EP1780311A1 - Manufacturing process for satin-matt surface - Google Patents

Manufacturing process for satin-matt surface Download PDF

Info

Publication number
EP1780311A1
EP1780311A1 EP05109770A EP05109770A EP1780311A1 EP 1780311 A1 EP1780311 A1 EP 1780311A1 EP 05109770 A EP05109770 A EP 05109770A EP 05109770 A EP05109770 A EP 05109770A EP 1780311 A1 EP1780311 A1 EP 1780311A1
Authority
EP
European Patent Office
Prior art keywords
layer
matt
workpiece
sulfamate
gloss
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.)
Granted
Application number
EP05109770A
Other languages
German (de)
French (fr)
Other versions
EP1780311B1 (en
Inventor
Wolf-Dieter Franz
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.)
Individual
Original Assignee
Individual
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 Individual filed Critical Individual
Priority to EP05109770A priority Critical patent/EP1780311B1/en
Priority to DE502005004040T priority patent/DE502005004040D1/en
Priority to ES05109770T priority patent/ES2306023T3/en
Priority to AT05109770T priority patent/ATE394526T1/en
Priority to US12/083,843 priority patent/US8105473B2/en
Priority to PCT/EP2006/067618 priority patent/WO2007045688A1/en
Publication of EP1780311A1 publication Critical patent/EP1780311A1/en
Application granted granted Critical
Publication of EP1780311B1 publication Critical patent/EP1780311B1/en
Not-in-force legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/10Electroplating with more than one layer of the same or of different metals
    • C25D5/12Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium
    • C25D5/14Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium two or more layers being of nickel or chromium, e.g. duplex or triplex layers
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/60Electroplating characterised by the structure or texture of the layers
    • C25D5/605Surface topography of the layers, e.g. rough, dendritic or nodular layers
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/60Electroplating characterised by the structure or texture of the layers
    • C25D5/605Surface topography of the layers, e.g. rough, dendritic or nodular layers
    • C25D5/611Smooth layers
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/627Electroplating characterised by the visual appearance of the layers, e.g. colour, brightness or mat appearance

Definitions

  • the present invention relates to the production of satin surfaces of workpieces, in particular automotive parts.
  • Galvanic processes are also known in which galvanic Ni layers are given an adjustable silk mattness by adding to the galvanic solution an organic additive which drops onto the surface like a droplet and leads to disturbances of the surface structure.
  • the degree of dullness or silk gloss must be set relatively inconveniently over the added amounts before starting a process and the organic additives must be filtered out in a process interruption before a new process start so as not to disturb the new process.
  • the setting mentioned must therefore be repeated with each new process start-up and is therefore complicated and disadvantageous in terms of reproducibility.
  • the invention is based on the technical problem of specifying an alternative method for producing satin matt metal surfaces on workpieces.
  • a method is provided with the steps of: producing a smooth surface on a workpiece, applying a matt Ni layer by electrodeposition without organic matting additives, applying a sulfamate-Ni layer.
  • the basic idea of the invention is to apply a matt Ni layer on a smooth workpiece surface and to adjust the mattness over the thickness of the Ni layer.
  • the invention is directed to galvanic Ni layers in which no organic matting additives are used. Rather, in a preferred embodiment of the invention may be a known Wattsche Ni layer, which is technically simple and easy to control.
  • the degree of gloss or degree of matting can be determined by various galvanic parameters, in particular by treatment time and / or Amperage, easy and well adjustable control. The need to filter the solutions for filtering organic matting additives is also eliminated.
  • the abovementioned sulfamate-Ni layer is preferably protected against environmental influences by means of a further finishing layer, it being understood that this finishing layer can also have a decorative function.
  • a galvanic Cr layer which may have a thickness between 0.1 and 3 microns, with a lower limit of 0.5 microns or an upper limit of 1 micron is particularly preferred.
  • a conventional and available through commercially available solutions gloss chrome process can be used because the satin finish of the surface is already present.
  • the invention is not limited to Cr layers.
  • Other decorative layers may also be used, such as Ag, Au or Pt metals.
  • black chrome layers are also suitable, Ti layers, in particular sputtered Ti layers, or else non-metallic layers such as (clear) lacquers or (sputtered) ceramic layers.
  • the smooth surface on the workpiece under the matte Ni layer may for example be a polished workpiece surface itself or even an applied metal layer. If an inventively preferred gloss Ni layer is used here, this has the particular advantage of very well leveling any surface defects and defects. Thus, it can improve the quality of the final gloss content of the finished metal surface according to the invention.
  • Galvanic processes for bright Ni layers are well known and need not be detailed here. There are commercial solutions available which may include, for example, Ni sulfate, organic brighteners and so-called levelers. Suitable current densities in this range are 1 to 3 A / dm 2 . It may also be advantageous to provide a shiny metal layer, for example a Cu layer, below the glossy Ni layer.
  • the matte galvanic Ni layer is preferably applied as a known and technically well-controlled Wattsche Ni layer, ie as a galvanic Ni layer without organic matting additives.
  • Current strengths in the range of 0.1 to 2 A / dm 2 , better 0.1 to 1 A / dm 2 are preferred here.
  • the layer thickness of the matt layer should be comparatively low and may be between 0.05 and 5 .mu.m, with upper limits of 4 .mu.m, 3 .mu.m, 2 .mu.m and more preferably 1 .mu.m and lower limits of 0.075 .mu.m and more preferably 0.1 .mu.m even cheaper.
  • the layer thickness is ultimately determined by optical / aesthetic considerations.
  • the electrodeposition of a sulfamate-Ni layer is also conventional and known.
  • the corresponding solutions contain nickel sulfamate, that is, the salt of amidosulfuric acid.
  • the sulphamate Ni layer rounds and reinforces the aforementioned bulbous or otherwise matte Ni layer, it does not really level it.
  • the sulfamate-Ni layer also enhances the grain size without changing fundamentals on the granularity described above as "nodular". It thus receives the matte character, possibly only slightly increases the gloss, but above all provides increased material strength for reasons of stability and resilience and for better wiping sensitivity or better dirt-repellent properties. The roughness reduced by the rounding provides less grip to soiling.
  • a favorable thickness for the suifamate Ni layer is in the range of 5 and 20 microns, with a lower limit of 10 and an upper limit of 15 microns are more preferred. It has already been mentioned that a protective topcoat is preferred. If the metallic Ni color is of interest, a clearcoat can also be used here.
  • a particular advantage of the invention in addition to the good optical properties and the good resilience and dirt resistance of surfaces according to the invention is that can be adjusted by galvanic parameters in a very simple manner, the degree of gloss or matte degree.
  • Different optical properties can be generated with one and the same basic process, that is, the same solution compositions, identical baths, etc. In particular, from batch to batch simply over the amperage, or even cheaper about the treatment time, the dullness are set. The thicker the matte Ni layer, the higher the matte degree.
  • Figures 1 - 5 show various intermediate stages of a method according to the invention.
  • FIG. 1 schematically shows a surface of the plastic door handle 1.
  • a glossy Ni layer 2 is deposited in a manner known per se.
  • the surface of the plastic door handle can be previously germinated and prepared, for example, with a chemically deposited thin metal layer for the electroplating process.
  • the glossy Ni layer 2 is deposited in a standard electroplating process at 2 A / dm 2 from an aqueous solution containing about 180 g / l nickel sulfate, about 150 g / l nickel chloride and about 50 g / l boric acid as a pH buffer and at Gloss Ni baths contains commercially available organic brighteners.
  • the bath Slotonik-50 of the company Schlötter comes into consideration.
  • the purpose of the glossy Ni layer 2 is to provide a glossy base that is as error-free as possible, and is distinguished by its good ability to level initially existing imperfections.
  • Their thickness is not really essential to the subsequent process and depends, on the one hand, on the overall material thickness targeted, especially with regard to durability, and on the surface defects to be leveled. Typical orders of magnitude are in the range of 10-30 microns.
  • a matt wadding Ni layer 3 is applied on the glossy Ni layer 2, according to FIG. 3, a matt wadding Ni layer 3 is applied. This is carried out at a current density of about 0.5 A / dm 2 from an aqueous solution containing 210 g / l nickel sulfate, 35 g / l nickel chloride and 40 g / l boric acid without further additives.
  • the preferred layer thickness range is between 0.1 and 1 ⁇ m, wherein the mattness of the finally resulting layer is adjusted via the layer thickness. In this embodiment, 0.2 microns are deposited.
  • FIG. 3 illustrates that this layer thickness only makes sense in terms of averaging.
  • the growth is very grainy or "bulbous”
  • the individual grains shown schematically in Figure 3 with increasing average layer thickness are larger and have decreasing average distances.
  • the grains are finally close, resulting in a matte layer that does not let the gloss of the underlying gloss Ni layer 2 through.
  • a sulfamate Ni layer 4 is deposited on the Watt Ni layer 3.
  • the grains are thereby reinforced, rounded the corners a bit and in particular the niches and angles lying on the edge of the grains filled.
  • a 12 ⁇ m thick layer is deposited at a galvanic current density of 1 A / dm 2 .
  • the aqueous solution contains 36% by volume of 60% by weight nickel sulphamate solution.
  • the galvanic solution contains 5 g / l nickel chloride and 35 g / l boric acid. Considered, for example, the bathroom Schlötter MS.
  • a finishing layer is optionally applied.
  • this is a conventional gloss Cr layer 5 of thickness 1.5 .mu.m.
  • the overall layer is well protected against environmental influences and resistant to oxidation. It ultimately shows a metallic Cr gloss, which is desirable here. Due to the somewhat rounding properties of the sulfamate-Ni layer, the sensitivity to dirt and the roughness are significantly improved and well suited for applications in the interior of motor vehicles.
  • the exemplary embodiment is a simple process control with a control of the essential layer properties over the treatment time, in particular a control of the mattness of the resulting silk gloss over the time of the Watt's nickel process.
  • the described disadvantages of organic matting additives omitted. The process is thus practicable, easy to reproduce and inexpensive.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Electroplating Methods And Accessories (AREA)
  • Laminated Bodies (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Glass Compositions (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)

Abstract

A method for the production of satin-finish metal surfaces on a workpiece (1) involves (a) making a smooth surface (2) on (1), (b) applying a matt nickel coating (3) by electroplating without using organic delustering agents and then (c) applying a sulfamate-nickel coating (4).

Description

Die vorliegende Erfindung bezieht sich auf die Herstellung seidenmatter Oberflächen von Werkstücken, insbesondere Automobilteilen.The present invention relates to the production of satin surfaces of workpieces, in particular automotive parts.

Es ist bekannt, durch galvanische Prozesse Metalloberflächen auf unterschiedlichsten Werkstücken herzustellen. Dabei sind sowohl glänzende Oberflächen als auch matte Oberflächen möglich.It is known to produce metal surfaces on a wide variety of workpieces by galvanic processes. Both glossy surfaces and matt surfaces are possible.

Bei bestimmten Anwendungen, insbesondere bei dekorativen Oberflächen im Automobilbereich, sind seidenmatte Metalloberflächen von Interesse. Bei der galvanischen Herstellung solcher Oberflächen stellt sich dabei das Problem, den Grad der Mattheit bzw. des Glanzes und damit die genaue Form des bei seidenmatten Oberflächen gewünschten Kompromisses zwischen Glanz und Mattheit reproduzierbar einstellen zu können.In certain applications, especially decorative surfaces in the automotive sector, semi-gloss metal surfaces are of interest. In the galvanic production of such surfaces, there is the problem of being able to reproducibly adjust the degree of dullness or gloss and thus the exact shape of the desired compromise between gloss and mattness in silk-matt surfaces.

Bekannt sind auch galvanische Verfahren, bei denen galvanische Ni-Schichten dadurch eine einstellbare Seidenmattheit erhalten, dass der galvanischen Lösung ein organischer Zusatz zugegeben wird, der sich tröpfchenartig auf die Oberfläche legt und zu Störungen der Oberflächenstruktur führt. Der Grad der Mattheit bzw. des Seidenglanzes muss dabei über die Zugabemengen vor Anfahren eines Prozesses relativ umständlich neu eingestellt werden und die organischen Zusätze müssen bei einer Prozessunterbrechung vor einem neuen Prozessanlauf ausgefiltert werden, um den neuen Prozess nicht zu stören. Die genannte Einstellung muss also mit jedem neuen Prozessanlauf neu erfolgen und ist daher aufwändig und hinsichtlich der Reproduzierbarkeit nachteilig.Galvanic processes are also known in which galvanic Ni layers are given an adjustable silk mattness by adding to the galvanic solution an organic additive which drops onto the surface like a droplet and leads to disturbances of the surface structure. The degree of dullness or silk gloss must be set relatively inconveniently over the added amounts before starting a process and the organic additives must be filtered out in a process interruption before a new process start so as not to disturb the new process. The setting mentioned must therefore be repeated with each new process start-up and is therefore complicated and disadvantageous in terms of reproducibility.

Weiterhin ist es bekannt, Oberflächen, etwa Cu-beschichtete Oberflächen sandzustrahlen und dann etwa mit Ni galvanisch zu beschichten. Der Seidenglanz lässt sich hierbei schlecht einstellen. Ferner zeigen sich leicht optische Fehler des Sandstrahlprozesses, etwa Glanzstellen durch während des Sandstrahlprozesses auf dem Werkstück aufliegende Partikel. Auch andere Oberflächenfehler treten vergleichsweise deutlich zu Tage.Furthermore, it is known to sandblast surfaces, such as Cu-coated surfaces, and then to electroplate with Ni, for example. The silk gloss can be adjusted badly. Furthermore, slight optical defects of the sandblasting process, such as sharp spots due to particles resting on the workpiece during the sandblasting process, are easily apparent. Other surface defects are also comparatively obvious.

Der Erfindung liegt das technische Problem zu Grunde, ein alternatives Verfahren zur Herstellung von seidenmatten Metalloberflächen auf Werkstücken anzugeben.The invention is based on the technical problem of specifying an alternative method for producing satin matt metal surfaces on workpieces.

Zur Lösung dieses Problems ist vorgesehen ein Verfahren mit den Schritten: Herstellen einer glatten Oberfläche auf einem Werkstück, Aufbringen einer matten Ni-Schicht durch galvanische Abscheidung ohne organische Mattierungszusätze, Aufbringen einer Sulfamat-Ni-Schicht.To solve this problem, a method is provided with the steps of: producing a smooth surface on a workpiece, applying a matt Ni layer by electrodeposition without organic matting additives, applying a sulfamate-Ni layer.

Bevorzugte Ausgestaltungen sind in den abhängigen Ansprüchen angegeben und werden im Folgenden näher erläutert.Preferred embodiments are specified in the dependent claims and are explained in more detail below.

Die Grundidee der Erfindung besteht darin, eine matte Ni-Schicht auf einer glatten Werkstückoberfläche aufzubringen und die Mattheit über die Stärke der Ni-Schicht einzustellen. Dabei richtet sich die Erfindung auf galvanische Ni-Schichten, bei denen keine organischen Mattierungszusätze verwendet werden. Vielmehr kann es sich bei einer bevorzugten Ausgestaltung der Erfindung um eine an sich bekannte Wattsche Ni-Schicht handeln, die technisch einfach und leicht beherrschbar ist.The basic idea of the invention is to apply a matt Ni layer on a smooth workpiece surface and to adjust the mattness over the thickness of the Ni layer. The invention is directed to galvanic Ni layers in which no organic matting additives are used. Rather, in a preferred embodiment of the invention may be a known Wattsche Ni layer, which is technically simple and easy to control.

Auf die matte Ni-Schicht soll dann eine weitere Sulfamat-Ni-Schicht aufgebracht werden. Diese hat erfindungsgemäß den Vorteil und die Funktion, die mehr oder weniger kornähnliche Struktur der matten Ni-Schicht etwas zu verrunden und damit etwas weniger rau und verschmutzungsempfindlich zu gestalten.On the matte Ni layer then another sulfamate-Ni layer should be applied. This has the advantage and the function of the invention to round the more or less grain-like structure of the matte Ni layer something and thus to make something less rough and sensitive to contamination.

Insgesamt ergibt sich aus dem Zusammenwirken der abhängig von der Stärke der matten Ni-Schicht noch durch einen mehr oder weniger ausgeprägten Restglanz in Erscheinung tretenden glatten Oberfläche auf dem Werkstück mit der durch die matte Ni-Schicht verliehenen Mattheit und schließlich der erläuterten Verrundung durch die Sulfamat-Ni-Schicht ein optisch attraktiver und vor allem gut reproduzierbarer Seidenglanz. Dieser steht in seiner optischen Qualität den erwähnten Ni-Schichten mit organischen Mattierungszusätzen in keiner Weise nach. Darüber hinaus lässt sich bei dem erfindungsgemäßen Verfahren der Glanzgrad bzw. Mattheitsgrad durch verschiedene galvanische Parameter, insbesondere durch Behandlungszeit und/oder Stromstärke, leicht und gut einstellbar steuern. Die Notwendigkeit der Filterung der Lösungen zum Ausfiltern von organischen Mattierungszusätzen entfällt zudem.Overall, the result of the interaction of depending on the strength of the matte Ni layer still by a more or less pronounced residual appearing smooth surface on the workpiece with the conferred by the matte Ni layer dullness and finally the explained rounding by the sulfamate -Ni-layer a visually attractive and above all well reproducible silk gloss. In its optical quality, this is in no way inferior to the mentioned Ni layers with organic matting additives. Moreover, in the method according to the invention, the degree of gloss or degree of matting can be determined by various galvanic parameters, in particular by treatment time and / or Amperage, easy and well adjustable control. The need to filter the solutions for filtering organic matting additives is also eliminated.

Die erwähnte Sulfamat-Ni-Schicht wird vorzugsweise durch eine weitere Abschlussschicht gegen Umwelteinflüsse geschützt, wobei diese Abschlussschicht natürlich auch dekorative Funktion haben kann. Bevorzugt ist insbesondere eine galvanische Cr-Schicht, die etwa eine Dicke zwischen 0,1 und 3 µm haben kann, wobei eine Untergrenze von 0,5 µm bzw. eine Obergrenze von 1 µm besonders bevorzugt in Betracht kommt. Hier kann ein konventioneller und durch kommerziell erhältliche Lösungen verfügbarer Glanzchromprozess verwendet werden, weil die seidenmatte Charakteristik der Oberfläche bereits vorhanden ist.The abovementioned sulfamate-Ni layer is preferably protected against environmental influences by means of a further finishing layer, it being understood that this finishing layer can also have a decorative function. Particularly preferred is a galvanic Cr layer, which may have a thickness between 0.1 and 3 microns, with a lower limit of 0.5 microns or an upper limit of 1 micron is particularly preferred. Here, a conventional and available through commercially available solutions gloss chrome process can be used because the satin finish of the surface is already present.

Die Erfindung ist jedoch nicht auf Cr-Schichten eingeschränkt. Es können auch andere dekorative Schichten Verwendung finden, etwa Ag, Au oder Pt-Metalle. In Betracht kommen auch Schwarzchromschichten, Ti-Schichten, insbesondere gesputterte Ti-Schichten, oder auch nichtmetallische Schichten wie (klare) Lacke oder (gesputterte) Keramikschichten.However, the invention is not limited to Cr layers. Other decorative layers may also be used, such as Ag, Au or Pt metals. Also suitable are black chrome layers, Ti layers, in particular sputtered Ti layers, or else non-metallic layers such as (clear) lacquers or (sputtered) ceramic layers.

Die glatte Oberfläche auf dem Werkstück unter der matten Ni-Schicht kann beispielsweise eine polierte Werkstückoberfläche selbst sein oder auch eine aufgebrachte Metallschicht. Wenn hier eine erfindungsgemäß bevorzugte Glanz-Ni-Schicht Verwendung findet, hat diese den besonderen Vorteil, etwaige Oberflächenfehler und -störungen sehr gut einzuebnen. Sie kann also den letztlich den Glanzanteil der fertigen erfindungsgemäßen Metalloberfläche mitbestimmenden Glanz in seiner Qualität verbessern. Galvanische Prozesse für Glanz-Ni-Schichten sind allgemein bekannt und müssen hier nicht im Einzelnen dargelegt werden. Es sind kommerzielle Lösungen verfügbar, die etwa Ni-Sulfat, organische Glanzzusätze und sog. Einebner enthalten können. Geeignete Stromdichten in diesem Bereich liegen bei 1 bis 3 A/dm2. Es kann ferner von Vorteil sein, unter der Glanz-Ni-Schicht schon eine glänzende Metallschicht, etwa eine Cu-Schicht, vorzusehen.The smooth surface on the workpiece under the matte Ni layer may for example be a polished workpiece surface itself or even an applied metal layer. If an inventively preferred gloss Ni layer is used here, this has the particular advantage of very well leveling any surface defects and defects. Thus, it can improve the quality of the final gloss content of the finished metal surface according to the invention. Galvanic processes for bright Ni layers are well known and need not be detailed here. There are commercial solutions available which may include, for example, Ni sulfate, organic brighteners and so-called levelers. Suitable current densities in this range are 1 to 3 A / dm 2 . It may also be advantageous to provide a shiny metal layer, for example a Cu layer, below the glossy Ni layer.

Die matte galvanische Ni-Schicht wird vorzugsweise als an sich bekannte und technisch gut beherrschte Wattsche Ni-Schicht aufgebracht, d. h. als galvanische Ni-Schicht ohne organische Mattierungszusätze. Hierbei entsteht eine mikroskopisch knollenartige Schichtstruktur, bei der sich über die Stromstärke und/oder Beschichtungszeit die Knollengrößen und Knollenabstände einstellen lassen, die letztlich die Mattheit bestimmen. Eine maximale Mattheit entsteht, wenn die Knollen praktisch abstandslos dicht liegen. Hier sind Stromstärken im Bereich von 0,1 bis 2 A/dm2, besser 0,1 bis 1 A/dm2, bevorzugt. Die Schichtstärke der matten Schicht sollte vergleichsweise gering sein und kann zwischen 0,05 und 5 µm liegen, wobei Obergrenzen von 4 µm, 3 µm, 2 µm und besonders bevorzugter Weise 1 µm sowie Untergrenzen von 0,075 µm und besonders bevorzugter Weise 0,1 µm noch günstiger sind. Die Schichtdicke wird letztlich nach optisch/ästhetischen Gesichtspunkten bestimmt.The matte galvanic Ni layer is preferably applied as a known and technically well-controlled Wattsche Ni layer, ie as a galvanic Ni layer without organic matting additives. This creates a microscopic bulbous layer structure, in which the tuber sizes and tuber intervals can be set via the current intensity and / or coating time, which ultimately determine dullness. A maximum dullness arises when the tubers are practically close to each other. Current strengths in the range of 0.1 to 2 A / dm 2 , better 0.1 to 1 A / dm 2 , are preferred here. The layer thickness of the matt layer should be comparatively low and may be between 0.05 and 5 .mu.m, with upper limits of 4 .mu.m, 3 .mu.m, 2 .mu.m and more preferably 1 .mu.m and lower limits of 0.075 .mu.m and more preferably 0.1 .mu.m even cheaper. The layer thickness is ultimately determined by optical / aesthetic considerations.

Die galvanische Abscheidung einer Sulfamat-Ni-Schicht ist ebenfalls konventionell und bekannt. Die entsprechenden Lösungen enthalten Nickelsulfamat, also das Salz der Amidoschwefelsäure. Die Sulfamat-Ni-Schicht verrundet und verstärkt zwar die erwähnte knollenartige oder in anderer Weise matte Ni-Schicht etwas, ebnet sie jedoch nicht wirklich ein. Die Sulfamat-Ni-Schicht verstärkt insbesondere auch die Korngröße, ohne an der oben mit "knollig" bezeichneten Körnigkeit Grundsätzliches zu ändern. Sie erhält also den Mattierungscharakter, erhöht evtl. den Glanz nur ein wenig, sorgt aber vor allem für eine aus Gründen der Stabilität und Belastbarkeit erhöhte Materialstärke und für eine bessere Wischempfindlichkeit bzw. bessere Schmutzabweisungseigenschaften. Die durch die Verrundung verringerte Rauheit bietet Verschmutzungen weniger Halt. Eine günstige Stärke für die Suifamat-Ni-Schicht liegt im Bereich von 5 und 20 µm, wobei eine Untergrenze von 10 bzw. eine Obergrenze von 15 µm bevorzugter sind. Es wurde bereits erwähnt, dass eine schützende Abschlussschicht bevorzugt ist. Wenn die metallische Ni-Farbe von Interesse ist, kann hier auch ein Klarlack Verwendung finden.The electrodeposition of a sulfamate-Ni layer is also conventional and known. The corresponding solutions contain nickel sulfamate, that is, the salt of amidosulfuric acid. Although the sulphamate Ni layer rounds and reinforces the aforementioned bulbous or otherwise matte Ni layer, it does not really level it. In particular, the sulfamate-Ni layer also enhances the grain size without changing fundamentals on the granularity described above as "nodular". It thus receives the matte character, possibly only slightly increases the gloss, but above all provides increased material strength for reasons of stability and resilience and for better wiping sensitivity or better dirt-repellent properties. The roughness reduced by the rounding provides less grip to soiling. A favorable thickness for the suifamate Ni layer is in the range of 5 and 20 microns, with a lower limit of 10 and an upper limit of 15 microns are more preferred. It has already been mentioned that a protective topcoat is preferred. If the metallic Ni color is of interest, a clearcoat can also be used here.

Ein besonderer Vorteil der Erfindung besteht neben den guten optischen Eigenschaften und der guten Belastbarkeit und Schmutzunempfindlichkeit erfindungsgemäßer Oberflächen darin, dass durch galvanische Parameter in sehr einfacher Weise der Glanzgrad bzw. Mattheitsgrad eingestellt werden kann. Es können mit ein und demselben Grundprozess, also gleich bleibenden Lösungszusammensetzungen, identischen Bädern usw., unterschiedliche optische Eigenschaften erzeugt werden. Insbesondere kann von Charge zu Charge einfach über die Stromstärke, oder noch günstiger über die Behandlungszeit, die Mattheit eingestellt werden. Je dicker die matte Ni-Schicht ist, umso höher ergibt sich der Mattheitsgrad.A particular advantage of the invention, in addition to the good optical properties and the good resilience and dirt resistance of surfaces according to the invention is that can be adjusted by galvanic parameters in a very simple manner, the degree of gloss or matte degree. Different optical properties can be generated with one and the same basic process, that is, the same solution compositions, identical baths, etc. In particular, from batch to batch simply over the amperage, or even cheaper about the treatment time, the dullness are set. The thicker the matte Ni layer, the higher the matte degree.

Die Erfindung wird im Folgenden anhand eines Ausführungsbeispiels näher erläutert, das in den Figuren schematisch dargestellt ist.The invention will be explained in more detail below with reference to an exemplary embodiment, which is shown schematically in the figures.

Die Figuren 1 - 5 zeigen verschiedene Zwischenstadien eines erfindungsgemäßen Verfahrens.Figures 1 - 5 show various intermediate stages of a method according to the invention.

Als Ausführungsbeispiel wird ein innerer Türgriff eines Pkw aus Kunststoff seidenmatt metallisiert. Figur 1 zeigt schematisch eine Oberfläche des Kunststofftürgriffs 1. Auf diese Oberfläche wird gemäß Figur 2 in an sich bekannter Weise eine Glanz-Ni-Schicht 2 abgeschieden. Dazu kann die Oberfläche des Kunststofftürgriffs zuvor bekeimt und beispielsweise mit einer chemisch abgeschiedenen dünnen Metallschicht für den Galvanikprozess vorbereitet werden.As an exemplary embodiment, an inner door handle of a passenger car made of plastic is metallized silk matt. FIG. 1 schematically shows a surface of the plastic door handle 1. On this surface, according to FIG. 2, a glossy Ni layer 2 is deposited in a manner known per se. For this purpose, the surface of the plastic door handle can be previously germinated and prepared, for example, with a chemically deposited thin metal layer for the electroplating process.

Die Glanz-Ni-Schicht 2 wird in einem Standardgalvanikprozess bei 2 A/dm2 aus einer wässrigen Lösung abgeschieden, die etwas 180 g/l Nickelsulfat, etwa 150 g/l Nickelchlorid und etwa 50 g/l Borsäure als pH-Puffer sowie bei Glanz-Ni-Bädern handelsübliche organische Glanzzusätze enthält. Beispielsweise kommt das Bad Slotonik-50 der Fa. Schlötter in Betracht.The glossy Ni layer 2 is deposited in a standard electroplating process at 2 A / dm 2 from an aqueous solution containing about 180 g / l nickel sulfate, about 150 g / l nickel chloride and about 50 g / l boric acid as a pH buffer and at Gloss Ni baths contains commercially available organic brighteners. For example, the bath Slotonik-50 of the company Schlötter comes into consideration.

Die Glanz-Ni-Schicht 2 hat die Aufgabe eine möglichst fehlerfreie glänzende Grundlage bereitzustellen und zeichnet sich durch ihre guten Fähigkeiten zur Einebnung anfänglich vorhandener lmperfektionen aus. Ihre Dicke ist für das nachfolgende Verfahren nicht wirklich wesentlich und hängt einerseits von der angestrebten Gesamtmaterialdicke, vor allem auch im Hinblick auf Strapazierfähigkeit, und von den einzuebnenden Oberflächenfehlern ab. Typische Größenordnungen liegen im Bereich von 10-30 µm.The purpose of the glossy Ni layer 2 is to provide a glossy base that is as error-free as possible, and is distinguished by its good ability to level initially existing imperfections. Their thickness is not really essential to the subsequent process and depends, on the one hand, on the overall material thickness targeted, especially with regard to durability, and on the surface defects to be leveled. Typical orders of magnitude are in the range of 10-30 microns.

Auf der Glanz-Ni-Schicht 2 wird gemäß Figur 3 eine matte Wattsche Ni-Schicht 3 aufgebracht. Dies erfolgt bei einer Stromdichte von etwa 0,5 A/dm2 aus einer wässrigen Lösung mit 210 g/l Nickelsulfat, 35 g/l Nickelchlorid und 40 g/l Borsäure ohne weitere Zusätze. Der bevorzugte Schichtdickenbereich liegt zwischen 0,1 und 1 µm, wobei über die Schichtdicke die Mattheit der letztlich resultierenden Schicht eingestellt wird. Bei diesem Ausführungsbeispiel werden 0,2 µm abgeschieden.On the glossy Ni layer 2, according to FIG. 3, a matt wadding Ni layer 3 is applied. This is carried out at a current density of about 0.5 A / dm 2 from an aqueous solution containing 210 g / l nickel sulfate, 35 g / l nickel chloride and 40 g / l boric acid without further additives. The preferred layer thickness range is between 0.1 and 1 μm, wherein the mattness of the finally resulting layer is adjusted via the layer thickness. In this embodiment, 0.2 microns are deposited.

Figur 3 veranschaulicht, dass diese Schichtstärke nur im Sinne einer Mittelwertsbildung sinnvoll ist. Tatsächlich erfolgt das Wachstum stark körnig oder "knollenartig", wobei die in Figur 3 schematisch eingezeichneten einzelnen Körner mit zunehmender gemittelter Schichtdicke größer werden und abnehmende mittlere Abstände haben. Bei deutlich größeren Schichtdicken liegen die Körner letztlich dicht vor, wodurch sich eine matte Schicht ergibt, die den Glanz der darunter liegenden Glanz-Ni-Schicht 2 nicht mehr hindurch lässt.FIG. 3 illustrates that this layer thickness only makes sense in terms of averaging. In fact, the growth is very grainy or "bulbous", the individual grains shown schematically in Figure 3 with increasing average layer thickness are larger and have decreasing average distances. At significantly greater layer thicknesses, the grains are finally close, resulting in a matte layer that does not let the gloss of the underlying gloss Ni layer 2 through.

Im nächsten Schritt, der in Figur 4 veranschaulicht ist, wird eine Sulfamat-Ni-Schicht 4 auf der Wattschen Ni-Schicht 3 abgeschieden. Die Körner werden hierdurch verstärkt, die Ecken etwas verrundet und insbesondere die am Rande der Körner liegenden Nischen und Winkel ausgefüllt.In the next step, illustrated in FIG. 4, a sulfamate Ni layer 4 is deposited on the Watt Ni layer 3. The grains are thereby reinforced, rounded the corners a bit and in particular the niches and angles lying on the edge of the grains filled.

Hier wird bei einer galvanischen Stromdichte von 1 A/dm2 eine 12 µm starke Schicht abgeschieden. Die wässrige Lösung enthält 36 Vol.-% 60 Gew.-%ige Nickelsulfamatlösung. Die galvanische Lösung enthält 5 g/l Nickelchlorid und 35 g/l Borsäure. In Betracht kommt beispielsweise das Bad Schlötter MS.Here, a 12 μm thick layer is deposited at a galvanic current density of 1 A / dm 2 . The aqueous solution contains 36% by volume of 60% by weight nickel sulphamate solution. The galvanic solution contains 5 g / l nickel chloride and 35 g / l boric acid. Considered, for example, the bathroom Schlötter MS.

Schließlich wird darauf, wie Figur 5 zeigt, optional eine Abschlussschicht aufgebracht. Bei diesem Ausführungsbeispiel handelt es sich dabei um eine übliche Glanz-Cr-Schicht 5 der Stärke 1,5µm. Hier kommt das Schlötter-Bad Slotochrom GC10 mit sechswertigem Cr oder Slotochrom 50 mit dreiwertigem Cr in Betracht.Finally, as shown in FIG. 5, a finishing layer is optionally applied. In this embodiment, this is a conventional gloss Cr layer 5 of thickness 1.5 .mu.m. Here is the Schlötter-Bad slotochrome GC10 with hexavalent Cr or Slotochrom 50 with trivalent Cr into consideration.

Damit ist die Gesamtschicht in Folge der Eigenschaften der Cr-Oberfläche gut gegen Umwelteinflüsse geschützt und oxidationsbeständig. Sie zeigt letztlich einen metallischen Cr-Glanz, der hier erwünscht ist. In Folge der etwas verrundenden Eigenschaften der Sulfamat-Ni-Schicht sind die Schmutzempfindlichkeit und die Rauheit deutlich verbessert und für Anwendungen im Innenraum von Kraftfahrzeugen gut geeignet.As a result of the properties of the Cr surface, the overall layer is well protected against environmental influences and resistant to oxidation. It ultimately shows a metallic Cr gloss, which is desirable here. Due to the somewhat rounding properties of the sulfamate-Ni layer, the sensitivity to dirt and the roughness are significantly improved and well suited for applications in the interior of motor vehicles.

Nach Wunsch können natürlich auch andere Abschlussschichten und damit andere Färbungen verwendet werden. Dies ändert am Grundprinzip der Erzeugung eines Seidenglanzes durch das Zusammenwirken einer glänzenden Metallschicht, hier der Glanz-Ni-Schicht, und einer darauf liegenden matten Ni-Schicht vergleichsweise geringer Stärke, nichts.If desired, of course, other top coats and thus other colors can be used. This changes the basic principle of generating a Silky sheen through the interaction of a shiny metal layer, here the glossy Ni layer, and a lying on top of it matte Ni layer of comparatively low strength, nothing.

Insgesamt handelt es sich bei dem Ausführungsbeispiel um eine einfache Prozessführung mit einer Kontrolle der wesentlichen Schichteigenschaften über die Behandlungszeit, insbesondere einer Kontrolle der Mattheit des resultierenden Seidenglanzes über die Zeit des Wattschen Nickelprozesses. Die geschilderten Nachteile organischer Mattierungszusätze entfallen. Der Prozess ist damit praxistauglich, gut reproduzierbar und kostengünstig.Overall, the exemplary embodiment is a simple process control with a control of the essential layer properties over the treatment time, in particular a control of the mattness of the resulting silk gloss over the time of the Watt's nickel process. The described disadvantages of organic matting additives omitted. The process is thus practicable, easy to reproduce and inexpensive.

Claims (14)

Verfahren zum Herstellen einer seidenmatten Metalloberfläche auf einem Werkstück (1) mit den Schritten: - Herstellen einer glatten Oberfläche (2) auf einem Werkstück (1), - Aufbringen einer matten Ni-Schicht (3) durch galvanische Abscheidung ohne organische Mattierungszusätze, - Aufbringen einer Sulfamat-Ni-Schicht (4). Method of producing a semi-matt metal surface on a workpiece (1) comprising the steps: - producing a smooth surface (2) on a workpiece (1), Application of a matt Ni layer (3) by electrodeposition without organic matting additives, - Applying a sulfamate-Ni layer (4). Verfahren nach Anspruch 1, mit dem zusätzlichen Schritt: Aufbringen einer weiteren Abschlussschicht (5) auf der Sulfamat-Ni-Schicht (4).The method of claim 1, further comprising the step of: applying a further capping layer (5) on the sulfamate Ni layer (4). Verfahren nach Anspruch 2, bei dem die Abschlussschicht eine galvanische Cr-Schicht (5) ist.The method of claim 2, wherein the cap layer is a Cr Cr layer (5). Verfahren nach Anspruch 2 oder 3, bei dem die Abschlussschicht (5) zwischen 0,1 und 3 µm stark ist.Method according to claim 2 or 3, wherein the finishing layer (5) is between 0.1 and 3 μm thick. Verfahren nach einem der vorstehenden Ansprüche, bei dem die glatte Werkstückoberfläche durch galvanische Abscheidung einer Glanz-Ni-Schicht (2) hergestellt wird.Method according to one of the preceding claims, in which the smooth workpiece surface is produced by electrodeposition of a bright Ni layer (2). Verfahren nach Anspruch 5, bei dem die Stromdichte auf dem Werkstück während der galvanischen Abscheidung zwischen 1 und 3 A/dm2 beträgt.Method according to Claim 5, in which the current density on the workpiece during the electrodeposition is between 1 and 3 A / dm 2 . Verfahren nach einem der vorstehenden Ansprüche, bei dem die matte Ni-Schicht als Wattsche Ni-Schicht (3) aufgebracht wird.Method according to one of the preceding claims, in which the matt Ni layer is applied as a wadding Ni layer (3). Verfahren nach Anspruch 7, bei dem die Stromdichte auf dem Werkstück während dem Aufbringen der Wattschen Ni-Schicht (3) zwischen 0,1 und 2 A/dm2 beträgt.A method according to claim 7, wherein the current density on the workpiece during the application of the Watt-Ni layer (3) is between 0.1 and 2 A / dm 2 . Verfahren nach einem der vorstehenden Ansprüche, bei dem die matte Ni-Schicht (3) zwischen 0,05 und 5 µm stark ist.Method according to one of the preceding claims, in which the matt Ni layer (3) is between 0.05 and 5 μm thick. Verfahren nach einem der vorstehenden Ansprüche, bei dem die Stromdichte auf dem Werkstück während dem Aufbringen der Sulfamat-Ni-Schicht (4) zwischen 0,1 und 2 A/dm2 beträgt.Method according to one of the preceding claims, wherein the current density on the workpiece during the application of the sulfamate-Ni layer (4) is between 0.1 and 2 A / dm 2 . Verfahren nach einem der vorstehenden Ansprüche, bei dem die Sulfamat-Ni-Schicht (4) zwischen 5 und 20 µm stark ist.A method according to any one of the preceding claims, wherein the sulfamate Ni layer (4) is between 5 and 20 μm thick. Verfahren nach einem der vorstehenden Ansprüche, bei dem das Werkstück ein Automobilteil (1) ist und die seidenmatte Metalloberfläche eine dekorative Oberfläche des Automobilteils (1) ist, insbesondere für den Innenraum eines Automobils.A method according to any one of the preceding claims, wherein the workpiece is an automobile part (1) and the semi-gloss metal surface is a decorative surface of the automobile part (1), especially for the interior of an automobile. Verfahren zur Herstellung seidenmatter Metalloberflächen auf einer Mehrzahl Werkstücke (1) beinhaltend ein Verfahren nach einem der vorstehenden Ansprüche, wobei die hergestellten Metalloberflächen (1) unterschiedlich matt sind und die unterschiedlichen Mattheiten durch unterschiedliche Stärken der matten Ni-Schicht (3) eingestellt werden.Method for producing semi-matt metal surfaces on a plurality of workpieces (1) comprising a method according to one of the preceding claims, wherein the metal surfaces (1) produced are differently matted and the different mattnesses are adjusted by different thicknesses of the matt Ni layer (3). Verfahren nach Anspruch 13, bei dem die jeweiligen Stärken der matten Ni-Schicht (3) über die Zeitdauer der galvanischen Abscheidung eingestellt werden.A method according to claim 13, wherein the respective thicknesses of the matte Ni layer (3) are adjusted over the period of the electrodeposition.
EP05109770A 2005-10-20 2005-10-20 Manufacturing process for satin-matt surface Not-in-force EP1780311B1 (en)

Priority Applications (6)

Application Number Priority Date Filing Date Title
EP05109770A EP1780311B1 (en) 2005-10-20 2005-10-20 Manufacturing process for satin-matt surface
DE502005004040T DE502005004040D1 (en) 2005-10-20 2005-10-20 Production of semi-gloss metal surfaces
ES05109770T ES2306023T3 (en) 2005-10-20 2005-10-20 PRODUCTION OF MATE METAL SURFACES LIKE SILK.
AT05109770T ATE394526T1 (en) 2005-10-20 2005-10-20 PRODUCTION OF SILK-MATTE METAL SURFACES
US12/083,843 US8105473B2 (en) 2005-10-20 2006-10-20 Production of satin metal surfaces
PCT/EP2006/067618 WO2007045688A1 (en) 2005-10-20 2006-10-20 Production of silky matter of metal surfaces

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP05109770A EP1780311B1 (en) 2005-10-20 2005-10-20 Manufacturing process for satin-matt surface

Publications (2)

Publication Number Publication Date
EP1780311A1 true EP1780311A1 (en) 2007-05-02
EP1780311B1 EP1780311B1 (en) 2008-05-07

Family

ID=35976738

Family Applications (1)

Application Number Title Priority Date Filing Date
EP05109770A Not-in-force EP1780311B1 (en) 2005-10-20 2005-10-20 Manufacturing process for satin-matt surface

Country Status (6)

Country Link
US (1) US8105473B2 (en)
EP (1) EP1780311B1 (en)
AT (1) ATE394526T1 (en)
DE (1) DE502005004040D1 (en)
ES (1) ES2306023T3 (en)
WO (1) WO2007045688A1 (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014180537A1 (en) * 2013-05-10 2014-11-13 Oerlikon Trading Ag, Trübbach Gloss degree adjustment of plastics substrates having a metallic finish
EP3170925A1 (en) * 2015-11-23 2017-05-24 Franz GmbH Method for producing a metal surface

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2488560A (en) * 2011-03-01 2012-09-05 Bentley Motors Ltd Vehicle trim components
US8529747B2 (en) * 2011-07-12 2013-09-10 The Boeing Company Methods for repairing steel components
FR3004735B1 (en) * 2013-04-23 2015-07-03 Dourdin PROCESS FOR REALIZING METALLIC PARTS
CN110760789A (en) * 2019-11-04 2020-02-07 丽水市建川五金制造有限公司 Surface fine treatment process for surface treatment door handle

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3152971A (en) * 1960-07-26 1964-10-13 Udylite Corp Electrodeposition of fine-grained lustrous nickel
GB1074389A (en) * 1964-12-15 1967-07-05 Res Holland Nv Improvements in or relating to nickel electro plating
US3449223A (en) * 1962-05-30 1969-06-10 Jules Marie Odekerken Method for covering objects with a decorative bright nickel/chromium coating,as well as objects covered by applying this method
US3644183A (en) * 1963-01-09 1972-02-22 Res Holland Nv Process for coating an object with a bright nickel/chromium coatin
GB1515361A (en) * 1975-07-09 1978-06-21 Electrofoils Ltd Metal finishing of metallic foils by electrodeposition
EP0431228A1 (en) * 1988-06-09 1991-06-12 Kanto Kasei Co., Ltd. Method of copper-nickel-chromium bright electroplating which provides excellent corrosion resistance and plating film obtained by the method
WO2004090198A2 (en) * 2003-04-11 2004-10-21 Hille & Müller GMBH Electrolytically coated cold-rolled strip, preferably to be used for the production of battery shells, and method for coating the same

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US926800A (en) * 1908-08-31 1909-07-06 Henry V Young Cover for automobile transmission-gears.
US3090733A (en) * 1961-04-17 1963-05-21 Udylite Res Corp Composite nickel electroplate
AU2003901058A0 (en) * 2003-03-10 2003-03-20 Microtechnology Centre Management Limited Electroplating pcb components

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3152971A (en) * 1960-07-26 1964-10-13 Udylite Corp Electrodeposition of fine-grained lustrous nickel
US3449223A (en) * 1962-05-30 1969-06-10 Jules Marie Odekerken Method for covering objects with a decorative bright nickel/chromium coating,as well as objects covered by applying this method
US3644183A (en) * 1963-01-09 1972-02-22 Res Holland Nv Process for coating an object with a bright nickel/chromium coatin
GB1074389A (en) * 1964-12-15 1967-07-05 Res Holland Nv Improvements in or relating to nickel electro plating
GB1515361A (en) * 1975-07-09 1978-06-21 Electrofoils Ltd Metal finishing of metallic foils by electrodeposition
EP0431228A1 (en) * 1988-06-09 1991-06-12 Kanto Kasei Co., Ltd. Method of copper-nickel-chromium bright electroplating which provides excellent corrosion resistance and plating film obtained by the method
WO2004090198A2 (en) * 2003-04-11 2004-10-21 Hille & Müller GMBH Electrolytically coated cold-rolled strip, preferably to be used for the production of battery shells, and method for coating the same

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014180537A1 (en) * 2013-05-10 2014-11-13 Oerlikon Trading Ag, Trübbach Gloss degree adjustment of plastics substrates having a metallic finish
RU2672058C2 (en) * 2013-05-10 2018-11-09 Эрликон Серфиз Солюшнз Аг, Пфеффикон Gloss degree adjustment of plastic substrates having metallic finish
US10273576B2 (en) 2013-05-10 2019-04-30 Oerlikon Surface Solutions Ag, Pfaffikon Gloss degree adjustment of plastics substrates having a metallic finish
EP3170925A1 (en) * 2015-11-23 2017-05-24 Franz GmbH Method for producing a metal surface
WO2017088982A1 (en) * 2015-11-23 2017-06-01 Franz GmbH Method for producing a metal surface
EP3604623A1 (en) * 2015-11-23 2020-02-05 Franz GmbH Method for producing a metal surface

Also Published As

Publication number Publication date
ES2306023T3 (en) 2008-11-01
US20090211913A1 (en) 2009-08-27
EP1780311B1 (en) 2008-05-07
DE502005004040D1 (en) 2008-06-19
US8105473B2 (en) 2012-01-31
ATE394526T1 (en) 2008-05-15
WO2007045688A1 (en) 2007-04-26

Similar Documents

Publication Publication Date Title
EP1780311B1 (en) Manufacturing process for satin-matt surface
DE2555834C2 (en) Process for the electrodeposition of chromium
DE102004041813A1 (en) Surface having an adhesion reducing microstructure and method of making the same
EP1798313B1 (en) Process for depositing crack-free, corrosion resistant and hard chromium and chromium alloy layers
DE1771323A1 (en) Process for coating metal surfaces with a fluorine-containing polymer
EP1587968A2 (en) Coating method
DE3933896C1 (en)
DE3230805A1 (en) OBJECT WITH A MULTI-LAYER GALVANICALLY DEPOSIT COVER AND A METHOD FOR PRODUCING THIS OBJECT
DE69008359T2 (en) METHOD FOR DEPOSITING COATING LAYERS ON ANODISABLE METAL SUBSTRATES AND PRODUCTS OBTAINED BY THEM.
EP1918425B1 (en) Greyish chromium surface
EP1876268B1 (en) Black chromium process free of Cr-VI
DE69112507T2 (en) Complete coating process.
DE1177451B (en) Metal object coated with several metallic layers to protect against atmospheric corrosion
DE202011103736U1 (en) Galvanically coated component
EP3170925B1 (en) Method for producing a metal surface
DE4011201C1 (en) Coating workpiece with chromium for improved corrosion resistance - comprises using aq. electrolyte soln. contg. chromic acid sulphate ions, and fluoro:complexes to increase deposition
EP3312307A1 (en) Method for efficient black chromium plating i
DE1163115B (en) Process for the production of corrosion-resistant galvanic coatings from chromium with the aid of intermediate layers
DE3830277C2 (en) Calibration tool and method for its manufacture
DE2237834A1 (en) ITEM MADE OF A METALLIC BASE BODY WITH A METALLIC COATING
DE19931915A1 (en) Process for anodizing a surface e.g. aluminum parts for vehicles comprises pickling the surface, and anodizing the surface to form an anodized layer on the surface
WO2008037501A2 (en) Method for applying a nickel layer with fluoropolymer particles
DE2030295A1 (en) Decorative micropore chromium coating - electroplated on bright and
DE1621156A1 (en) Process for electroplating plastic parts
DE102015011404A1 (en) Component for an operating device of a motor vehicle with a partially structured surface

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU LV MC NL PL PT RO SE SI SK TR

AX Request for extension of the european patent

Extension state: AL BA HR MK YU

17P Request for examination filed

Effective date: 20070327

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

AKX Designation fees paid

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU LV MC NL PL PT RO SE SI SK TR

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU LV MC NL PL PT RO SE SI SK TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

Free format text: NOT ENGLISH

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

Free format text: LANGUAGE OF EP DOCUMENT: GERMAN

REF Corresponds to:

Ref document number: 502005004040

Country of ref document: DE

Date of ref document: 20080619

Kind code of ref document: P

REG Reference to a national code

Ref country code: CH

Ref legal event code: NV

Representative=s name: BOVARD AG PATENTANWAELTE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20080507

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20080507

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20080507

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2306023

Country of ref document: ES

Kind code of ref document: T3

NLV1 Nl: lapsed or annulled due to failure to fulfill the requirements of art. 29p and 29m of the patents act
PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: PL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20080507

Ref country code: LV

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20080507

REG Reference to a national code

Ref country code: IE

Ref legal event code: FD4D

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20080907

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20080507

Ref country code: LT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20080507

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20080507

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20080507

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20080807

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20080507

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20081007

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20080507

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed

Effective date: 20090210

BERE Be: lapsed

Owner name: FRANZ, WOLF-DIETER

Effective date: 20081031

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20080807

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20080507

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MC

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20081031

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20081031

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20081020

Ref country code: HU

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20081108

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20080507

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: TR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20080507

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20080808

REG Reference to a national code

Ref country code: CH

Ref legal event code: PFA

Owner name: FRANZ, WOLF-DIETER

Free format text: FRANZ, WOLF-DIETER#BRAHMSWEG 15#82538 GERETSRIED (DE) -TRANSFER TO- FRANZ, WOLF-DIETER#BRAHMSWEG 15#82538 GERETSRIED (DE)

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: ES

Payment date: 20121023

Year of fee payment: 8

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20150709

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20131021

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 11

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 12

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 13

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 14

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: IT

Payment date: 20191021

Year of fee payment: 15

Ref country code: FR

Payment date: 20191022

Year of fee payment: 15

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20191023

Year of fee payment: 15

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20201020

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20201031

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20201020

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20201020

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: AT

Payment date: 20211001

Year of fee payment: 17

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: CH

Payment date: 20211001

Year of fee payment: 17

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20220518

Year of fee payment: 18

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

REG Reference to a national code

Ref country code: AT

Ref legal event code: MM01

Ref document number: 394526

Country of ref document: AT

Kind code of ref document: T

Effective date: 20221020

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20221031

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20221031

Ref country code: AT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20221020

REG Reference to a national code

Ref country code: DE

Ref legal event code: R119

Ref document number: 502005004040

Country of ref document: DE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20240501