WO2007057478A1 - Part having an outer polymer surface with a metallic finish, production method thereof and use of same - Google Patents

Part having an outer polymer surface with a metallic finish, production method thereof and use of same Download PDF

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Publication number
WO2007057478A1
WO2007057478A1 PCT/ES2005/000618 ES2005000618W WO2007057478A1 WO 2007057478 A1 WO2007057478 A1 WO 2007057478A1 ES 2005000618 W ES2005000618 W ES 2005000618W WO 2007057478 A1 WO2007057478 A1 WO 2007057478A1
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Prior art keywords
layer
carbon
diamond
outer surface
part according
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PCT/ES2005/000618
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Spanish (es)
French (fr)
Inventor
Josu Goikoetxea Larrinaga
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Fundacion Tekniker
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    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/26Deposition of carbon only

Abstract

The invention relates to a part having an outer polymer surface with a metallic finish, including at least one doped or non-doped diamond-like carbon (DLC) film which is deposited on the outer polymer surface using vapour phase deposition techniques. The DLC film provides the part with a metallic finish and imperviousness to organic solvents, as well as good resistance to corrosion, abrasion, moisture, thermal shocks and, in general, to any other agents to which it may be exposed during normal use. In turn, said DLC film can be coated with a decorative metallic film. The invention also relates to a method of producing the aforementioned part as well as the use of same in decorative elements having a metallic appearance.

Description

PART WITH OUTER SURFACE POLIMÉR1CA metallic finish. METHOD FOR MANUFACTURING AND USES THEREOF

FIELD OF THE INVENTION The present invention belongs to the field of coatings. More particularly, the invention relates to a polymeric piece with outer surface which is coated with a layer of diamond-like carbon, and to a process for their manufacture and use of the same. Said coated part having a metallic finish, and adequate resistance to corrosion and other agents to which it is exposed during normal use, particularly to organic solvents.

BACKGROUND OF THE INVENTION

Currently, the conventional method of fabricating a part with polymeric outer surface of metallic finish that has a suitable resistance to corrosion and other agents, consists of applying a succession of metal coatings by plating baths. Typically, a first copper coating of about 10 microns, then a nickel coating of about 20 microns and finally a coating of about 0.3 microns chromium is applied. Besides this electrolytic process, a number of processes in which a metallic finish a piece with outer surface polymer through the use of thin coatings applied by PVD (Physical Vapor Deposition) is conferred are known, within which techniques are encompassed thermal evaporation, sputtering, ion plating or cathodic arc. The advantage of these coatings applied by PVD is that the thickness of metal applied can be very small, about 0.1 microns, for which reason the use of metals which can be polluting and harmful to health of workers and Ia users is reduced in a large proportion. However, currently the use of PVD coatings for these applications is very limited, mainly due to not being able to achieve the level of performance demanded Ia majority of these metallic coatings.

One of the requirements to be met by a coating of this type is to present sufficient resistance to corrosion caused by the environment or by attack from chemicals included in the formulation of products that could reasonably be used for cleaning. To ensure adequate strength in this direction there are a number of patents in which the thin coating applied by PVD is internally protected by a lacquer or basecoat which Ia waterproofed substances could issue plastic and externally by other lacquer, or topcoat, which waterproofs Ia abroad. Thus, the patent US 3,783,012 Morita et al., June 1974, and presented a process in which an undercoat on a plastic substrate is applied, on which a reflective layer of aluminum was deposited by thermal evaporation and subsequently protected the assembly with a new lacquer. 4,039,722 US patent Dickie et al., August 1977, improved this patent by employing a ultraviolet curing lacquer formulation specified for the basecoat and topcoat for. Japanese Patent 53-61194 subsequently Ia of Soshiki et al., May 1978, in turn improved the existing patents by the application of the layer of reflective chromium sputtering, followed by the application of a specific lacquer composition had a adequate resistance to UV yellowing. This line of development which employs a protective lacquer coating applied to the PVD has known a large back development by many patents, such as for example DE 42 09 406 or DE 197 02 566 Ia.

Although a resistance to corrosion that may be sufficient for some applications, Ia most applications of plastic parts metallized can not use this type of PVD coating with subsequent lacquering because the upper lacquer does not achieve even the level of resistance providing metallized conventional electrolytic and, in particular, it is often insufficient in resistance to abrasion, or other solvents.

Moreover, there are also patents that hard chromium coatings, or nitrides or carbonitrides of transition metals on plastic parts in which these coatings are left unprotected with a lacquer, applied on the basis Ia high resistance to corrosion presenting these compounds. Of this type are, for example, the US 6,399,219 or US patent, patent GB2358196 English. The latter, in particular, ensures create a barrier to the diffusion of water vapor from the piece with polymeric outer surface to the vacuum by means of a chromium layer applied by PVD on specific conditions. As is well known, precisely Ia excellent resistance to corrosion of the layers of electrolytic chromium applied on nickel are based largely on that chromium has a natural tendency to microfracturarse and, consequently, has a dense network of microcracks on the surface of nickel, on an attack of the corrosion of diffuse occurs and it is this diffuse nature of the corrosion attack causing Ia the high resistance to corrosion of nickel layers with microfracturado chromium. This natural tendency to microfracturarse of chromium coatings makes obtaining sealing layers which can be used as diffusion barriers, as mentioned in patent GB2358196, resulting very complicated, with difficulties in reproduclbilidad results. Consequently, most common Io is that such layers present microfractures through which a liquid can penetrate and enter the plastic substrate. Because of that this type of PVD coatings applied directly on plastic parts are not able to provide that necessary resistance to overcome a common test in industries that manufacture plastic parts metallized, which involves rubbing the metal coating with a cloth soaked in ethanol, exerting a given pressure for a number of cycles. In this type of test, ethanol penetrates through microfractures having the PVD coating, access the surface of the piece with outer surface polymer whose chemical nature has been altered by sputtering which has undergone during the start of the coating, and this etched surface, causing weakening, Io that, combined with the strong intrinsic stresses PVD coating, causes this to detach from the plastic substrate.

In turn, patent US 6,399,219 avoids the formation of microfractures, or grain boundaries extending across width Ia PVD coating by means of stacking a plurality of coatings of different nature, preferably based on nitrides or carbonitrides and metals alternately, a number that can reach up to 100 layers. Compared to the invention presents the process is complicated, long, does not guarantee fully Ia absence of microcracks extending from the outer surface to Ia interface polymer-PVD and, because the reaction between nitrogen and the carbonaceous gas and the metal used to form the nitride or carbonitride is a highly exothermic reaction, such coatings generates a lot of heat in the polymer surface, so that this often is affected detrimentally, given their limited resistance to temperature compared to metals on which such coatings usually applied.

Thus there is in the state of the art the need for parts coated outer surface polymer which have a metallic finish and high resistance to organic solvents as well as good properties with regard to the adherence of the coating and the resistance thereof to corrosion, to

Ia abrasion to humidity and thermal shock.

The present inventors have found that the coating of a part whose outer surface is polymeric with a layer of diamond-like carbon, called DLC also layer (Diamond like carbon), allows to obtain a finish with metallic appearance and virtually immune and impermeable to organic solvents that also has good properties of resistance to other physical or chemical agents.

This type of coating is applied conventionally in applications that take advantage of their self-lubricating character to reduce friction and wear of the slip elements. Thus, it is well known its application on the surface of the hard drives used to store information, so as to prevent (accidental friction of said surface with the playhead causes deterioration of the surface of the disc and the consequent loss of information or deterioration of the device, as is described, inter alia, in US 5,830,331, US 6,086,796 and US 5,822,153 patents. it is also well known application in mechanical components subject to friction and wear, as mentioned in the patents US 6046758 and US 5593719, or as an antireflective coating for infrared described in patent US 5,502,442. There are also a few patents that Ia use of DLC are mentioned as a barrier against corrosion such as US 6,150,719 patent, US 6,740,393, or US 6,893,720. OBJECT OF THE INVENTION

The present invention therefore aims to provide a piece with polymeric outer surface with a metallic finish comprising at least one layer of diamond-like carbon, doped or not, deposited on said outer surface polymer.

Another object of the invention is a process for manufacturing said part with polymeric outer surface with a metallic finish.

Finally, another object of the invention is the use of said piece with polymeric outer surface with a metallic finish.

DETAILED DESCRIPTION OF THE INVENTION

In one aspect of the invention, integral with outer surface polymer with metallic finish comprising at least one layer of diamond-like carbon, doped or not, deposited on said outer surface polymer is provided (hereinafter "part of the invention") .

In the context of the invention, the term "polymeric piece with outer surface" refers to a fully polymeric part or a piece on which surface is deposited a thermoplastic polymer coating, thermoset or resin.

In a particular embodiment, said outer surface polymer may contain substances customary filling in these applications, preferably mica, talc or glass fiber. This polymer surface may play a role of leveling the surface, or defect coverage, to provide a smooth surface for subsequent coatings.

In a particular embodiment, said workpiece is a non-polymeric part

(Metallic or ceramic, for example) whose outer surface is coated with a polymer layer could be used, for example, to confer on the surface of the piece a shiny, without buffing the surface of the workpiece. In another particular embodiment, said workpiece is a totally polymeric part. Fully polymeric pieces can be of ABS (acrylonitrile-butadiene-styrene), PC (polycarbonate), mixtures thereof, PBT (polybutylene terephthalate), Noryl (mixture of polyphenylene oxide (PPO) and polystyrene) and, in general, other thermoplastics with adequate heat resistance.

Non-polymeric parts may be metal (zamak, aluminum, steel, brass, etc.) or ceramic (alumina, corundum, etc.).

As previously indicated, polymer outside the layer that coats may be a thermoplastic polymer coating, thermosetting resin or the many existing and well known types, but preferred are ultraviolet (UV) curing by enhanced features.

Moreover, the expression "diamond-like carbon" or DLC (Diamond like carbon) refers to a range of metastable materials consisting mainly of amorphous carbon. Some may contain up to 50 atomic% of hydrogen, while others contain less than 1%. DLC contains a significant proportion of sp3 bonds between carbon atoms, which may vary between 50% and 85%, whichever makes diamond-like to a certain degree. It can reach a high hardness, self-lubricating, wear resistance, chemical inertness, optical transparency, and is a semiconductor broadband. They can be doped with many different elements including metals, nitrogen, fluorine or silicon, which purpose joined to the possibility of modifying the ratio of hydrogen and sp3 makes offer a wide variety of properties. reviews the state of the art can be found in A. Grill, Diamond and Related

Materials 8 (1999) 428-434, and J. Robertson, Materials Science and Engineering R

37 (2002) 129-281.

Thus, in a particular embodiment of the part of the invention, the diamond-like carbon layer is doped. In one, the layer of diamond-like carbon preferred embodiment is doped with transition metals, such as, for example, chromium, zirconium, titanium, or other elements such as, for example, silicon, boron, aluminum, fluorine or nitrogen. The layer of diamond-like carbon undoped (hereinafter "DLC") or doped (hereinafter "Me-DLC") must be large enough to be impermeable to solvents thickness, or the amount of solvent Io transferred be as little as not affecting the underlying polymeric surface, for which purpose it may be sufficient to apply a coating of 40 nanometers, depending on the nature specifically on the applied layer, since there is a huge variety of features between different types of DLC layers and me -DLC, depending on the details of the deposition process. Specifically, the coating should be thick enough Io impermeable to exceeding without damage consistent ten test cycles rubbed with cloth soaked in ethanol 50% diluted in water, at a pressure of 900 grams.

Therefore, in a particular embodiment of the part of the invention, the minimum thickness of the layer of diamond-like carbon is 40 nm. The optimal coating thickness is between 100 and 200 nm.

If whichever is desired is applied to the piece glossy black metallic appearance can be applied a second layer of DLC, optimized to give a black color with the hue desired color on the waterproofing DLC ​​coating or even the coating waterproofing can be made sufficiently thick Io to achieve the desired degree of opacity and without any subsequent coating.

Alternatively, it may be applied over the layer of DLC a Io thin enough only to serve to increase brightness, without substantially modifying its black color metallic coating.

Also, on the layer of DLC or Me-DLC, in turn, can be applied any metal coating is required to obtain the desired color, taking care that the DLC present Ia tenacity to the tensions of the metal coating deposited thereon not cause fracture and detachment.

Thus, in another particular embodiment, the piece of the invention further comprises a decorative metal layer deposited on last DLC layer Ia or Me-DLC.

Especially suitable, for its resistance to abrasion and the corrosion are decorative based transition metal layers, in particular chromium, or nitrides, carbides or carbonitrides thereof, with which can be obtained a wide variety of colors including chromium type colors, stainless steel, brass, gold, old gold, bronze or copper. The color layer may be of a thickness between 20 and 200 nanometers, just sufficient to give the required color, or may thicken to increase its resistance to abrasion, in the measurement that tolerates Ia Io tenacity DLC. As noted, the metal coatings also include nitrides, carbides and carbonitrides of transition metals as their conductor and an electrically appearance character make them interchangeable for the purposes pursued by the invention.

Therefore, in another preferred embodiment, said decorative metallic layer is a layer of a transition metal or a nitride, carbide or carbonitride thereof. In a further preferred embodiment, said decorative metallic layer is a layer of chromium, zirconium or titanium, or a nitride, carbide or carbonitride thereof.

The color coating applied on the layer of DLC can lead in turn an applied above that is transparent and present antihuellas properties coating, that is, its surface characteristics are such, referring particularly to the surface energy, fingerprints not they tend to remain visible on its surface.

Thus, in a particular embodiment, the piece of the invention comprises a transparent layer with properties antihuellas deposited on the layer decorative metallic.

Preferably, such coatings are crystallographically amorphous, so that no grain boundaries present which may serve to anchor moisture droplets. Of this type are for example, metal oxide coatings such as, for example, titanium oxide carried out at low temperature, the mixed oxides of aluminum and silicon, or some types of DLC, especially very hydrogenated or, conversely, the lack of hydrogen-rich sp3.

Therefore, in a preferred embodiment, said transparent layer is a layer of a metal oxide or diamond-like carbon.

DLC layer may be adhered to the part with outer surface polymer through an intermediate layer, very thin, which facilitates the adherence and may be a metal layer, one of whose functions is electrically make conductive the polymeric surface whereon it is to be applied layer so that it may be subject an electrical polarization effectively, especially if this is pulsating. For operation, more advantageous Io is used as bonding layer a layer of the same transition metal which is subsequently used to give the metallised, optionally by Io Io more practical is that this layer of Cr, Zr or Ti. The thickness of the layer is simply necessary to facilitate the adherence, therefore they need not be greater than 40 nanometers. This layer is not a protective layer against the diffusion of water in the polymeric material. The positive contribution facing the adherence of this intermediate layer may, in addition to doing conducting the polymeric surface, as mentioned, for reasons of chemical affinity with the substrate and the layer of DLC deposited thereon, due and the cleaning effect of the surface of the polymeric substrate is achieved sputtered during the first phase of the coating or by the beneficial effect on the evolution of the first phase of the coating process caused by the evaporation of pure metal in the chamber, and this reacts with the harmful residual gases remaining in the chamber at the beginning of the coating process, and facilitates the anchoring of the coating takes place in a clean and controlled environment, as described later.

Thus, in another particular embodiment, the piece of the invention comprises an intermediate metal layer between the outer surface of the first layer polymer and diamond like carbon. In another aspect of the invention provides a process for manufacturing a part with outer surface with a metallic finish polymer comprising applying at least one layer of diamond-like carbon on said outer surface by a polymeric deposition technique vapor.

In a particular embodiment of the method of the invention, this technique is a technique of chemical deposition in vapor phase. In another particular embodiment, said technique is a technique of physical vapor phase deposition.

Physical vapor deposition or PVD phase (Physical Vapor Deposition) is a technique of applying coatings in vacuum is characterized by using physical methods for the formation of steam which is then deposited on the parts. The oldest method consists of thermal evaporation, either resistive heating or electron gun. Subsequently, methods employing electric shock for the formation of the steam in the form of large discharges the entire surface of the cathode (sputtering or sputtering, US 4,166,018, US 4,162,954, and J. Vossen and W. Kern "Thin developed film Processes II ", Academic Press, 1991) or by discharges all its intensity concentrated in a single point of the cathode (arc evaporators, US 3,793,179, US 3,836,451, US 4,430,184, and R. Boxman et al," Handbook of

Vacuum Are Science and Technology ", Noyes Pub., 1995). These types of evaporators electric shock require vacuum is not complete, but there is a very tenuous atmosphere that serves as a means for the development of the discharge in the chamber, therefore they usually introduced a controlled suitable for the development of coating gas amount.

Chemical vapor phase deposition or CVD (Chemical Vapor Deposition), (see SMRossnagel, JJCuomo and WD Westwood, ed .: "Handbook of Plasma Processing Technology", Noyes Publications, 1990, and CEMorosanu "Thin Films by Chemical Vapor Deposition" , Elsevier, 1990) is also a vacuum coating technique but in this case the chemical species are deposited are introduced into the reaction chamber as gases. The deposition technique DLC is the application of a radio frequency discharge to a part which is in a vacuum chamber with an atmosphere of a carbonaceous compound which decomposes on the surface of the workpiece by action of the RF discharge, forming the DLC (US 4,382,100). Alternatively, the technique of ion gun (plasma beam source), it is possible to develop an accessory that breaks the discharge gas and the carbonaceous directing the carbonaceous gas activated towards the part to be coated, on which is deposited (US

3,961,103, US 5,482,602).

The DLC coating or Me-DLC is applied by means of PVD techniques, vaporizing graphite by sputtering or cathodic arc, or by CVD techniques, which are based on the decomposition of a gaseous hydrocarbon by effect of an electric shock, or by means combining both effects, as mentioned, for example, in US 6331332 patent document.

The ratio of carbon and the dopant metal of the layer of Me-DLC affects many characteristics of the layer, including Ia tenacity, the level of internal stresses and Ia crystallinity of the layer. Rich layers dopant metal are tenacious and low level of internal stresses, whichever is beneficial for the application, but in contrast, have a higher degree of crystallinity and therefore its effectiveness as a barrier is smaller for the same thickness layer, therefore they need to adjust the proportion between the amount of carbon and metal in the layer depending on the requirements that arise in the application. For example, if a decorative layer of zirconium carbonitride is required, due to its color, and having a thickness much greater than 100 nanometers to increase its resistance to abrasion, it is necessary to use an underlying layer of a type I -DLC especially tenacious to withstand the stresses of the layer of zirconium carbonitride without causing fracture. Moreover, if the toughness requirements that Ie imposed on the layer are not severe because of that decorative layers of low thickness and such as to generate considerable tension and itself instead used, it is required that Ia this layer a very high degree of stability against organic solvents the chemical composition of the carbonaceous layer must incorporate a small amount of metal dopant.

One advantage of obtaining a waterproof coating to organic solvents, applied by PVD, based on carbonaceous compounds instead of using the metal compounds mentioned above, is that its coefficient of expansion is more similar to the polymeric substrate than the metal compounds, for which reason the differences in expansion between coating and substrate that occur during the PVD coating are smaller and thus are less likely to cause microcracks in the case of the carbonaceous coating. To avoid this type of microfractures by expansion differences may be advantageous to grade the composition of the DLC coating so that its closest to Ia strata integral with outer surface polymer present a larger coefficient of expansion, similar to the polymeric material, while the closest to the metallic coatings applied over layers are more compact and present a lower coefficient of expansion, more similar to the metal coating applied above.

The subsequent metal coating is applied by any of the known techniques of PVD, such as sputtering, cathodic arc, ion beam, among others.

Thus, in a particular embodiment, the method of the invention comprises an additional step of applying a metal layer on last layer Ia diamond like carbon by physical vapor phase deposition.

In another particular embodiment, the method of the invention comprises an additional step of applying an intermediate metal layer between the outer surface of the first layer polymer and diamond-like carbon by physical vapor phase deposition. Such deposition may be accomplished by any known PVD techniques such as sputtering or cathodic arc, for example.

In another aspect of the invention, the use of a piece having a polymer outer surface with a metallic finish is provided, as previously described, in decorative elements of metallic appearance. Such elements may be emblems cars, appliances elements, locks, etc.

A preferred embodiment of making a piece of the invention is presented.

PREFERRED EMBODIMENT The current application of such coatings to polymeric or polymer-coated parts is performed in coaters cathodic arc arched surface rectangular evaporation wide, equipped with a magnetic guide as described in patent EP1382711, and are operated with an anode isolated from the walls of the chamber for the arc discharge.

The cathode material is chromium or zirconium evaporation.

Prior to its introduction into the machine vacuum polymeric or polymer-coated parts are cleaned with aqueous baths. Typically, in the case of manufacturing automobile emblems, these parts are manufactured by injection ABS. For introduction into the machine vacuum parts they are mounted on metal holder be conveyed to the plastic part one basically negative electrical bias relative to the walls of the chamber. These slides were mounted on a table with a planetary motion so that all points of the pieces will be equally exposed to the ion flux emanating from the evaporators.

In preparation for introduction into the chamber vacuum, parts mounted on the sample holder, heated and dried in a stove low temperature by circulating dry, filtered air, and remain there until the time of introduction into the chamber of empty.

Once the pieces have been introduced in the vacuum chamber is evacuated to a vacuum level of 3 x 10 ~ 5 mbar (3 X 10 "3 Pa). At this time it is possible to use an electric discharge developed in an atmosphere containing oxygen to perform a cleaning of the polymeric surface to be coated. to this a mixture of an inert gas (usually argon) and oxygen is introduced into the chamber to a pressure of about 40 x 10 "3 mbar (4 Pa), and is blown an electrical discharge between two electrodes located on either side of Ia substrate carrier table, so that the discharge includes at least one area of ​​the table.

The discharge is maintained more easily if pulsating character at a frequency of 10 kHz, as well as being more effective for the cleaning. Ia simultaneously table is kept rotating and Ia suction gas of the chamber occurs simultaneously replenished in Ia right amount to keep the overall pressure and the concentration of active species.

After performing cleaning with oxygen for several minutes it is performed again vacuum in the chamber, to an equivalent to the start of the cleaning process level.

Once the vacuum reached the coating process begins. The first phase consists of a short metal coating made without applying bias parts, at a nominal pressure of 1.5 x 10 "3 mbar (0.15 Pa) argon. Evaporation is performed by cathodic arc and metal evaporated may be any of the transition metals, but usually, for practical reasons, the same metal which is subsequently used in the coating process for the layer decorative metal, therefore they usually this is used first metal phase is performed with chromium or zirconium. the function of this phase is that of harness Ia high kinetic energy Ia ions arc reach the surface of the parts to be coated for further cleaning of the surface. Moreover, with the implantation of metal ions in the polymer surface, it is possible to reduce electrical surface resistivity Ia of the piece, so that a pulsed bias applied to the pieces can to be effective.

it follows immediately after a phase deposition of Me-DLC. This phase takes place at 0.01 mbar (1 Pa) and the atmosphere containing 25% argon, 50% nitrogen and 25% acetylene. During this phase an electric potential pulsing parts applies, 20 kHz, to be coated. This electrical bias voltage is low, typically of around 30 volts. The combined effect of bombardment with metal ions emitted by the arc evaporator and the electrical bias applied to the parts causes a weak discharge thereon, in which the acetylene Ia atmosphere inside the chamber is decomposed to deposit occurs on parts carbonaceous me-DLC layer, a carbonaceous layer being doped with the metal being evaporated simultaneously.

This layer is grown to a thickness of at least 0.1 microns. Subsequently, this layer applies Me-DLC Ia decorative layer itself. Case of chromium, this arc is evaporated in an inert atmosphere at a pressure of about 8 x 10 "3 mbar (0.8 Pa). Typically the best results in terms of reducing internal stresses of the layer, are obtained by developing this stage with zero bias. this phase of the coating time necessary to obtain a chromium layer in volume to 100 nanometers is prolonged.

Depending on the intensity of the bombardment to which the parts which in turn depends, among other factors, the ratio between the amount of charge and the number of evaporators used, and their electric operating current is subjected, it may be necessary to interrupt the coating process at certain intervals (every few minutes) and stand for a similar time, to prevent heat generated by the bombardment and Ia condensation of species on the polymeric surface can cause a temperature increase of this that impairs its mechanical characteristics and subsequently cause adhesion problems.

Thus manufactured parts have successfully passed the following tests:

• Resistance to humidity: 4 days at 60 0 C and 100% relative humidity

• Thermal shock: 4 cycles of permanence at 80 0 C for 7 hours followed by 16 hours at -30 0 C

• Adhesion: test DIN 53151 lattice shear • Abrasion tests for 40 cycles rubbing with cotton and denim methyl alcohol soaked, acid sweat and basic sweat, 900g pressure.

• Corrosion: 144 hours in the accelerated corrosion test CASS

• Resistance to chemicals: immersion for 30 minutes at 60 0 C in super petrol, gasoline 98, diesel fuel and 95.

Claims

What is claimed
1. Piece with polymeric outer surface with a metallic finish characterized by comprising at least one layer of diamond-like carbon, doped or not, deposited on said outer surface polymer.
2. Part according to claim 1, wherein the layer of diamond-like carbon is doped.
3. Part according to claim 2, characterized in that the layer of diamond-like carbon is doped chromium, zirconium, titanium, silicon, boron, aluminum, nitrogen or fluorine.
4. Part according to claim 1, wherein the minimum thickness of the layer of diamond-like carbon is 40 nm.
5. Part according to claim 1, characterized by comprising a decorative metal layer deposited on Ia last layer of diamond-like carbon.
6. Part according to claim 5, wherein said decorative metallic layer is a layer of a transition metal or a nitride, carbide or carbonitride thereof.
7. Part according to claim 6, wherein said decorative metallic layer is a layer of chromium, zirconium or titanium, or a nitride, carbide or carbonitride thereof.
8. Part according to claim 5, characterized by comprising a transparent layer with properties antihuellas deposited on the layer decorative metallic.
9. Part according to claim 8, wherein said transparent layer is a layer of a metal oxide or diamond-like carbon.
10. Part according to claim 1, characterized in that it is a non-polymeric part coated with a polymeric layer.
11. Part according to claim 1, characterized in that it is a totally polymeric part.
12. Part according to claim 1, wherein the outer surface comprises polymeric fillers.
13. Part according to claim 12, wherein the outer surface comprises polymeric mica, talc or glass fiber.
14. Part according to any one of claims 1 to 13, characterized in that it comprises an intermediate metal layer between the outer surface of the first layer polymer and diamond like carbon.
15. Method for producing a workpiece with outer surface with a metallic finish polymer comprising applying at least one layer of diamond-like carbon on said outer surface by a polymeric deposition technique vapor.
16. Process according to claim 15, characterized in that the chemical deposition used in the vapor phase.
17. Process according to claim 15, characterized in that the physical deposition used in the vapor phase.
18. Process according to claim 15, comprising an additional step of applying a metal layer on Ia last layer of diamond-like carbon by physical vapor phase deposition.
19. Process according to claim 15, comprising an additional step of applying an intermediate metal layer between the outer surface of the first layer polymer and diamond-like carbon by physical vapor phase deposition.
20. Use of a piece with a polymeric outer surface with a metallic finish according to claims 1 to 14 in decorative elements of metallic appearance.
PCT/ES2005/000618 2005-11-15 2005-11-15 Part having an outer polymer surface with a metallic finish, production method thereof and use of same WO2007057478A1 (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2109012A (en) * 1981-10-21 1983-05-25 Rca Corp Novel and improved diamond like film and process for producing same
US6086796A (en) * 1997-07-02 2000-07-11 Diamonex, Incorporated Diamond-like carbon over-coats for optical recording media devices and method thereof
US20030053784A1 (en) * 2001-09-19 2003-03-20 Labrake Dwayne L. Optical and optoelectronic articles

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2109012A (en) * 1981-10-21 1983-05-25 Rca Corp Novel and improved diamond like film and process for producing same
US6086796A (en) * 1997-07-02 2000-07-11 Diamonex, Incorporated Diamond-like carbon over-coats for optical recording media devices and method thereof
US20030053784A1 (en) * 2001-09-19 2003-03-20 Labrake Dwayne L. Optical and optoelectronic articles

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