US20110226629A1 - Process for optophysical surface treatment of polymer substrates and device for implementing the process - Google Patents

Process for optophysical surface treatment of polymer substrates and device for implementing the process Download PDF

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Publication number
US20110226629A1
US20110226629A1 US13/058,529 US200913058529A US2011226629A1 US 20110226629 A1 US20110226629 A1 US 20110226629A1 US 200913058529 A US200913058529 A US 200913058529A US 2011226629 A1 US2011226629 A1 US 2011226629A1
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Prior art keywords
treatment
substrate
metallization
corona
surface treatment
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US13/058,529
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Samuel Stremsdoerfer
Guy Stremsdoerfer
Yunny Meas
Lorena Magalon
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Jet Metal Tech
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Jet Metal Tech
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Assigned to JET METAL TECHNOLOGIES reassignment JET METAL TECHNOLOGIES ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: MAGALON, LORENA, MEAS, YUNNY, STREMSDOERFER, GUY, STREMSDOERFER, SAMUEL
Publication of US20110226629A1 publication Critical patent/US20110226629A1/en
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    • 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
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/18—Pretreatment of the material to be coated
    • C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
    • C23C18/2006—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C59/00—Surface shaping of articles, e.g. embossing; Apparatus therefor
    • B29C59/10—Surface shaping of articles, e.g. embossing; Apparatus therefor by electric discharge treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C59/00—Surface shaping of articles, e.g. embossing; Apparatus therefor
    • B29C59/16—Surface shaping of articles, e.g. embossing; Apparatus therefor by wave energy or particle radiation, e.g. infrared heating
    • 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
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/18—Pretreatment of the material to be coated
    • C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
    • C23C18/2006—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30
    • C23C18/2026—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30 by radiant energy
    • C23C18/204—Radiation, e.g. UV, laser
    • 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
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/18—Pretreatment of the material to be coated
    • C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
    • C23C18/28—Sensitising or activating
    • C23C18/30—Activating or accelerating or sensitising with palladium or other noble metal
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C35/00—Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
    • B29C35/02—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould
    • B29C35/08—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation
    • B29C35/0805—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation using electromagnetic radiation
    • B29C2035/0827—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation using electromagnetic radiation using UV radiation

Definitions

  • the technical field of the invention is that of the surface treatment of polymer or copolymer substrates, e.g. ABS (Acrylonitrile Butadiene Styrene), in particular for covering same with metallic films.
  • ABS Acrylonitrile Butadiene Styrene
  • the present invention also relates to non-electrolytic metallization methods of substrates for decoration, e.g. chrome plating of automobile parts and for aeronautics.
  • the present invention relates to the non-electrolytic metallization of substrates for electronics, in particular the fabrication of conductive paths.
  • the most common pre-treatment is a chemical surface oxidation treatment via sulfochromic attack, described in particular in U.S. Pat. No. 3,769,061, GB-A-1240294 and GB-A-1291351.
  • This very corrosive treatment enables a micro-porous/nano-porous surface to be obtained to facilitate the mechanical anchoring of the metallic film.
  • the sulfochromic mixture is a mixture of sulfuric acid and potassium or sodium chromate H 2 S0 4 /(K 2 ,Na 2 )Cr 2 O 7 .
  • This mixture is very toxic and dangerous for the environment: the chromium VI salts contained in the mixture are declared by the European Union, to be category 1 and 2 human carcinogens.
  • surface treatment via sulfochromic attack does not give satisfactory adherence results when the non-electrolytic metallization is carried out using the Jet Metal Technologies company's methods, described in particular in FR-A-2 763 962 and in the French patent application filed with the number 06 10287. Indeed, because the oxidation is very deep and the metallic film very thin, the pores created by oxidation induce a phenomenon of delamination of the metallic film with time.
  • Ozone is a flammable gas which spontaneously decomposes into molecular oxygen. It is also toxic by inhalation and corrosive.
  • a physical pre-treatment is also known using plasma under reduced pressure, with heating under a controlled atmosphere.
  • Another known physical pre-treatment of the surface is the flaming treatment.
  • Another objective of the invention is that of providing a device for the in-line implementation of the whole treatment and metallization method for substrates.
  • the object of the present invention is a surface treatment method for a substrate, characterized in that the method comprises a combined UV/Corona treatment of the, preferably polymer, substrate surface.
  • polymer designates the homo-polymers and the copolymers such as, e.g. Acrylonitrile Butadiene Styrene (ABS).
  • ABS Acrylonitrile Butadiene Styrene
  • UV/Corona treatment it is understood e.g. that the substrate undergoes one or more times, a Corona electrical discharge treatment and on or more times, a UV exposure of UV treatment.
  • These UV and Corona treatments are simultaneous or non-simultaneous, and can be performed in any order.
  • the corona treatment term means, e.g. that the substrate to be metalized undergoes electrical discharges e.g. of a power of 1 to 100 kilowatts 35 (kW) with a material intended to this effect and comprising one or more, preferably two or three, discharge heads (or probe).
  • electrical discharges e.g. of a power of 1 to 100 kilowatts 35 (kW) with a material intended to this effect and comprising one or more, preferably two or three, discharge heads (or probe).
  • the term “Corona treatment” should be understood in the largest sense thereof, namely including the treatment using atmospheric plasma “air plasma”, “flame plasma”, and chemical plasma.
  • UV treatment corresponds e.g. to the passage of the substrate to be metalized underneath an Ultra-Violet lamp, of which the emission spectrum is e.g. of 200 nm to 600 nm, with an energy peak at the wavelength of 365 nm, e.g. an HK 125® lamp marketed by PHILIPS®.
  • an Ultra-Violet lamp of which the emission spectrum is e.g. of 200 nm to 600 nm, with an energy peak at the wavelength of 365 nm, e.g. an HK 125® lamp marketed by PHILIPS®.
  • the combined UV/Corona treatment of the substrate surface occurs just prior to the metallization stage, without an intermediate step.
  • the time interval between the combined UV/Corona treatment and the metallization step is e.g. less than or equal to a few minutes.
  • this time duration is less than or equal to 30 (thirty) minutes, preferably less than or equal to 5 (five) minutes and more preferably less than or equal to 1 (one) minute, or even a few seconds.
  • the substrate is a polymer, preferably chosen from amongst:
  • the combined UV/Corona treatment is chosen from amongst the following treatments: an alternation of a UV treatment and a Corona treatment, simultaneous UV and Corona treatments, a treatment comprising one or more alternation sequences and one or more sequences of simultaneous UV and Corona treatments and combinations thereof.
  • the combined UV/Corona treatment comprises at least one alternation of a UV treatment and a Corona treatment.
  • the alternation is preferably a series of UV followed by Corona.
  • the combined UV/Corona treatment comprises 1 to 120 times the alternation of a 0.01 second to 30 (thirty) minute UV treatment and a 0.01 second to 30 (thirty) minute Corona treatment.
  • the alternation of a combined UV/Corona treatment comprises 3 to 16 alternations, namely 5 to 15 alternations and even more preferably 4 to 14 alternations; e.g. 6 or 12 alternations.
  • the duration of the Corona treatment during the combined Corona/UV treatment in alternation lasts preferably 0.1 seconds to 5 (five) minutes, namely 0.5 seconds to 2 (two) minutes and even more preferentially 1 (one) second to 1 (one) minute.
  • the duration of the UV treatment in the UV/Corona alternation lasts preferably 30 (thirty) seconds to 15 (fifteen) minutes, namely 1 (one) to 5 (five) minutes, and even more preferentially from 1 (one to 2 (two) minutes.
  • the duration of the Corona treatment is e.g. the duration during which a unit of area of the surface to be treated is exposed or undergoes a Corona discharge using a Corona device of which the probe (or discharge head) has a given area, e.g. of 10 cm 2 , which corresponds to the unit area to be treated.
  • the duration of the Corona treatment can last e.g. 15 seconds for a unit area of 10 cm 2 of a 100 cm 2 flat surface to be treated. This is equivalent to a 15 (fifteen) second total Corona treatment of the surface, and to a 75 (seventy five) second combined UV/Corona treatment, corresponding to 60 (sixty) seconds of UV treatment and 15 seconds of Corona treatment.
  • the alternation can start and end indifferently, either by the Corona treatment or the UV treatment during the combined Corona/UV treatment in alternation. Preferably, it is started with the UV treatment.
  • the object of the present invention is also a surface treatment method where the combined UV/Corona treatment as defined above is followed by a non-electrolytic metallization of the substrate treated as described.
  • the non-electrolytic metallization is a non-electrolytic metallization by the spraying of one or more redox (oxidation-reduction) solutions in the form of aerosol(s).
  • the redox solution used during non-electrolytic metallization are sprayed in the form of aerosol(s) over the substrate and are preferably obtained from solutions, advantageously aqueous, of one or more oxidizing metallic cations and one or more reducing compounds. These redox solutions are preferably obtained by dilution of concentrated stock solutions.
  • the diluent is preferably water.
  • the spraying aerosol(s) is/are produced by the nebulizing and/or atomizing of solution(s) and/or dispersion(s) to obtain a fog of droplets smaller than 100 micrometers, preferably 60 micrometers and even more preferably 0.1 to 50 micrometers.
  • the spraying of metallic solutions preferably takes place continuously and the substrate is driven into movement and undergoes spraying.
  • the spraying is continuous.
  • the spraying is carried out in alternation with relaxation times.
  • the sprayings lasts e.g. 0.5 to 1000 seconds, preferably from 1 (one) to 800 seconds and even more preferably 2 (two) to 600 seconds for a 1 dm 2 area to be metalized.
  • the substrate can be driven into at least partial rotation during the spraying of the metallization.
  • one or more metallic cationic solutions and one or more reducing solutions are continuously and simultaneously sprayed, in one or more aerosols, over the surface to be treated.
  • the mixture between the oxidizing solution and the reducing solution can be made just prior to the formation of the aerosol to be sprayed or by fusion between an aerosol produced from the oxidizing solution and an aerosol produced from the reducing solution, preferably prior to entering into contact with the surface of the substrate to be metalized.
  • one or more metallic cationic solutions then one or more reducing solutions are successively sprayed, by intermediary of one or more aerosols.
  • the spraying of the redox solution is carried out by the separate spraying of one or more solutions of one or more metallic oxidizers and one or more solutions of one or more reducers.
  • This second possibility corresponds to an alternate spraying of the reducing solution or solutions and of the metallic salt or salts.
  • the association of a plurality of oxidizing metallic cations to form a multilayer of different metals or alloys is such that the different salts are, preferably, naturally sprayed separately from the reducer, but also separately one from the others, and successively. It is obvious that, in addition to the different nature of the metallic cations, using different counter-anions can be considered.
  • a metastable mixture of the oxidizer(s) and the reducer(s) is produced, and after having sprayed the mixture, the latter is activated, so that the transformation into metal is initiated, preferably by bringing into contact with an initiator, advantageously brought by intermediary of one or more aerosols, prior to, during or following the spraying of the reaction mixture.
  • an initiator advantageously brought by intermediary of one or more aerosols
  • the redox solutions sprayed during the metallization step of the substrate are one or more solutions of a metallic oxidizer and one or more solutions of a reducer.
  • the concentrations of metallic salts in the oxidizing solution to be sprayed are of 0.1 g/l to 100 g/l and preferably from 1 (one) to 60 g/l, and the concentrations of metallic salts of the stock solutions are from 0.5 g/l to 10 3 g/l, or the dilution factor of the stock solutions is from 5 to 500.
  • the metallic salts are chosen from amongst the following compounds: silver nitrate, nickel sulfate, copper sulfate, tin chloride, and mixtures thereof.
  • reducers are preferably made from amongst the following compounds: borohydride, di-methyl-amino-borane, hydrazine, sodium hypophosphite, formaldehyde, lithium aluminum hydride, reducing sugars such as glucose and sodium erythorbate, and mixtures thereof.
  • the selection of the reducer imposes taking into account the pH and the targeted properties of xc the metallization film. These routine adjustments can be done by a person skilled in the art.
  • the concentrations of reducer in the reducing solution to be sprayed are from 0.1 g/l to 100 g/l and preferably from 1 (one) to 60 g/l, and the concentrations of reducer in the stock solutions are from 0.5 g/l to 10 3 g/l, or the dilution factor of the stock solution is from 5 to 100.
  • particles are incorporated into at least one of the redox solutions, to be sprayed at the time of metallization.
  • the particles are thus trapped in the metallic deposit.
  • These hard particles are e.g. diamond, ceramics, carbon nanotubes, metallic particles, rare earths oxides, polytetratluoroethylene (PTFE), graphite, metallic oxides and mixtures thereof.
  • PTFE polytetratluoroethylene
  • the rinsing step i.e. bringing into contact the entire surface or part of the surface with one or more sources of rinsing liquid, is carried out by spraying a rinsing liquid aerosol, preferably water.
  • the wetting prior step mentioned above consists of covering the surface of the substrate with a liquid film.
  • the choice of the wetting liquid is made from within the following group: deionized water or non-deionized water, with the possible addition of one or more anionic, cationic or neutral surfactants, an alcoholic solution comprising one or more alcohols (e.g. isopropyl alcohol, ethanol) and mixtures thereof.
  • deionized water with an addition of an anionic surfactant and ethanol is chosen as the wetting liquid.
  • the liquid is essentially aqueous for obvious reasons of industrial convenience. The duration of the wetting depends upon the area of the considered substrate and of the flow rate of the spraying of the wetting aerosol.
  • the sensitization step for the surface of the substrate can be implemented by means of a sensitization solution, particularly stannous chloride, e.g. according to the implementation mode described in FR-A-2 763 962.
  • a rinsing step using a rinsing liquid such as described above is carried out immediately following the sensitization step, without an intermediate step.
  • the metalized substrate can undergo a thermal treatment just following the rinsing step which follows the spraying step, to reinforce adherence.
  • the thermal treatment preferably takes place in an infrared oven or tunnel at a temperature from 50° C. to 150° C., more preferably from 60° C. to 120° C. and even more preferably of about 100° C., for a duration of 5 minutes to 3 hours, preferably between 15 minutes and 90 minutes, and more preferably of about 60 minutes.
  • the thermal treatment can also be a drying step which consists of draining the rinsing water. It can be advantageously carried out at a temperature between 20° C. and 40° C. using e.g. a system of pulsed compressed air at 5 bar/pulse at a temperature of 20° C. to 40° C.
  • the non-electrolytic metallization is a non-electrolytic metallization by immersion in one or more baths containing one or more redox solutions.
  • This method is called “chemical metallization” by a person skilled in the art.
  • Non-electrolytic metallization by immersion in one or more baths containing one or more redox solutions means that the non-electrolytic metallization comprises, in this order, at least the following steps:
  • the parts to be treated are immersed in a bath mainly containing three agents: a metallic salt, a reducer and a complexing agent which prevents the spontaneous reduction and the precipitation of the bath.
  • the metallic deposit produced is a chemical nickel deposit.
  • ATOTECH® chemical and redox solutions can be used for such a deposit:
  • the method comprises, in addition to and following the non-electrolytic metallization step, a step for producing a finishing layer.
  • the step of producing a finishing layer is preferably the production of an electrolytic thickening of the metalized surface.
  • the electrolytic thickening is preferably achieved by immersing the substrate, which is at least partially metalized, in a solution bath containing electrolytes and, by passing a sufficiently high electric current between the existing electrode in the electrolytic bath and the substrate which is at least partially metalized.
  • the electrolytes are metallic ions suitable for being deposited onto the metalized surface of the substrate, e.g. chosen amongst the ions of the following metals: chrome, nickel, silver or copper, such as Cr 6+ , Ni 2+ , Ag + and Cu 2+ .
  • a stacking of a plurality of metallic layers produced by successive steps can occur, such as a thickening of copper followed by a layer of nickel and a final layer of chromium.
  • the technique of electrolytic thickening is well known to a person skilled in the art. E.g, the quantity of current required to produce a 1 micrometer copper layer on a substrate having a metalized area of 1 dm 2 is 0.5 to 20 A from a solution of Cu 2+ ions at 250 g/l.
  • the thickness of the finishing layer produced by electrolytic thickening is from 2 to 40 micrometers.
  • the substrate is preferably partially metalized. Partial metallization is possible namely by masking part of the surface of the substrate prior to metallization.
  • the effluents coming from the different steps of the method are advantageously retreated and recycled to be used in the method, and to limit the ecological impact.
  • the retreatment and the recycling of the effluents comprise, in this order, the following steps/
  • the flocculent added to the effluents is preferably a charged organic polymer, such as same marketed by SNF FLOERGER®.
  • the separation of the supernatant and the sludge is advantageously achieved by filtration on sintered filters or by overflowing.
  • the sludge can then be disposed of and directed towards a specialized centre for retreating or reusing waste.
  • the obtained filtrate can be neutralized, in particular by adding an acid solution with a normality of 0.1 to 10 N until the filtrate reaches a pH of 5 to 6.
  • the acids used for neutralizing in particular the ammonia existing in the filtrate are chosen amongst hydrochloric acid, sulfuric acid, nitric acid and mixtures thereof.
  • the distillation of the filtrate is preferably achieved using an evaporator, and the filtrate is heated at a temperature of 90 to 120° C.
  • the residue which remains at the bottom of the boiler at the end of the distillation is disposed of and sent to a specialized center for retreating or reusing waste.
  • the distilled water can be reused in the metallization method, and in particular for the dilution of stock solutions and for the rinsing and wetting steps.
  • the advantages of the method according to the invention are numerous.
  • the surface treatment makes possible the control of the metallization reaction and improvement of the adherence of the metallic film to the surface.
  • No chemical product is used for the combined UV/Corona treatment.
  • the effluents of the metallization, discharged by the process and which are, on an industrial scale, more than one ton per day, are retreated and reused by the process.
  • the distilled water which comes out of the retreatment module is pure and can be used as such for the dilution of the oxidizer and reducer stock solutions, and for rinsing and wetting.
  • the electrolytic thickening which can be produced has the advantage of being selective: same only takes places on the metalized surface of the substrate, which enables embossed patterns to be created, such as conductive paths.
  • the object of the present application is also a method for treating surfaces including a combined UV/Corona treatment and a metallization of substrates, as defined in the above description, where a plurality of substrates are treated in line without breaking the chain.
  • the method does not require any handling performed by man, with the exception of the steps of loading the substrate to be metalized and unloading the metalized substrate.
  • the industrial device for the implementation of the method described above comprises, in addition, the following elements:
  • the module for combined UV/Corona surface treatment comprises one or more Corona discharge heads and one or more UV lamps. It can be, e.g. a Corona discharge tunnel marketed by the DMG® company under the name C22® and a reference UV lamp HK125® from the brand PHILIPS®.
  • the non electrolytic metallization module comprises means of non-electrolytic metallization which are the current means of spraying solutions, in particular same described as in FR-A-2 763 962, or means of immersion such as electroplating lines via baths.
  • the means of spraying comprise, e.g. a set of HVLP (High Volume Low Pressure) spray guns, said guns being each linked to one or more pumps supplied with a solution.
  • a first pump/gun system is provided for the wetting step.
  • a second pump/gun system is provided for the sensitization step and a third for the rinsing.
  • the spraying of metallic oxidizer and reducer solutions is carried out using at least two pump/gun systems: a system for the oxidizer solution, and a system for the reducer solution.
  • the number of guns is between 1 and 30, linked to at least one pump. The same applies to the spraying of the reducer solution which counts 1 to 30 guns.
  • a final pump/gun system is provided for rinsing following the spraying of metallization solutions.
  • the means of immersion are, e.g. containers (tanks or vats) in which liquid solutions are put.
  • the lines which are used are e.g. of the type marketed by the CORELEC® company.
  • the non-electrolytic metallization module can also include means of thermal treatment for the metallic film, e.g. using an IR oven or tunnel, or a system of pulsed compressed air at 5 bar/air pulsed at a temperature comprised between 20 and 40° C.
  • the module for producing a finishing layer comprises means of producing an electrolytic thickening of the metalized surface, particularly an electrolytic bath filled with solution containing electrolytes, at least one electrode and a device for the circulation of an electric current.
  • the device can be, in addition, equipped with a module for retreating and recycling effluents.
  • This module for retreating and recycling effluents comprises means of recuperating effluents, which are, e.g. recuperation channels, such as chicane screens which direct the effluents towards a recuperation container, and which are intended to protect the mechanism of the conveyer on which are arranged the substrates to be metalized.
  • recuperation channels such as chicane screens which direct the effluents towards a recuperation container, and which are intended to protect the mechanism of the conveyer on which are arranged the substrates to be metalized.
  • This module for retreating and recycling effluents also comprises:
  • the purified water is directed, via means of conveying liquids, e.g. pipes and pumps, towards the different modules of the method, to be reused.
  • liquids e.g. pipes and pumps
  • the substrates to be metalized are placed on a means of moving the substrates from one module to another.
  • a means of moving the substrates from one module to another can be, e.g. a conveyer, particularly a belt and pin conveyer, when a metallization module is used, which comprises means of spraying. It can be, e.g. a swing tray whenever the metallization module consists of means of immersion.
  • the means of moving the substrates is equipped with means of driving into rotation the substrates about the axes thereof.
  • the present invention also relates to a metalized substrate obtained using the method as described above, the substrate being in particular an automobile part or a part used in aeronautics.
  • the present invention also has as object, a metalized substrate obtained using the method as previously described, the substrate being in particular a part used in electronics such as a conductive path or a radio frequency identification (RFID) antenna.
  • RFID radio frequency identification
  • FIG. 1 shows a global diagram of the embodiment of the metallization method according to the invention
  • FIG. 2 shows a diagram of a device according to the invention
  • FIG. 3 shows a transverse cross-section of a substrate metalized using the method according to the invention.
  • FIG. 4 shows a transverse cross-section of a substrate metalized using the method according to the invention.
  • FIG. 1 a summary diagram of the essential and optional steps of the embodiment of the metallization method according to the invention, is shown.
  • FIG. 2 is a schematic representation of a device for embodying a method according to the invention.
  • This device comprises the following three modules:
  • the combined UV/Corona treatment module 3 comprises a UV treatment cabin 4 and a Corona treatment cabin 5 .
  • the non-electrolytic metallization module 6 comprises a spraying zone 7 equipped with guns 8 linked to pumps 9 , each pump being linked to its own solution vat.
  • Pump 10 is reserved for wetting the surface.
  • Pump 11 is provided for the step of sensitizing the surface of the substrate and pump 12 for rinsing.
  • Pumps 13 and 14 are pumps linked to redox solutions.
  • Pump 15 is a rinsing pump.
  • the optional module for producing a finishing layer 16 is a cabin for electrolytic thickening consisting of a container containing an electrolytic solution 17 and electrodes 18 and 19 in between which circulates a sufficiently high current for producing electrolytic thickening. Electrode 18 plunges into the electrolytic solution bath and electrode 19 is linked to the metalized substrate.
  • the substrate to metalize 1 is placed on a swing tray 2 which conveys same towards the combined UV/Corona treatment module 3 where same undergoes a combined UV/Corona treatment via the UV treatment cabin 4 and Corona treatment cabin 5 .
  • the swing tray 2 makes round trips between the treatment cabins UV′ and Corona 5 , in alternation.
  • the substrate which is treated is then conveyed towards the non-electrolytic metallization module 6 installed after the combined UV/Corona treatment module 3 .
  • pump 10 wets the surface, e.g. with water.
  • pump 11 sprays a solution of stannous chloride.
  • This sensitization is followed by a rinsing step, e.g. with water, using pump 12 .
  • Pumps 13 and 14 then spray the redox solutions required for the production of the metallic film. Pump 13 is e.g. linked to the solution of metallic ions and pump 14 is linked to the reducer solution. The actuation of these pumps can be simultaneous or consecutive.
  • a rinsing step is provided using pump 15 linked to a solution of rinsing liquid, e.g. water.
  • the substrate thus metalized is finally conveyed towards the optional module for producing a finishing layer 16 where the substrate undergoes electrolytic thickening.
  • the substrate is plunged into the electrolytic solution bath, electrode 18 is plunged into the electrolytic solution bath, electrode 19 is attached to the substrate to be metalized and a current is circulated between the two electrodes.
  • the substrate 20 which has been metalized using the method according to the invention can then be unloaded after the production of the finishing layer.
  • FIGS. 3 and 4 each show a schematic transverse cross-section of a substrate metalized by an embodiment of the method of the invention.
  • the metalized substrate consists of three layers A, B and C.
  • Layer A stands for the substrate, e.g. a substrate made of ABS
  • layer B is the metallic film, e.g. a chromium film
  • layer C is the result of electrolytic thickening in a bath containing nickel sulfate.
  • the metalized substrate also consists of three layers called A′, B′ and C′.
  • A′ is a substrate, e.g. an ABS-PC.
  • Layer B′ is a metallic layer, e.g. made of nickel, obtained via metallization with masking part of the surface.
  • Layer C′ is a copper layer, which is the result of electrolytic thickening in a bath containing copper sulfate. The deposition of this layer C′ is selective and only takes place on the surface of the layer B′.
  • the rotating part is then treated using an alternating UV/Corona treatment according to the following conditions:
  • ABS part is thus obtained, with a metallic primary layer made of electrically conductive nickel on which a finishing range is produced using electrolytic thickening according to a protocol and using a material and products known per se.
  • This thickening consists of the following successive layers: copper (20 microns)+nickel (5 microns)+chromium (0.5 microns).
  • the rotating part is then treated using an alternating UV/Corona treatment according to the following conditions:
  • the mask is removed from a part of the surface.
  • the part is thus partially metalized and immersed in an electrolytic solution bath of copper ions, marketed as CUPRACIDE ULTRA® by the company ATOTECH®.
  • An electrode is placed in the bath and a 2 A current is applied between the electrode and the substrate.
  • the duration of the electrolysis is 700 seconds and thickening is of 20 microns.
  • ABS-PC part A metalized and copper-thickened ABS-PC part is thus obtained.
  • ABS of the NOVODUR® range from BAYER®, 10 cm long by 10 cm wide and 1 cm thick, and of which part of the surface is masked in order to produce a printed circuit pattern, is driven into rotation on a rotating plate at 5 rpm.
  • the rotating part is then treated using an alternating UV/Corona treatment according to the following conditions:
  • the part which has been metalized (under a nickel layer) is immersed in an electrolytic solution bath of copper ions at 250 g/l.
  • An electrode is placed inside the bath and a 2 A current is applied between the electrode and the substrate.
  • the duration of the electrolysis is of 700 seconds and thickening is of 20 microns.
  • the range is completed by an electrolytic deposit of nickel of 5 microns and a chromium layer of 0.5 microns. This copper/nickel thickening is carried out in the same way as in example 1.
  • a chromium-metalized ABS part is thus obtained for applications in the automobile field, in particular.
  • a standardized Peel Test ASTM B533 is run on the part which was obtained. A mean value of 0.75 N/mm is obtained.

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US13/058,529 2008-08-12 2009-08-05 Process for optophysical surface treatment of polymer substrates and device for implementing the process Abandoned US20110226629A1 (en)

Applications Claiming Priority (3)

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FR0855532A FR2934964B1 (fr) 2008-08-12 2008-08-12 Procede de traitement optophysique de surface de substrats polymere et dispositif pour la mise en oeuvre du procede
FR0855532 2008-08-12
PCT/EP2009/060164 WO2010018115A1 (fr) 2008-08-12 2009-08-05 Procédé de traitement optophysique de surface de substrats polymères et dispositif pour la mise en oeuvre du procédé

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FR2988104A1 (fr) * 2012-03-15 2013-09-20 Eurocopter France Procede de fabrication d'une piece comprenant une ame obtenue sans outillage
FR3133199A1 (fr) 2022-03-04 2023-09-08 Jet Metal Technologies Procede de fabrication d’un article tridimensionnel a motif(s) metallique(s)

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EP2318564B1 (fr) 2013-01-02
FR2934964B1 (fr) 2010-10-22
JP2011530656A (ja) 2011-12-22
MX2011001709A (es) 2011-04-05
WO2010018115A1 (fr) 2010-02-18
CN102177276A (zh) 2011-09-07
EP2318564A1 (fr) 2011-05-11
FR2934964A1 (fr) 2010-02-19

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