WO2007057478A1 - Piece a surface exterieure polymere presentant un fini metallique, procede de fabrication et utilisations de ladite piece - Google Patents

Piece a surface exterieure polymere presentant un fini metallique, procede de fabrication et utilisations de ladite piece 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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WO
WIPO (PCT)
Prior art keywords
layer
diamond
polymeric
metallic
piece
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Application number
PCT/ES2005/000618
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English (en)
Spanish (es)
Inventor
Josu Goikoetxea Larrinaga
Original Assignee
Fundacion Tekniker
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.)
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Publication date
Application filed by Fundacion Tekniker filed Critical Fundacion Tekniker
Priority to PCT/ES2005/000618 priority Critical patent/WO2007057478A1/fr
Publication of WO2007057478A1 publication Critical patent/WO2007057478A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING 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
    • C23C—COATING 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
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical 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
    • C23C16/26—Deposition of carbon only

Definitions

  • the present invention belongs to the field of coatings. More particularly, the invention relates to a piece with a polymeric outer surface that is coated with a diamond-type carbon layer, as well as to a process for its manufacture and the use thereof. Said coated piece has a metallic finish, as well as an adequate resistance to corrosion and other agents to which it is exposed during its usual use, particularly to organic solvents.
  • the conventional method of manufacturing a piece with a polymeric outer surface with a metallic finish that has adequate resistance to corrosion and other agents consists in applying a succession of metallic coatings by means of electrolytic baths. Normally, a first copper coating of about 10 microns is applied, then a nickel coating of about 20 microns and finally a chromium coating of about 0.3 microns.
  • a number of processes are known in which a metallic finish is conferred to a piece with a polymeric outer surface by means of the use of thin coatings applied by PVD (Physical Vapor Deposition), within which techniques of thermal evaporation, sputtering, ion plating or cathode arc.
  • US 6,399,219 patent avoids the formation of microfractures, or grain joints that extend over the entire width of the PVD coating by means of stacking a multitude of coatings of different nature, preferably based on nitrides or carbonitrides and metals alternated, in a number that can reach up to 100 strata.
  • the present inventors have discovered that the coating of a piece whose outer surface is polymeric with a diamond-like carbon layer, also called a DLC (Diamond like carbon) layer, allows to obtain a metallic-looking finish that is virtually immune and impervious to organic solvents. which also has good resistance properties to other physical or chemical agents.
  • a diamond-like carbon layer also called a DLC (Diamond like carbon) layer
  • the present invention is intended to provide a piece with a polymeric outer surface with a metallic finish comprising at least one diamond-type carbon layer, doped or not, deposited on said polymeric outer surface.
  • Another object of the invention is a process for manufacturing said part with a polymeric outer surface with a metallic finish.
  • Another object of the invention is the use of said piece with polymeric exterior surface with metallic finish.
  • a piece with a polymeric outer surface with a metallic finish comprising at least one diamond-type carbon layer, doped or not, deposited on said polymeric outer surface (hereinafter referred to as "part of the invention") .
  • the term "piece with polymeric outer surface” refers to a totally polymeric piece or to a piece on whose surface a thermoplastic, thermoset or resin polymeric coating has been deposited.
  • said polymeric outer surface may contain fillers common in these applications, preferably mica, talc or glass fiber.
  • This polymeric surface can fulfill a function of leveling the surface, or covering defects, in order to provide a homogeneous surface for subsequent coatings.
  • said part is a non-polymeric part
  • said part is a totally polymeric part.
  • the fully polymeric parts can be ABS (acrylonitrile-butadiene-styrene), PC (polycarbonate), mixtures of both, PBT (polybutyl terephthalate), Noryl® (mixture of phenylene polyoxide (PPO) and polystyrene) and, in general, of other thermoplastics with adequate thermal resistance.
  • the non-polymeric pieces can be metallic (zamak, aluminum, steel, brass, etc.) or ceramic (alumina, corundum, etc.).
  • the polymeric outer layer that covers them can be a thermoplastic, thermoset or resin polymeric coating of the many existing and well-known types, although those of ultraviolet (UV) curing are preferred for their improved characteristics.
  • UV ultraviolet
  • DLC diamond like carbon
  • sp3 bonds between carbon atoms can vary between 50% and 85%, which makes them similar to diamond to a certain degree. It can achieve high hardness, self-lubrication, wear resistance, chemical inertia, optical transparency, and is a broadband semiconductor. They can be doped with a multitude of elements including metals, nitrogen, fluorine or silicon, which together with the possibility of modifying their proportion of hydrogen and sp3 bonds makes it offer a very wide variety of properties. Reviews of the state of the art can be found in A. Gr ⁇ ll, Diamond and Related
  • the diamond-type carbon layer is doped.
  • the diamond-type carbon layer is doped with transition metals, such as, for example, chromium, zirconium, titanium, or with other elements, such as, for example, silicon, boron, aluminum, fluorine or nitrogen.
  • the diamond type carbon layer without doping (hereinafter “DLC”) or doped (hereinafter “Me-DLC”) must have the thickness necessary to be impervious to solvents, or that the amount of solvent that passes through it is so small as not to affect the underlying polymeric surface, for which it may be sufficient to apply a coating of 40 nanometers, depending on the particular nature of the applied layer, since there is a huge variety of characteristics between different types of DLC and Me layers -DLC, depending on the details of the deposition process.
  • the coating must be thick and impermeable enough to pass a test consisting of ten cycles of rubbing with a cloth soaked in 50% ethanol diluted in water without any damage, exerting a pressure of 900 grams.
  • the minimum thickness of the diamond-type carbon layer is 40 nm.
  • the thickness of the optimal coating is between 100 and 200 nm.
  • a second layer of DLC can be applied, optimized to give a black color with the desired color shade, on the waterproofing DLC coating or even this coating Waterproofing can be made thick enough to achieve the desired degree of opacity and dispense with any subsequent coating.
  • a thin enough metal coating can be applied on the DLC layer so that it only serves to increase its brightness, without substantially modifying its black color.
  • any metallic coating that is required to obtain the desired color can be applied, taking care that the DLC has the necessary toughness so that the stresses of the metallic coating deposited on it do not cause its fracture and detachment.
  • the piece of the invention comprises, in addition, a decorative metallic layer deposited on the last layer of DLC or Me-DLC.
  • the decorative layers based on transition metals in particular chromium, or those of nitrides, carbides or carbonitrides thereof, with which a wide variety of colors can be obtained , including colors like chrome, stainless steel, brass, gold, old gold, bronze or copper.
  • the color layer may be between 20 and 200 nanometers thick, simply sufficient to give the required color, or it may be thickened to increase its resistance to abrasion, to the extent that the toughness of the DLC is tolerated.
  • the metallic coatings also include the nitrides, carbides and carbonitrides of transition metals, since their conductive character of electricity and their external appearance makes them interchangeable for the purposes pursued by the invention.
  • said decorative metal layer is a layer of a transition metal or of a nitride, carbide or carbonitride thereof.
  • said decorative metal layer is a layer of chromium, zirconium or titanium, or of a nitride, carbide or carbonitride thereof.
  • the color coating applied on the DLC layer can in turn have a coating applied on it that is transparent and has anti-fingerprint properties, that is, that its surface characteristics are such, referring above all to the surface energy, that fingerprints do not They tend to remain visible on their surface.
  • the piece of the invention comprises a transparent layer with anti-fingerprint properties deposited on the decorative metal layer.
  • these types of coatings will be crystallographically amorphous, so that they do not have grain joints that can serve as an anchor to moisture droplets.
  • oxide coatings Metals such as, for example, those of titanium oxide made at low temperature, mixtures of aluminum and silicon oxides, or some types of DLC, especially those that are highly hydrogenated or, conversely, lacking hydrogen and rich in sp3 bonds .
  • said transparent layer is a layer of a diamond-like metal or carbon oxide.
  • the DLC layer can be adhered to the piece with polymeric outer surface through an intermediate layer, very thin, which facilitates the adhesion and that can be a metallic layer, one of whose functions is to make the polymeric surface electrically conductive on which the layer is to be applied, so that an electric polarization can be applied effectively, especially if it is pulsating.
  • an intermediate layer very thin, which facilitates the adhesion and that can be a metallic layer, one of whose functions is to make the polymeric surface electrically conductive on which the layer is to be applied, so that an electric polarization can be applied effectively, especially if it is pulsating.
  • it is most advantageous to use as a bond layer a layer of the same transition metal that will subsequently be used to give the metallized, if necessary, so that the most practical is that this layer be Cr, Zr or Ti.
  • the thickness of the layer is simply that necessary to facilitate adhesion, so it does not need to be greater than 40 nanometers.
  • This layer does not form a protection layer against diffusion of the water contained in the polymeric material.
  • the positive contribution towards the adhesion of this intermediate layer may be due, in addition to the fact that the polymeric surface is conductive, as mentioned, due to chemical affinity with the substrate and the DLC layer deposited on it, as well as to the effect of cleaning the surface of the polymeric substrate that is achieved by ionic bombardment 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 that this reacts with the pernicious residual gases that remained in the chamber at the beginning of the coating process, and facilitates that the process of anchoring the coating develops in a cleaner and controlled environment, as described below.
  • the piece of the invention comprises an intermediate metallic layer between the polymeric outer surface and the first diamond-type carbon layer.
  • a process for manufacturing a piece with a polymeric outer surface with a metallic finish that comprises applying at least one layer of diamond-type carbon on said polymeric outer surface by means of a vapor phase deposition technique.
  • said technique is a chemical vapor deposition technique. In another particular embodiment, said technique is a physical vapor deposition technique.
  • PVD Physical Vapor Deposition
  • the physical vapor deposition or PVD is a vacuum coating application technique that is characterized by using physical methods for the formation of steam that will then be deposited on the pieces.
  • the oldest method consists of thermal evaporation, either by resistive heating or electron gun.
  • methods were developed that used electric discharges for the formation of that vapor, either in the form of extensive discharges throughout the cathode surface (sputtering or ionic bombardment, US 4,166,018, US 4,162,954, and J. Vossen and W.
  • Vacuum are Science and Technology ", Noyes Pub., 1995). These types of evaporators by electric discharge require that the vacuum is not complete, but that in the chamber there is a very thin atmosphere that serves as a means for the development of the discharge, Therefore, a controlled amount of suitable gases is usually introduced during the development of the coating.
  • Chemical vapor deposition or CVD (Chemical Vapor Deposition), (see SMRossnagel, JJ Cuomo 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 that are deposited are introduced into the reaction chamber in the form of gases.
  • the technique of deposition of DLC consists in the application of a radiofrequency discharge on a piece that is in a vacuum chamber with an atmosphere of a Carbon compound that decomposes on the surface of the piece by the action of the RF discharge, forming the DLC (US 4,382,100).
  • the DLC or Me-DLC coating is applied by means of PVD techniques, evaporating graphite by sputtering or by cathode arc, or by CVD techniques, which are based on the decomposition of a gaseous hydrocarbon due to the effect of an electric shock, or by means that combine both effects, as mentioned, for example, in US Patent 6,331,332.
  • the proportion between the carbon and the doping metal of the Me-DLC layer affects numerous characteristics of the layer, among them the toughness, the degree of internal stresses and the crystallinity of the layer.
  • the layers rich in doping metal are tough and with a low degree of internal stress, which is beneficial for the application, but, as a counterpart, they have a greater degree of crystallinity and, therefore, their effectiveness as a barrier is less for the same thickness layer, so you have to adjust the proportion between the amount of carbon and metal in the layer depending on the requirements that arise in the application.
  • 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 will be necessary to use an underlying layer of a type of Me -DLC especially tenacious to be able to tolerate the tensions of the zirconium carbonitride layer without causing its fracture.
  • the tenacity requirements that are imposed on the layer are not so severe, because decorative layers of low thickness and nature are used that generate little stress and yes, however, it is required that the Layer has a very high degree of stability against organic solvents.
  • the chemical composition of the carbonaceous layer must incorporate a small amount of doping metal.
  • the composition of the DLC coating so that its strata closer to the part with a polymeric outer surface have a greater coefficient of expansion, similar to that of the polymeric material, while that the strata closest to the metal coatings applied above are more compact and have a lower coefficient of expansion, more similar to that of the metal coating applied above.
  • the subsequent metallic coating is applied by any of the known PVD techniques, such as sputtering, cathode arc, beam ion, among others.
  • the process of the invention comprises an additional step of applying a metallic layer on the last layer of diamond-type carbon by physical vapor deposition.
  • the process of the invention comprises an additional step of applying an intermediate metallic layer between the polymeric outer surface and the first diamond-type carbon layer by physical vapor deposition.
  • Said deposition can be performed by any of the known PVD techniques, such as sputtering or cathode arc, for example.
  • a piece with a polymeric outer surface with metallic finish is provided, as previously described, in metallic-looking decorative elements.
  • Such elements may be car emblems, faucet elements, locks, etc.
  • the evaporation cathode material is chromium or zirconium.
  • the polymeric or polymeric coated parts Prior to its introduction into the vacuum machine, the polymeric or polymeric coated parts are cleaned with aqueous baths. Typically, in the case of manufacturing automobile emblems, these parts are manufactured by ABS injection.
  • the pieces For its introduction in the vacuum machine, the pieces are mounted on metal sample holders, which will transmit to the plastic part an electrical polarization, basically negative, with respect to the walls of the chamber. These sample holders are mounted on a table with a planetary movement so that all parts of the pieces will be equally exposed to the flow of ions emanating from the evaporators.
  • the parts mounted on the sample holder are heated and dried in low temperature stoves, through which dry and filtered air circulates, and remain there until they are introduced into the chamber of empty.
  • the vacuum chamber Once the pieces have been introduced into the vacuum chamber, it 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 shock developed in an atmosphere which contains oxygen to perform a cleaning of the polymeric surface to be coated. To this end, a mixture of an inert gas (generally argon) and oxygen is introduced into the chamber to a pressure of about 40 x 10 "3 mbar (4 Pa), and an electric shock is skipped between two electrodes located on both sides of the table holder, so that the discharge includes at least one area of this table.
  • an inert gas generally argon
  • the discharge is maintained more easily if it is pulsating, at a frequency of the order of 10 kHz, in addition to being more effective for cleaning.
  • the table is kept rotating and the gas aspiration of the chamber is produced at the same time as it is replenished in the right amount for maintain the global pressure and the concentration of active species.
  • vacuum is performed again in the chamber, to a level equivalent to that of the beginning of the cleaning process.
  • the first phase consists of a short metallic coating, made without applying polarization to the pieces, at a nominal pressure of 1.5 x 10 "3 mbar (0.15 Pa) of argon. Evaporation is carried out by cathode arc and metal evaporated can be any of the transition metals, but usually, for practical reasons, the same metal is used that will be used later in the coating process to make the decorative metal layer, so usually this first metal phase is made with chrome or zirconium The function of this phase is to take advantage of the high kinetic energy with which the arc ions reach the surface of the pieces to be coated to perform a further cleaning of this surface.In addition, with the implantation of metal ions on the polymeric surface, it is possible to reduce the surface electrical resistivity of the piece, so that a pulsating polarization applied to the pieces can reach To be effective.
  • a deposition phase of Me-DLC is followed.
  • This phase takes place at 0.01 mbar (1 Pa) and the atmosphere contains 25% argon, 50% nitrogen and 25% acetylene.
  • a pulsating electrical potential at 20 kHz, is applied to the pieces to be coated.
  • This electrical polarization is low voltage, around 30 Volts usually.
  • the combined effect of the bombardment with metal ions emitted by the arc evaporator and the electrical polarization applied to the pieces causes a weak discharge on them, in which the acetylene of the atmosphere inside the chamber decomposes to deposit on the pieces a carbonaceous layer of Me-DLC, being a carbonaceous layer doped with the metal that is evaporating simultaneously.
  • This layer is allowed to grow to a thickness of at least 0.1 microns. Subsequently, on this Me-DLC layer the decorative layer itself is applied. If it is chromium, it evaporates by arc in an inert atmosphere, at a pressure around 8 x 10 "3 mbar (0.8 Pa). Usually the best results, in terms of reducing internal stresses of the layer, They are obtained by developing this phase of the process with zero polarization.This phase of the coating extends the time necessary to obtain a chrome layer of at 100 nanometers.
  • Adhesion test for trellis cut DIN 53151 • Abrasion: rubbing tests for 40 cycles with cotton and denim soaked in methyl alcohol, acid sweat and basic sweat, with a pressure of 900 grams.

Abstract

L'invention concerne une pièce à surface extérieure polymère présentant un fini métallique qui comprend au moins une couche de carbone de type diamant ou couche de carbone sous forme de diamant amorphe (DLC), dopée ou non, déposée sur la surface extérieure polymère au moyen de techniques de dépôt en phase vapeur. Cette couche de carbone sous forme de diamant amorphe confère à la pièce un fini métallique et une imperméabilité aux dissolvants organiques ainsi que de bonnes propriétés de résistance à la corrosion, à l'abrasion, à l'humidité, aux chocs thermiques et, en général, à d'autres agents auxquels elle est susceptible d'être exposée pendant son utilisation habituelle. Cette couche de carbone sous forme de diamant amorphe peut être recouverte, à la fois, par une couche métallique décorative. L'invention concerne également un procédé de fabrication de cette pièce ainsi que l'utilisation de cette pièce dans des éléments décoratifs d'aspect métallique.
PCT/ES2005/000618 2005-11-15 2005-11-15 Piece a surface exterieure polymere presentant un fini metallique, procede de fabrication et utilisations de ladite piece WO2007057478A1 (fr)

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PCT/ES2005/000618 WO2007057478A1 (fr) 2005-11-15 2005-11-15 Piece a surface exterieure polymere presentant un fini metallique, procede de fabrication et utilisations de ladite piece

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Application Number Priority Date Filing Date Title
PCT/ES2005/000618 WO2007057478A1 (fr) 2005-11-15 2005-11-15 Piece a surface exterieure polymere presentant un fini metallique, procede de fabrication et utilisations de ladite piece

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WO2007057478A1 true WO2007057478A1 (fr) 2007-05-24

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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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