesserung möglich. Innenanoden problematisch, weil unlöslich kaum verwendbar im hochchloridhaltigen, sauren Elektrol. c) Legierung optimaler Korrosionsschutz schon mit 0,3 - 1,0% Fe mind. 10% Ni im Überzug für optimalen Korrosionsschutz gefordert. d) Sonstiges einfach zu wartender Elektrolyt mit nur geringer Konzentration an Leg-Metall (0,1-0,5g/l Fe) stromdichte-unabhängige Legierungszusammensetzung. komplizierter, fast gesättigtes Bad, mit hohem Gehalt an Leg-Metall (>10g/lNi). Leg-Zusammensetzung ist stromdichteempfindlich. The corrosion protection of approx. 1000 hours salt spray test for Zn-Fe chromated achieved with the untempered samples proves that the bath according to the invention achieves corrosion protection values that could previously only be achieved with a special zinc-nickel process from acid baths, which, however has the disadvantages shown in the table. table Differences between Zn-Ni (acidic) and Zn-Fe, (alkaline based on sugar) feature Zn-Fe Zn-Ni a) bathroom alkaline angry no sewage problems highly ammoniacal (> 200g / l) therefore harmful to wastewater b) anodes insoluble iron anodes, zinc is chemically dissolved. separate Zn- u. Ni anodes double circuit required Internal anodes possible for quality improvement. Internal anodes are problematic because they are insoluble and can hardly be used in high-chloride acid electrol. c) alloy optimal corrosion protection with 0.3 - 1.0% Fe at least 10% Ni in the coating required for optimal corrosion protection. d) Other easy to maintain electrolyte with only a low concentration of Leg metal (0.1-0.5g / l Fe) current density-independent alloy composition. complicated, almost saturated bath, with a high content of leg metal (> 10g / lNi) . Leg composition is sensitive to current density.

Claims (9)

1. Alkalisches wässriges Bad zur galvanischen Abscheidung von Zink-Eisen Legierungen enthaltend als wesentlicher Bestandteil ein Zinkat und eine Ei­senverbindung, dadurch gekennzeichnet, daß die Eisenverbindung in Form einer Verbindung des Eisens mit einem Polyhydroxidaldehyd enthalten ist.1. Alkaline aqueous bath for the galvanic deposition of zinc-iron alloys containing as an essential component a zincate and an iron compound, characterized in that the iron compound is contained in the form of a compound of iron with a polyhydroxy aldehyde. 2. Alkalisches wässriges Bad gemäß Anspruch 1, dadurch gekennzeichnet, daß die Eisenverbindung in Form einer Verbindung des Eisens mit einem Monosaccharid, Disaccharid oder Trisaccharid enthalten ist.2. Alkaline aqueous bath according to claim 1, characterized in that the iron compound is contained in the form of a compound of iron with a monosaccharide, disaccharide or trisaccharide. 3. Wässriges alkalisches Bad gemäß Anspruch 1, dadurch gekennzeichnet, daß die Eisenverbindung in Form von Eisensaccharat enthalten ist.3. Aqueous alkaline bath according to claim 1, characterized in that the iron compound is contained in the form of iron saccharate. 4. Alkalisches wässriges Bad gemäß Anspruch 1, dadurch gekennzeichnet, daß das Zinkat in Form von Natriumzinkat enthalten ist.4. Alkaline aqueous bath according to claim 1, characterized in that the zincate is contained in the form of sodium zincate. 5. Alkalisches wässriges Bad gemäß Anspruch 1, dadurch gekennzeichnet, daß Zink in Konzentrationen von 1 bis 40 g/Liter, vorzugsweise 4 bis 12 g/Liter, Alkalihydroxid in Konzentrationen von 60 bis 200 g/Liter, vorzugsweise 80 bis 140 g/Liter, Eisen in Konzentrationen von 0,001 bis 10 g/Liter, vorzugs­weise 0,05 bis 4 g/Liter und Saccharose (Zucker) in Konzentrationen von 1 bis 100 g/Liter, vorzugsweise 30 bis 60 g/Liter, enthalten ist.5. Alkaline aqueous bath according to claim 1, characterized in that zinc in concentrations of 1 to 40 g / liter, preferably 4 to 12 g / liter, alkali hydroxide in concentrations of 60 to 200 g / liter, preferably 80 to 140 g / liter , Iron in concentrations of 0.001 to 10 g / liter, preferably 0.05 to 4 g / liter and sucrose (sugar) in concentrations of 1 to 100 g / liter, preferably 30 to 60 g / liter. 6. Alkalisches wässriges Bad gemäß Anspruch 1, dadurch gekennzeichnet, daß es Glanzbildner und Glättungsmittel enthält.6. Alkaline aqueous bath according to claim 1, characterized in that it contains brighteners and smoothing agents. 7. Verfahren zur galvanischen Abscheidung von Zink-Eisen-Legierungen, dadurch gekennzeichnet, daß alkalische wässrige Bäder gemäß den Ansprüchen 1 bis 6 verwendet werden.7. A method for the galvanic deposition of zinc-iron alloys, characterized in that alkaline aqueous baths are used according to claims 1 to 6. 8. Verfahren gemäß Anspruch 7, dadurch gekennzeichnet, daß dieses bei Tempera­turen von 0 bis 60 °C und mit Stromdichten von 0,1 bis 10 A/dm² durchgeführt wird.8. The method according to claim 7, characterized in that this is carried out at temperatures from 0 to 60 ° C and with current densities of 0.1 to 10 A / dm². 9. Hochkorrosionsbeständige Zink-Eisen-Legierung mit einem Eisengehalt von 0,05 bis 20 %, hergestellt nach den Verfahren gemäß Ansprüchen 7 und 8.9. Highly corrosion-resistant zinc-iron alloy with an iron content of 0.05 to 20%, produced by the method according to claims 7 and 8.
EP89110247A 1988-06-09 1989-06-07 Alcaline aqueous bath for the galvanic deposition of zinc-iron alloys Expired - Lifetime EP0346740B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3819892A DE3819892A1 (en) 1988-06-09 1988-06-09 ALKALINE AQUEOUS BATH FOR GALVANIC DEPOSITION OF ZINC-IRON ALLOYS
DE3819892 1988-06-09

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EP0346740A1 true EP0346740A1 (en) 1989-12-20
EP0346740B1 EP0346740B1 (en) 1992-08-26

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EP (1) EP0346740B1 (en)
JP (1) JP2768498B2 (en)
AT (1) AT395023B (en)
CA (1) CA1337805C (en)
DE (2) DE3819892A1 (en)
ES (1) ES2035436T3 (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018115413A1 (en) * 2016-12-22 2018-06-28 Carl Freudenberg Kg Aqueous, alkaline electrolyte for depositing zinc-containing layers onto surfaces of metal piece goods
US11578419B2 (en) 2016-12-22 2023-02-14 Cari, Freudenberg Kg Aqueous, alkaline electrolyte for depositing zinc-containing layers onto surfaces of metal piece goods

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DE3819892A1 (en) 1989-12-14
ES2035436T3 (en) 1993-04-16
JPH02118094A (en) 1990-05-02
AT395023B (en) 1992-08-25
DE58902124D1 (en) 1992-10-01
US4923575A (en) 1990-05-08
ATA133589A (en) 1992-01-15
JP2768498B2 (en) 1998-06-25
EP0346740B1 (en) 1992-08-26
CA1337805C (en) 1995-12-26

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