EP1780311A1 - Manufacturing process for satin-matt surface - Google Patents
Manufacturing process for satin-matt surface Download PDFInfo
- 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
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- 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.)
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 6
- 238000000034 method Methods 0.000 claims abstract description 35
- 239000002184 metal Substances 0.000 claims abstract description 14
- 229910052751 metal Inorganic materials 0.000 claims abstract description 14
- 239000000654 additive Substances 0.000 claims description 8
- 238000004070 electrodeposition Methods 0.000 claims description 6
- IIACRCGMVDHOTQ-UHFFFAOYSA-M sulfamate Chemical compound NS([O-])(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-M 0.000 claims description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 abstract description 44
- 239000011248 coating agent Substances 0.000 abstract description 3
- 238000000576 coating method Methods 0.000 abstract description 3
- 238000009713 electroplating Methods 0.000 abstract description 3
- KERTUBUCQCSNJU-UHFFFAOYSA-L nickel(2+);disulfamate Chemical compound [Ni+2].NS([O-])(=O)=O.NS([O-])(=O)=O KERTUBUCQCSNJU-UHFFFAOYSA-L 0.000 abstract description 3
- 229910052759 nickel Inorganic materials 0.000 abstract description 2
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 8
- 230000007547 defect Effects 0.000 description 5
- 230000003287 optical effect Effects 0.000 description 5
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 3
- 239000004327 boric acid Substances 0.000 description 3
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 2
- 239000006259 organic additive Substances 0.000 description 2
- 238000005488 sandblasting Methods 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 238000012935 Averaging Methods 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000004922 lacquer Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000006174 pH buffer Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000005871 repellent Substances 0.000 description 1
- 230000000284 resting effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- IIACRCGMVDHOTQ-UHFFFAOYSA-N sulfamic acid Chemical compound NS(O)(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
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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
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/10—Electroplating with more than one layer of the same or of different metals
- C25D5/12—Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium
- C25D5/14—Electroplating 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
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/60—Electroplating characterised by the structure or texture of the layers
- C25D5/605—Surface topography of the layers, e.g. rough, dendritic or nodular layers
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/60—Electroplating characterised by the structure or texture of the layers
- C25D5/605—Surface topography of the layers, e.g. rough, dendritic or nodular layers
- C25D5/611—Smooth layers
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/627—Electroplating 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.
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- Organic Chemistry (AREA)
- Electroplating Methods And Accessories (AREA)
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Abstract
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
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
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
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
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
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
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)
Priority Applications (6)
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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 |
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EP05109770A EP1780311B1 (en) | 2005-10-20 | 2005-10-20 | Manufacturing process for satin-matt surface |
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EP1780311A1 true EP1780311A1 (en) | 2007-05-02 |
EP1780311B1 EP1780311B1 (en) | 2008-05-07 |
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US (1) | US8105473B2 (en) |
EP (1) | EP1780311B1 (en) |
AT (1) | ATE394526T1 (en) |
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ES (1) | ES2306023T3 (en) |
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
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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)
Publication number | Priority date | Publication date | Assignee | Title |
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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 |
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- 2005-10-20 ES ES05109770T patent/ES2306023T3/en active Active
- 2005-10-20 AT AT05109770T patent/ATE394526T1/en active
- 2005-10-20 DE DE502005004040T patent/DE502005004040D1/en active Active
- 2005-10-20 EP EP05109770A patent/EP1780311B1/en not_active Not-in-force
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Also Published As
Publication number | Publication date |
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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 |
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