EP0770710B2 - Process for electroplating nickel with satin finish - Google Patents

Process for electroplating nickel with satin finish Download PDF

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Publication number
EP0770710B2
EP0770710B2 EP96116639A EP96116639A EP0770710B2 EP 0770710 B2 EP0770710 B2 EP 0770710B2 EP 96116639 A EP96116639 A EP 96116639A EP 96116639 A EP96116639 A EP 96116639A EP 0770710 B2 EP0770710 B2 EP 0770710B2
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Prior art keywords
electrolyte
process according
adducts
nickel
operated
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French (fr)
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EP0770710A1 (en
EP0770710B1 (en
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Carmen Elligsen
Gerd Schöngen
Detlef Kowczyk
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LPW Chemie GmbH
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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

Definitions

  • the invention relates to a method for galvanic Separation of glare-free nickel deposits on a metallic surface.
  • Nikkel precipitation also includes nickel alloy precipitation.
  • metallic surface also metallized surfaces of non-metallic Objects.
  • a concentration of adducts in the range of 5 to 100 mg / l worked.
  • the deposition is operated that the electrolyte has a temperature in the range from 40 to 75 ° C.
  • the adducts are selected so that the adducts in the working electrolyte form a finely dispersed emulsion that turns out to be turbidity manifests.
  • the droplets of the emulsion are used as the reason considered that there is a glare-free surface forms. Glare-free is in need of improvement. The printout does not become glare for identification the.
  • the cloud point that is, the electrolyte temperature at which the surfactant fails, from the chemical structure and the concentration depends on the substances in the electrolyte. additionally the salt load of the electrolyte also goes into the Height of the cloud point.
  • the danger of agglomeration is too large Conglomerates of emulsion drops that are satin-like Disrupt separation, so big that special Measures are mandatory to complete the procedure to be able to use it permanently in practice.
  • the invention is based on the technical problem the procedure of the structure described at the beginning and the intended use described at the beginning to be reproducible so that an essential improved defined glare control is achieved.
  • the usual base gloss agents used are "sulfonic acids such as benzenesulfonic acid, naphthalene trisulfonic acid, alkanesulfonic acids or also sulfonamides or sulfonimides or the corresponding alkali salts" or mixtures thereof, in an amount of 0.5 to 10 g / l.
  • a substance from the group "the unsaturated aliphatic sulfonic acids or their alkali metal salts" or mixtures thereof are used for the purpose of producing the glare-free nickel deposits.
  • the concentration of the adducts added is expediently chosen in the range from 0.5 to 10 g / l.
  • the electrolyte is preferably operated in a temperature range of 50 to 65 ° C during the electrolytic deposition. Wetting agents and organic sulfinic acids or their alkali salts can also be added to the electrolyte.
  • the invention is based on the knowledge that even without the formation of a visible, cloudy emulsion and corresponding organic foreign bodies in the Electrolytes achieved high quality glare control is when proceeding according to the teaching of the invention becomes.
  • the nickel layer applied according to the invention has a completely different structure than that after generated known methods described above. This is discussed below in connection with exemplary embodiments explained. It can be left open whether according to the invention is still drop-shaped at all Precipitations occur. Drop-shaped precipitates are within the scope of the invention, the mainly about the surface tension as drops are stabilized. In any case, the effects occur for the high quality reproducible glare-free are required - and surprisingly disruptive conglomerates that disrupt freedom from glare and need to be filtered, not observed.
  • the current densities can largely be adapted to the operating conditions. It has proven useful to operate the electrolyte with a current density of 0.1 to 10 A / dm 2 .
  • the electrolyte is preferably operated with a current density of approximately 4 A / dm 2 .
  • the treatment time for the nickel deposition is largely arbitrary and can be adapted to the operating conditions, in particular also the layer thickness. Within the scope of the invention, the treatment time for the nickel deposition is preferably 1 to 120 minutes, preferably about 10 minutes. is.
  • the electrolyte can always be operated without secondary circulation. Secondary circuit free means that a secondary circuit with filter devices or cooling devices is not required.
  • An electrolyte was used to separate out a glare-free nickel deposit 265 g / l NiSO 4 x 7 H 2 O, 53 g / l NiCl 2 x 6 H 2 O, 33 g / l H 3 BO 3 , 1 g / l of benzoic acid sulfonimide sodium salt and 30 mg of propylene oxide / ethylene oxide block polymer (molecular weight 2500) were added.
  • the non-glare of the coating according to Example 1 is compared to the embodiment according to Example 2 clearly improved.

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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)
  • Electrolytic Production Of Metals (AREA)
  • Physical Vapour Deposition (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)

Abstract

A process for electroplating metal surfaces with non-reflective nickel coatings is operated at 40-75 degrees C with a Watts electrolyte, an electrolyte based on sulphamate, sulphonate or fluoroborate, or a mixture, with the addition of: (A) a conventional basic brightener; and (B) substituted and/or unsubstituted ethylene oxide (EO) adducts, or propylene oxide (PO) adducts, or EO-PO adducts in a concentration of up to 5 mg/l (to produce the non-reflective effect). The concentration of (B) and the temperature of the electrolyte are set as above so that the operating electrolyte appears clear on visual inspection, with practically no scattering of transmitted light.

Description

Die Erfindung betrifft ein Verfahren zur galvanischen Abscheidung von blendfreien Nickelniederschlägen auf einer metallischen Oberfläche. Der Begriff Nikkelniederschläge umfaßt auch Nickellegierungsniederschläge. Der Begriff metallische Oberfläche umfaßt auch metallisierte Oberflächen von nichtmetallischen Gegenständen.The invention relates to a method for galvanic Separation of glare-free nickel deposits on a metallic surface. The term Nikkel precipitation also includes nickel alloy precipitation. The term includes metallic surface also metallized surfaces of non-metallic Objects.

Bei dem bekannten Verfahren, von dem die Erfindung ausgeht (DE 16 21 085 A1), wird mit einem Watts'schen Elektrolyten gearbeitet, dem ein übliches Grundglanzmittel beigegeben wird. Zum Begriff Watts'scher Elektrolyt wird verwiesen auf LPW "Taschenbuch für Galvanotechnik", Band 1, Verfahrenstechnik, 13. Ausgabe 1988, (S. 173 bis 177). Im Rahmen der bekannten Maßnahmen, von denen die Erfindung ausgeht, werden zum Zwecke der Erzeugung der blendfreien Nickelniederschläge substituierte und/oder unsubstituierte Äthylenoxid-Addukte oder Propylenoxid-Addukte oder Äthylenoxid-Propylenoxid-Addukte verwendet und dem Elektrolyten beigegeben. Dabei wird mit einer Konzentration der Addukte im Bereich von 5 bis 100 mg/l gearbeitet. Die Abscheidung wird so betrieben, daß der Elektrolyt eine Temperatur im Bereich von 40 bis 75° C aufweist. Die Addukte werden so ausgewählt, daß die Addukte im arbeitenden Elektrolyten eine feindisperse Emulsion bilden, die sich als Trübung äußert. Die Tröpfchen der Emulsion werden als Grund dafür angesehen, daß sich eine blendreie Oberfläche bildet. Die Blendfreiheit ist jedoch verbesserungsbedürftig. Zwar wird der Ausdruck blendfrei zur Kennzeichnung der. Oberfläche der Nickelabscheidung im Rahmen der bekannten Maßnahmen benutzt, der erreichte Effekt ist jedoch eher ein satinartiger Glanz und dieser Ausdruck wird für die im Rahmen der bekannten Maßnahmen erreichbaren Effekte in der Praxis auch verwendet (vgl. DE 16 21 085). Die Blendfreiheit ist also verbesserungsbedürftig. Im einzelnen ist zu den bekannten Maßnahmen folgendes zu bemerken: Die zum Zwecke der Erzeugung der satinartig glänzenden Nikkelniederschläge im Rahmen der bekannten Maßnahmen beigegebenen Substanzen sind nichtionogene Tenside. Diese fallen bei höherer Elektrolyttemperatur aus. Sie bilden einen organischen Fremdstoff im Elektrolyten, und zwar in Form einer Emulsion. Es versteht sich, daß natürlich nicht jedes beliebige nichtionogene Tensid Verwendung finden kann, da der Trübungspunkt, das heißt, die Elektrolyttemperatur, bei der das Tensid ausfällt, von der chemischen Struktur und der Konzentration der Substanzen im Elektrolyten abhängt. Zusätzlich geht ebenfalls die Salzfracht des Elektrolyten in die Höhe des Trübungspunktes ein. Trotz des mehr oder weniger fein verteilten Zustandes der Emulsionstropfen ist die Gefahr der Zusammenballung zu unpassend großen Konglomeraten aus Emulsionstropfen die die satinglanzartige Abscheidung stören, so groß, daß besondere Maßnahmen zwingend erforderlich sind, um das Verfahren dauerhaft in der Praxis einsetzen zu können. Es ist erforderlich, den Elektrolyten in einem entsprechend dimensionierten Nebenkreislauf abzukühlen, damit der Trübungspunkt des nichtionogenen Tensides deutlich unterschritten wird und dieses sich im Elektrolyten löst. Anschließend wird der Elektrolyt wieder auf die erforderliche Arbeitstemperatur aufgeheizt. Der Betrieb und die Steuerung der bekannten Maßnahmen müssen sehr vorsichtig erfolgen, wenn anders sich auch schwarze Poren bilden können. Insoweit sind die Blendfreiheit und die Reproduzierbarkeit nicht ausreichend und nicht störungsfrei gesichert.In the known method of which the invention goes out (DE 16 21 085 A1), with a Watts electrolyte, which is a common one Basic gloss agent is added. To the subject Watts' electrolyte is referred to LPW "paperback für Galvanotechnik ", Volume 1, Process Engineering, 13th edition 1988, (pp. 173 to 177). As part of the known measures, of which the invention comes out for the purpose of generating the glare-free nickel deposits substituted and / or unsubstituted ethylene oxide adducts or propylene oxide adducts or ethylene oxide-propylene oxide adducts used and added to the electrolyte. there is with a concentration of adducts in the range of 5 to 100 mg / l worked. The deposition is operated that the electrolyte has a temperature in the range from 40 to 75 ° C. The adducts are selected so that the adducts in the working electrolyte form a finely dispersed emulsion that turns out to be turbidity manifests. The droplets of the emulsion are used as the reason considered that there is a glare-free surface forms. Glare-free is in need of improvement. The printout does not become glare for identification the. Surface of the nickel deposition in the frame the known measures used that achieved However, the effect is more of a satin-like sheen Expression is used for the well known Measures achievable effects in practice too used (see. DE 16 21 085). So there is no glare in need of improvement. In detail is among the well-known Measures to note the following: Purposes of the production of the satin-like nickel deposits as part of the known measures added substances are non-ionic Surfactants. These drop at a higher electrolyte temperature out. They form an organic foreign substance in the electrolyte, in the form of an emulsion. It understands that, of course, not just any non-ionic Surfactant can be used because the cloud point, that is, the electrolyte temperature at which the surfactant fails, from the chemical structure and the concentration depends on the substances in the electrolyte. additionally the salt load of the electrolyte also goes into the Height of the cloud point. Despite the more or less finely divided state of the emulsion drops the danger of agglomeration is too large Conglomerates of emulsion drops that are satin-like Disrupt separation, so big that special Measures are mandatory to complete the procedure to be able to use it permanently in practice. It is required to match the electrolyte in a to cool the dimensioned secondary circuit so that the Cloud point of the nonionic surfactant clearly is undershot and this dissolves in the electrolyte. Then the electrolyte is returned to the required level Working temperature warmed up. Operation and the control of the known measures must be very be done carefully if there are also black ones Can form pores. So far are the glare free and the reproducibility is insufficient and not trouble-free secured.

Um die beschriebenen Mängel zu vermeiden, ist es bekannt (DE 23 27 881 C2), mit besonderen Fremdsubstanzen zu arbeiten. Im Rahmen der insoweit bekannten Maßnahmen werden organische Fremdsubstanzen im Elektrolyten durch Reaktion zumindest einer kationenaktiven bzw. amphoteren Substanz mit organischen Anionen wenigstens einer Verbindung erzeugt. Diese Anionen liefernden Substanzen sind unter anderem Alkyl- oder Arylsulfate, -sulfonsäuren sowie -sulfinsäuren wie Sulfonamide und Sulfonimide. Für den entblendeten, aber glänzenden Charakter soll der Elektrolyt zusätzlich bekannte primäre und/oder sekundäre Glanzmittel enthatten. Diese organischen Fremdstoffe ergeben für gewisse Produktionszeitspannen eine dekorativ brauchbare Entblendung in Form eines Matteffektes. Nach dieser Zeitspanne müssen die Fremdsubstanzen jedoch infolge von Agglomerationserscheinungen abgefiltert werden. Das ist aufwendig. Hinzu kommt, daß für den nächsten Arbeitszyklus die organischen Fremdsubstanzen jeweils erneut gebildet werden müssen, was ebenfalls aufwendig ist.To avoid the shortcomings described, it is known (DE 23 27 881 C2), with special foreign substances to work. As part of the known Measures become organic foreign substances in the electrolyte by reaction of at least one cation-active or amphoteric substance with organic Anions of at least one compound generated. This Anions supplying substances include alkyl or aryl sulfates, sulfonic acids and sulfinic acids such as sulfonamides and sulfonimides. For the glare-free, but the electrolyte should also have a shiny character known primary and / or secondary brighteners enthatten. These organic foreign substances result a decorative for certain production periods usable glare control in the form of a matt effect. After this period, the foreign substances must however filtered out due to agglomeration phenomena become. It is expensive. On top of that the organic foreign substances for the next working cycle must be formed again each time which is also expensive.

Der Erfindung liegt das technische Problem zugrunde, das Verfahren des eingangs beschriebenen Aufbaus und der eingangs beschriebenen Zweckbestimmung so zu führen, daß reproduzierbar eine wesentlich verbesserte definierte Blendfreiheit erreicht wird.The invention is based on the technical problem the procedure of the structure described at the beginning and the intended use described at the beginning to be reproducible so that an essential improved defined glare control is achieved.

Zur Lösung dieses technischen Problems ist Gegenstand der Erfindung ein Verfahren zur galvanischen Abscheidung von blendfreien Nickelniederschlägen auf einer metallischen Oberfläche mit den Merkmalen:

  • 1.1) es wird mit einem Elektrolyten der Gruppe aWatts'scher Elektrolyt, Elektrolyte auf Basis von Sulfamat, Sulfonat, Fluoroborat" oder Mischungen davon gearbeitet, dem ein übliches Grundglanzmittel beigegeben worden ist,
  • 1.2) es werden zum Zwecke der Erzeugung der blendfreien Nickelniederschläge substituierte und/oder unsubstituierte Äthylenoxid-Addukte oder Propylenoxid-Addukte oder Äthylenoxid-Propylenoxid-Addukte verwendet und dem Elektrolyten beigegeben,
  • 1.3) die Konzentration der gemäß 1.2) beigegebenen Addukte wird in einen Bereich von größer Null bis kleiner 5 mg/l gewählt,
  • 1.4) bei der galvanischen Abscheidung wird der Elektrolyt in einem Temperaturbereich von 40 bis 75° C betrieben,
    • mit der Maßgabe, daß die Konzentration gemäß 1.3) und die Temperatur gemäß 1.4) so gewählt werden, daß der arbeitende Elektrolyt bei Augeninspektion klar erscheint und bei Lichtdurchfall eine diffuse Streuung praktisch nicht zeigt. Elektrolyt steht für elektrolytisches Bad.To solve this technical problem, the subject of the invention is a method for the galvanic deposition of glare-free nickel deposits on a metallic surface with the features:
  • 1.1) an electrolyte from Group a Watts electrolyte, electrolytes based on sulfamate, sulfonate, fluoroborate "or mixtures thereof is used, to which a customary basic gloss agent has been added,
  • 1.2) substituted and / or unsubstituted ethylene oxide adducts or propylene oxide adducts or ethylene oxide-propylene oxide adducts are used and added to the electrolyte for the purpose of producing the glare-free nickel precipitates,
  • 1.3) the concentration of the adducts added according to 1.2) is selected in a range from greater than zero to less than 5 mg / l,
  • 1.4) during electrodeposition, the electrolyte is operated in a temperature range from 40 to 75 ° C,
    • with the proviso that the concentration in accordance with 1.3) and the temperature in accordance with 1.4) are selected so that the working electrolyte appears clear when the eyes are inspected and practically does not show any diffuse scattering when the light passes through. Electrolyte stands for electrolytic bath.

    Im allgemeinen wird man mit einem Elektrolyten arbeiten, der eine Richtanalyse mit 70 bis 140 g/l Nickel, 1 bis 20 g/l Chlorid, 30 bis 50 g/l H3BO3 und im Rest das Grundglanzmittel sowie die Addukte und außerdem Wasser aufweist. Nach bevorzugter Ausführungsform der Erfindung werden als übliche Grundglanzmittel "Sulfonsäuren wie Benzolsulfonsäure, Naphthalintrisulfonsäure, Alkansutfonsäuren oder auch Sulfonamide oder Sulfonimide bzw. die entsprechenden Alkalisalze" oder Mischungen davon verwendet, und zwar in einer Menge von 0,5 bis 10 g/l. Zum Zwecke der Erzeugung der blendfreien Nickelniederschläge werden nach bevorzugter Ausführungsform der Erfindung eine Substanz der Gruppe "der ungesättigten aliphatischen Sulfonsäuren bzw. deren Alkalisalze" oder Mischungen davon verwendet. Die Konzentration der beigegebenen Addukte wird zweckmäßigerweise im Bereich von 0,5 bis 10 g/l gewählt. - Vorzugsweise wird bei der elektrolytischen Abscheidung der Elektrolyt in einem Temperaturbereich von 50 bis 65° C betrieben. Dem Elektrolyten können weiterhin Netzmittel sowie organische Sulfinsäuren bzw. deren Alkalisalze zugesetzt werden.In general, you will work with an electrolyte, the directional analysis with 70 to 140 g / l of nickel, 1 to 20 g / l of chloride, 30 to 50 g / l of H 3 BO 3 and the rest of the basic gloss and adducts and also water having. According to a preferred embodiment of the invention, the usual base gloss agents used are "sulfonic acids such as benzenesulfonic acid, naphthalene trisulfonic acid, alkanesulfonic acids or also sulfonamides or sulfonimides or the corresponding alkali salts" or mixtures thereof, in an amount of 0.5 to 10 g / l. According to a preferred embodiment of the invention, a substance from the group "the unsaturated aliphatic sulfonic acids or their alkali metal salts" or mixtures thereof are used for the purpose of producing the glare-free nickel deposits. The concentration of the adducts added is expediently chosen in the range from 0.5 to 10 g / l. - The electrolyte is preferably operated in a temperature range of 50 to 65 ° C during the electrolytic deposition. Wetting agents and organic sulfinic acids or their alkali salts can also be added to the electrolyte.

    Die Erfindung geht von der Erkenntnis aus, daß auch ohne Bildung einer sichtbaren, trüben Emulsion und entsprechender organischer Fremdkörper in dem Elektrolyten eine qualitativ hochwertige Entblendung erreicht wird, wenn nach der Lehre der Erfindung verfahren wird. Die erfindungsgemäß aufgebrachte Nickelschicht hat eine ganz andere Struktur als die nach dem eingangs beschriebenen bekannten Verfahren erzeugte. Das wird weiter unten im Zusammenhang mit Ausführungsbeispielen erläutert. Es kann dahingestellt bleiben, ob erfindungsgemäß überhaupt noch tropfenförmige Ausfällungen auftreten. Tropfenförmige Ausfällungen sind im Rahmen der Erfindung Ausfällungen, die hauptsächlich über die Oberflächenspannung als Tropfen stabilisiert sind. Jedenfalls treten die Effekte ein, die für die qualitativ hochwertige reproduzierbare Blendfreiheit erforderlich sind - und überraschenderweise werden störende Konglomerate, die die Blendfreiheit stören und abgefiltert werden müssen, nicht beobachtet.The invention is based on the knowledge that even without the formation of a visible, cloudy emulsion and corresponding organic foreign bodies in the Electrolytes achieved high quality glare control is when proceeding according to the teaching of the invention becomes. The nickel layer applied according to the invention has a completely different structure than that after generated known methods described above. This is discussed below in connection with exemplary embodiments explained. It can be left open whether according to the invention is still drop-shaped at all Precipitations occur. Drop-shaped precipitates are within the scope of the invention, the mainly about the surface tension as drops are stabilized. In any case, the effects occur for the high quality reproducible glare-free are required - and surprisingly disruptive conglomerates that disrupt freedom from glare and need to be filtered, not observed.

    Im Rahmen der Erfindung können die Stromdichten weitgehend den betrieblichen Verhältnissen angepaßt werden. Bewährt hat es sich, den Elektrolyten mit einer Stromdichte von 0,1 bis 10 A/dm2 zu betreiben. Vorzugsweise wird der Elektrolyt mit einer Stromdichte von etwa 4 A/dm2 betrieben. Auch die Behandlungszeit für die Nickelabscheidung ist weitgehend beliebig und betrieblichen Verhältnissen anpaßbar, insbesondere auch der Schichtdicke. Vorzugsweise wird im Rahmen der Erfindung mit einer Behandlungszeit für die Nickelabscheidung gearbeitet, die 1 bis 120 min., vorzugsweise zugsweise etwa 10 min. beträgt. Der Elektrolyt kann stets nebenkreislauffrei betrieben werden. Nebenkreislauffrei bedeutet, daß ein Nebenkreislauf mit Filtereinrichtungen oder Kühleinrichtungen nicht erforderlich ist.Within the scope of the invention, the current densities can largely be adapted to the operating conditions. It has proven useful to operate the electrolyte with a current density of 0.1 to 10 A / dm 2 . The electrolyte is preferably operated with a current density of approximately 4 A / dm 2 . The treatment time for the nickel deposition is largely arbitrary and can be adapted to the operating conditions, in particular also the layer thickness. Within the scope of the invention, the treatment time for the nickel deposition is preferably 1 to 120 minutes, preferably about 10 minutes. is. The electrolyte can always be operated without secondary circulation. Secondary circuit free means that a secondary circuit with filter devices or cooling devices is not required.

    Beispiel 1:Example 1:

    Zur Abscheidung eines blendfreien Nickelniederschlages wurde einem Elektrolyten mit 550 g/l NiSo4 x 7 H2O, 50 g/l NiCl2 x 6 H2O, 40 g/l H3BO3, 2,6 g/1 Benzoesäuresulfonimid-Natriumsalz, 1,8 g/l 2-Propensulfonat-Natriumsalz und 1,5 mg/l Polyethylenglykolmethylether (Molmasse 5000) zugesetzt. Bei einem pH-Wert von 3,8 bis 4,4 und einer Temperatur von 55° C lieferte der klare Elektrolyt bei einer Stromdichte von 5 A/dm2 und einer Behandlungszeit von 10 min. bei leichter Warenbewegung auf einem Messingblech eine blendarme Nickelschicht mit einem Metallic-Effekt. Bild 1 zeigt die Oberfläche dieses Nickelniederschlages im Maßstab 600:1An electrolyte was used to separate out a glare-free nickel deposit 550 g / l NiSo 4 x 7 H 2 O, 50 g / l NiCl 2 x 6 H 2 O, 40 g / l H 3 BO 3 , 2.6 g / 1 of benzoic acid sulfonimide sodium salt, 1.8 g / l of 2-propenesulfonate sodium salt and 1.5 mg / l of polyethylene glycol methyl ether (molar mass 5000) were added. At a pH of 3.8 to 4.4 and a temperature of 55 ° C, the clear electrolyte provided at a current density of 5 A / dm 2 and a treatment time of 10 min. When goods move slightly on a sheet of brass, a low-glare nickel layer with a metallic effect. Figure 1 shows the surface of this nickel deposit on a scale of 600: 1

    In Bild 1 erkennt man einen Niederschlag in Form einer Tropfenstruktur, der ein Tröpfendurchmesser von 1 bis 7 µm zugeordnet werden kann.In picture 1 you can see a precipitation in form a drop structure with a droplet diameter of 1 to 7 µm can be assigned.

    Beispiel 2:Example 2:

    Zur Abscheidung eines blendfreien Nickelniederschlages wurde einem Elektrolyten mit 265 g/l NiSO4 x 7 H2O, 53 g/l NiCl2 x 6 H2O, 33 g/l H3BO3, 1 g/l Benzoesäuresulfonimid-Natriumsalz sowie 30 mg Propylenoxid-Ethylenoxid-Blockpolymer (Molmasse 2500) zugesetzt. Bei einem pH-Wert von 4,2 bis 4,4 und einer Temperatur von 52° C lieferte der trübe Elektrolyt bei einer Stromdichte von 5 A/dm2, Arbeitszeit 10 min., bei leichter Warenbewegung auf einem Messingblech einen seidenmatten, blendarmen Nickelniederschlag. Bild 2 zeigt die Oberfläche dieses Niederschlages in Maßstab 600:1An electrolyte was used to separate out a glare-free nickel deposit 265 g / l NiSO 4 x 7 H 2 O, 53 g / l NiCl 2 x 6 H 2 O, 33 g / l H 3 BO 3 , 1 g / l of benzoic acid sulfonimide sodium salt and 30 mg of propylene oxide / ethylene oxide block polymer (molecular weight 2500) were added. At a pH of 4.2 to 4.4 and a temperature of 52 ° C, the cloudy electrolyte with a current density of 5 A / dm 2 , working time 10 min., With a slight movement of the goods on a brass sheet, a silky, low-glare nickel deposit , Figure 2 shows the surface of this precipitate in scale 600: 1

    Man erkennt einen Niederschlag in Form einer Tropfenstruktur, der ein Tröpfchendurchmesser von 5 bis 20 µm zugeordnet werden kann.You can see a precipitation in the form of a Teardrop structure with a droplet diameter of 5 up to 20 µm can be assigned.

    Die Blendfreiheit der Beschichtung nach Beispiel 1 ist gegenüber der Ausführungsform nach Beispiel 2 deutlich verbessert.The non-glare of the coating according to Example 1 is compared to the embodiment according to Example 2 clearly improved.

    Claims (10)

    1. A process for the galvanic deposition of non-glare nickel precipitates on a metallic surface with the features:
      1.1) an electrolyte of the group "Watts-type electrolyte, electrolytes based on sulphamate, sulphonate, fluoroborate" or mixtures thereof is worked with, to which a standard basic lustering agent has been added,
      1.2) for the purpose of producing the non-glare nickel precipitates, substituted and/or unsubstituted ethylene oxide adducts or propylene oxide adducts or ethylene oxide propylene oxide adducts are used and added to the electrolyte,
      1.3) the concentration of the adducts added according to 1.2) is selected in a range from greater than zero up to less than 5 mg/l,
      1.4) during the galvanic deposition, the electrolyte is maintained in a temperature range from 40 to 75 °C,
      provided that the concentration according to 1.3) and the temperature according to 1.4) are selected such that the working electrolyte appears clear upon visual inspection and displays virtually no diffuse scatter with transmitted light.
    2. A process according to claim 1, wherein a Watts electrolyte is employed which has a set analysis of
         70 to 140 g/l nickel,
         1 to 20 g/l chloride,
         30 to 50 g/l H3BO3,
      balance basic brighteners, adducts and water.
    3. A process according to either one of claims 1 or 2, wherein a substance from the group comprising 2-sulphobenzoic acid imide, 1,3-benzenedisulphonic acid and naphthalenetrisulphonic acid or alkali salts thereof or mixtures thereof, or from the group comprising arylsulphonic acids, alkylsulphonic acids, sulphonamides and sulphonimides or alkali salts thereof or mixtures thereof, is used as the basic brightener in an amount of 0.5 to 10 g/l.
    4. A process according to any one of claims 1 to 3, wherein a substance from the group comprising unsaturated aliphatic sulphonic acids or alkali salts thereof or mixtures thereof is used as the basic brightener.
    5. A process according to claim 4, wherein the concentration of basic brightener is selected within a range from 0.5 to 10 g/l.
    6. A process according to any one of claims 1 to 5, wherein during the electrolytic deposition the electrolyte is operated within a temperature range from 50 to 65°C.
    7. A process according to any one of claims 1 to 6, wherein the electrolyte is operated at a current density of 0.1 to 10 A/dm2.
    8. A process according to any one of claims 1 to 7, wherein the electrolyte is operated at a current density of about 4 A/dm2.
    9. A process according to any one of claims 1 to 8, wherein a treatment time is employed for nickel deposition which amounts to 1 to 120 minutes, preferably about 10 minutes.
    10. A process according to any one of claims 1 to 9, wherein the electrolyte is operated free from auxiliary circulation.
    EP96116639A 1995-10-27 1996-10-17 Process for electroplating nickel with satin finish Expired - Lifetime EP0770710B2 (en)

    Applications Claiming Priority (3)

    Application Number Priority Date Filing Date Title
    DE9540011U 1995-10-27
    DE19540011A DE19540011C2 (en) 1995-10-27 1995-10-27 Process for the galvanic deposition of glare-free nickel or nickel alloy deposits
    DE19540011 1995-10-27

    Publications (3)

    Publication Number Publication Date
    EP0770710A1 EP0770710A1 (en) 1997-05-02
    EP0770710B1 EP0770710B1 (en) 1999-01-07
    EP0770710B2 true EP0770710B2 (en) 2002-08-14

    Family

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    Application Number Title Priority Date Filing Date
    EP96116639A Expired - Lifetime EP0770710B2 (en) 1995-10-27 1996-10-17 Process for electroplating nickel with satin finish

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    US (1) US5897763A (en)
    EP (1) EP0770710B2 (en)
    JP (1) JPH09202987A (en)
    AT (1) ATE175453T1 (en)
    DE (2) DE19540011C2 (en)
    ES (1) ES2128135T5 (en)

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    Publication number Priority date Publication date Assignee Title
    US6251253B1 (en) * 1999-03-19 2001-06-26 Technic, Inc. Metal alloy sulfate electroplating baths
    US6248228B1 (en) * 1999-03-19 2001-06-19 Technic, Inc. And Specialty Chemical System, Inc. Metal alloy halide electroplating baths
    WO2000056952A1 (en) * 1999-03-19 2000-09-28 Technic, Incorporated Electroplating baths
    US6797141B1 (en) * 1999-11-25 2004-09-28 Enthone Inc. Removal of coagulates from a non-glare electroplating bath
    US6306275B1 (en) * 2000-03-31 2001-10-23 Lacks Enterprises, Inc. Method for controlling organic micelle size in nickel-plating solution
    DE10025552C1 (en) * 2000-05-19 2001-08-02 Atotech Deutschland Gmbh Acidic electroplating nickel bath and process for depositing a satin nickel or nickel alloy coating
    DE10222962A1 (en) 2002-05-23 2003-12-11 Atotech Deutschland Gmbh Acidic galvanic bath electrolyte and process for the electrolytic deposition of satin-shining nickel deposits
    ATE507327T1 (en) * 2006-01-06 2011-05-15 Enthone ELECTROLYTE AND METHOD FOR DEPOSITING A MATTE METAL LAYER
    PL2620529T3 (en) * 2012-01-25 2014-09-30 Atotech Deutschland Gmbh Method for producing matt copper deposits
    JP6760166B2 (en) 2017-03-23 2020-09-23 トヨタ自動車株式会社 A method for forming a nickel film and a nickel solution for use in the method.
    US11505867B1 (en) 2021-06-14 2022-11-22 Consolidated Nuclear Security, LLC Methods and systems for electroless plating a first metal onto a second metal in a molten salt bath, and surface pretreatments therefore

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    DE1621085A1 (en) † 1967-05-16 1971-03-11 Henkel & Cie Gmbh Acid galvanic bath for the production of satin nickel deposits

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    US3839166A (en) * 1967-05-16 1974-10-01 Henkel & Cie Gmbh Method for obtaining nickel deposits with satin finish
    US3839165A (en) * 1967-08-26 1974-10-01 Henkel & Cie Gmbh Nickel electroplating method
    BE794695A (en) * 1972-01-29 1973-05-16 W Kampschulte & Cie K G Dr GALVANIC NICKEL BATH FOR SEPARATING MATT SATIN NICKEL COATINGS
    DE2327881B2 (en) * 1973-06-01 1978-06-22 Langbein-Pfanhauser Werke Ag, 4040 Neuss Process for the galvanic deposition of matt-glossy nickel or nickel / cobalt deposits
    JPS56152988A (en) * 1980-04-30 1981-11-26 Nobuyuki Koura Nickel satin finish plating bath of heavy ruggedness
    JPS61238993A (en) * 1985-04-16 1986-10-24 Dai Ichi Kogyo Seiyaku Co Ltd Additive for electroplating bath
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    Also Published As

    Publication number Publication date
    JPH09202987A (en) 1997-08-05
    DE19540011C2 (en) 1998-09-10
    ES2128135T5 (en) 2003-03-01
    ES2128135T3 (en) 1999-05-01
    ATE175453T1 (en) 1999-01-15
    EP0770710A1 (en) 1997-05-02
    US5897763A (en) 1999-04-27
    EP0770710B1 (en) 1999-01-07
    DE59601103D1 (en) 1999-02-18
    DE19540011A1 (en) 1997-04-30

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