FR2840550A1 - Metallization of article made of high temperature polymer plastic material used in connectors involves cleaning, plasma etching, grafting and metallizing by immersing article into bath at preset temperature - Google Patents

Abstract

An article made from high temperature polymer plastic material is cleaned, plasma etched, grafted, and metallized by immersing the article into bath at 50-70 degrees C.

Description

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Method of metallizing plastic supports
The present invention relates to a method of metallization of plastic supports, in particular high-temperature plastic. The object of the invention is to lead, in particular for the field of the electronics industry, to the production of connectors and more generally high temperature resistant supports and used for hybrid assemblies, which are light, easy to manufacture, and which have great electrical insulation properties, while allowing by metallization the necessary electrical conductions.

 It is known, particularly from document US-A-5 407 622, the production of metallized circuits in two or three dimensions by a double molding process using in particular a first molding of a plastic material undergoing an activation step making it metallizable, a second molding of a non-metallisable plastic material leaving exposed zones of the first part and then a metallization step. The description of this process indicates that the adhesion promotion (activation) step utilizes chemical oxidation by a solution rendering the plastic surface hydrophilic. US-A-4,812,275 also relates to a double molding process. For this process, the adhesion promotion is achieved by a chemical etching making the surface to be metallized rough.

 Another technique for which a catalyst precursor is deposited is described in document US Pat. No. 5,153,023. According to this document, a selective metallization is carried out by locally heating the zones where it is desired to attach the catalyst and then rinsing the piece to dissolve the precursor in places that you do not want to metallize.

 An old double molding technology is described in GB-A-1 254 308. According to this document two materials are used, one metallizable, the other not. The composite article is then treated by a metallization process comprising a step of etching the surface of the article, a treatment step, and an electrochemical catalytic deposition step.

 Typically, the chemical techniques of cleaning, sensitizing and activating a surface to be coated exist. We put in

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 This involves immersion processes in specific baths in order to fix palladium seeds on the surface. These conventional techniques can be summarized as follows: a surface preparation step, comprising cleaning and stripping, is followed by adsorption of a catalyst and then of a metallization.

 Previous treatments use chemical solutions. Thus each type of plastic has a range of surface preparation which is specific to it. These treatment ranges have the great disadvantage of including many steps ranging from 16 to 22 steps depending on the nature of the polymer. On the other hand, these multiple steps require a fairly long processing time of up to 65 minutes before the start of any metallization. This makes it difficult, complex and expensive to treat the plastic substrates to be metallized, especially when there are several types of polymeric materials to be metallized. These methods are also expensive reprocessing solutions. In addition, the activation or catalysis solutions used in these processes mainly use colloidal palladium-tin solutions (PdSn) which are expensive, polluting and very sensitive to temperature variation. Thus a temperature below 10 C can partially or totally disable these activation solutions and make them unusable. On the other hand the use of etching and chemical etching solutions makes the plastic surface rough enough which makes it unusable for many applications in connection, precision welding, electronics and packaging that require very flat surfaces. and very smooth. Note that this roughness is necessary in the case of conventional methods to ensure good mechanical adhesion. To this must be added that a large number of high temperature plastics including those used in the connectors, such as LCP, PPS and PBT, are considered non-metallizable by the conventional wet chemical methods already described. This severely limits the industrial possibilities of exploiting the characteristics of these polymers. Some grades of these plastics contain very specific additives (compounding) to render them metallizable chemically but this to the detriment of their mechanical performance and dielectric properties. Which makes them unsuitable for use in connectivity.

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 The defects of these processes are therefore the slowness of the chemical processes, the number of steps required, the use of expensive and polluting palloid colloidal solutions, the impossibility of metallizing the high temperature engineering plastics, the obtaining of rough pieces to the location of the metallized part and the risks of separation in the case of a smooth surface. Indeed, the metallization results in these cases of a mechanical adhesion, it is not sufficiently intimate.

 In the invention, to solve these problems, it has been the idea to use a nitrogen or ammonia plasma in order to obtain a chemical adhesion of the metal deposit on a smooth material. The nitrogen or ammonia plasma is produced in a bell receiving the article to be metallized. In the bell, a primary vacuum is produced, an injected gas being either one of the gases NH3, N2, or (N2 + H2), or a mixture of these gases. Plasma is obtained by electromagnetic energy (low frequencies, radiofrequency), by microwave or by microwave discharges.

 Activation tests of certain plastic materials by a plasma have been carried out and are known from the documents: "Interest of NH3 and N2 Plasmas for Polymers Surface Treatment Before Electroless Metallization", published in Plasmas and Polymers, Vol 1, N 2, 1996 , page 113-126, due to M. ALAMI, M. CHARBONNIER, and M. ROMAND, D1, "Plasma Chemical Modification of Polycarbonate Surfaces for Electroless Plating" published in J. Adhesion, Vol 57, Pages 77-90, of the same authors, D2, "Plasma surface functionalization of polycarbonate: Application to electroless nickel and copper plating" M. Charbonnier, M. Romand, E. Harry, M. Alami; Journal of Applied Electrochemistry, January 2001, Volume 31, No. 1, pp. 57-63, D3, "Electroless Plating of Polymers: XPS Study of Initiation Mechanisms"; M. CHARBONNIER; Mr. ALAMI and Mr. ROMAND; Journal of Applied Electrochemistry, April 1998, Volume 28, No. 4, pp. 449-453, D4, Plasma Treatment Process for Palladium Chemisorption onto Polymers before Electroless Deposition. Charbonnier, M .; Alami, M .; Romand, M., Journal of the Electrochemical Society, 1996, vol. 143, no. 2, pp. 472-480, D5.

 However, as far as the first document D1 envisages such a treatment for polymers in general, it describes as a practical example only amorphous polystyrene, polycarbonate and polyamide, whose

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 Supporting qualities in the field of electronics are unattractive because of their temperature limit and the high water absorption rate of the polyamide.

 The second, the third and the fourth documents, D2, D3 and D4, only mention details of the treatment of polycarbonates and its mechanisms. These materials are not retained in the field of electronics and components, because their lower quality in terms of temperature resistance, electrical insulation, industrial workability, and mechanical capabilities.

 In contrast, in the field of electronic circuits and connectors, high-temperature plastics of the semi-crystalline and / or liquid crystal type, typically of polyester, polybutylene-terephthalate PBT or LCP, of the type, are preferred. polyphenylene sulphide PPS, or syndiotactic polystyrene SPS type.

 These polymeric plastics can be described as high temperature polymers because their melting temperatures are 220 ° C. for PBT and are greater than 350 ° C. for the other three cited above.

 By comparison, the melting temperatures of the other polymers known to be metallizable by plasma or other process are much lower, of the order of 90 C for ABS or PVC and 120 C for polycarbonate.

 However, the high temperature engineering plastic materials are known for their inertia vis-à-vis chemical treatments for metallization. This inertia is significantly enhanced in cases where these plastics are partially crystalline. This has led to limiting attempts to metallize these high temperature materials.

 As for document D5, it uses exactly the same work as D1 on polycarbonate and amorphous polystyrene. In addition, the authors clearly describe that the maximum thicknesses reached by their process are less than 2 m. This is obviously not usable industrially in the connection where metal films with a thickness greater than 20 m are often required.

 Another teaching tending to exclude the skilled person from the plasma process is the use by the authors of documents D1 to D5 of a laboratory-type specific nickel bath which only

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 temperatures above 85 C, which has an acidic pH and which is systematically degraded by decomposition, as mentioned in particular in document D4. This significantly limits the choice of plating baths and does not allow to operate on an industrial scale.

 In addition, the metallization tests in the laboratory on high temperature polymer materials mentioned above, with methods by activation by plasmas, in particular the method described in documents D1 to D5, show bad or at least random metallization results. A use of industrial plating baths with plasma activation described in the same documents does not allow metallization on high temperature plastics as well as low temperature plastics described in these same documents. Therefore, it is accepted that these technical plastic materials are not metallizable by these plasmas.

 An even more dissuasive effect for the metallization of high temperature plastic materials is the fact that these materials are generally loaded by additives (fillers and compounds) such as glass fibers for example which are widely used in industry. However, glass fibers increase the inertia of plastics vis-à-vis the various activation methods. This makes it possible to explain the random nature of the process described in these documents.

 In spite of this a priori and to solve these problems, the present invention was launched in a search for conditions in which a so-called Electroless metallization with prior plasma etching could be conceivable.

 Such Electroless metallization, that is to say without use of a current source, comprises in particular 1) a degreasing of the substrate, 2) a plasma etching, 3) an activation of the surface of the support, in particular by immersion in a dilute solution palladium chloride, rinsing with water, 4) a chemical reduction by a bath of hypophosphite or formaldehyde and 5) a metallization itself.

This metallization comprises an immersion in a metallization bath.

 While the first tests were unsuccessful as mentioned above, it was discovered that the metallization that was expected did not occur under good conditions if the different baths used

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 were not initiated. Their systematic initiation was then carried out and it was then possible to measure that the metallization then took place satisfactorily. The priming baths include the immersion in these baths of a room, a blade, nickel freshly pickled in a solution of HCl.

 Then we tried to do without the necessity of priming, and we then found that the temperature of the baths had to be better controlled. It has thus been discovered that the metallization baths, which in the state of the art were heated to 85 ° C., should have a temperature of between 50 ° C. and 70 ° C., preferably between 55 ° C. and 65 ° C.

 In order to better control this temperature during the metallization, in particular very large baths have been chosen in relation to the volume of the articles to be treated, so that the immersion of these articles in the bath does not greatly modify the temperature. Another solution could from this point of view consist in preheating the articles to be treated.

 According to the invention, and to further improve the metallization bypassing the need for priming and to better activate the high temperature technical materials, we have mixed with the gas used for the plasma (N2 or NH3) an inert rare gas such as neon, helium or argon. The inert gas is added in a proportion of 0.1 to 6% by volume, which increases the dissociation of nitrogen and / or ammonia or their mixtures into reactive compounds of 7 to 8% in free radicals and in ionic or atomic species excited.

 The activation time is of the order of 5 seconds to 5 minutes and the power density varies between 0. 1 and 1. 1 W / cm 2, preferably between 0.3 and 0.7 W / cm 2. The frequency of the electromagnetic activation can be of the order of 75 Hz until the microwaves. The result of the activation is the breaking of carbon and carbon-hydrogen bonds on the article and the grafting of nitrogen compounds NH, NH 2, N 2 +, and more generally amides, amines, imines or imides.

 The part can then be immersed in an ionic solution comprising palladium salts (for example PdCl 2 or PdSO 4 + HCl), which allows the grafting of palladium ions. This palladium will then be chemically reduced in a bath containing a reducing agent such as hypophosphite, formaldehyde, or hydrosulfite. This grafting followed by a reduction allows

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 then, by dipping the grafted part in a chemical metallization bath, to produce a first thin metallization layer which will then be completed to give a thick metallization by electrochemical or galvanic deposition. A characteristic of the resulting product is that analysis of nitrogen compounds and palladium is found at the metal / polymer interface, the thick metallization layer preferably having a thickness of between 0.2 m and 20 m.

 According to the invention, the process has been extended to materials originally considered in the art as non-metallizable such as PBT, PPS, SPS and LCP. These materials could finally be metallized according to the process and according to the improvement of the invention.

 In addition, the plasma etching method can be controlled so as to allow selective metallization on an article formed of two different plastic supports, this without activation step between the two molding steps. It is indeed possible, for reasons of selective metallization, to activate a part of an article, to glue or overmold on this activated part another non-activated part of the article, and then to metallize the article. together, the metallization is only realized on the prepared part (as indicated in US-A-5 407 622). This would avoid an engraving operation. However, this technique which involves the manipulation of an activated part may lead to the local deactivation of this activated part during bonding, or overmoulding on the non-activated part, especially in the presence of pollutants and contaminants such as fats and grease. the oils.

 In the invention, this problem has been solved by gluing or overmolding the two parts prior to activation, but retaining for these different parts different plastic materials.

Then, at the time of plasma activation, the conditions of the activation are modified so that only one of the two parts is activated. Typically, the duration of the activation is modified. For example, it is limited to 10 seconds (ie less than 15 seconds), a part in LCP or SPS is activated in 5 seconds while the other part, respectively in PBT or PPS, can be activated only after 60 seconds , not being activated. Indeed tests were carried out on a mixed part in PBT - SPS and on a mixed part in PPS - LCP. They determined that by optimizing

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 the plasma parameters (time and energy) a sufficient differentiated reaction to the grafting is obtained to allow, after the palladium ion grafting step, a selective metallization by a first layer in an auto-catalytic chemical copper bath with stabilizing agents. It thus appears that the improvement of the process of the invention consists in carrying out a differential activation of a bi-material product allowing a selective metallization, in particular by a fast metallization step.

 The subject of the invention is therefore a process for metallizing a high-temperature polymer plastic article comprising cleaning steps, plasma etching steps, grafting steps, and metallization steps by immersion in a metallization bath, for which the bath metallization is brought to a temperature between 50 C and 70 C.

 The invention therefore also relates to a metallization process of a high-temperature polymer plastic article comprising cleaning steps, plasma etching, grafting and then metallization by immersion in a metallization bath, such as the metallisation bath is preliminarily initiated.

 The invention also relates to a method of metallizing a high-temperature polymer plastic article comprising cleaning steps, etching by plasma, grafting and metallization by immersion in a metallization bath, for which the The article comprises parts made of different plastics, and such that the operating conditions of these steps are adjusted in such a way that the grafting and then the metallization are effective on one of these parts and not on the other.

 The main subject of the invention is a plastic part at least partially coated with a metal deposit comprising a first non-metallized plastics material, - a second plastics material coated at least in part by the metallic deposit, the metal deposit comprising at the interface with the second material of the attachment sites comprising nitrogen species and palladium species, comprises a first layer called initial layer having a first thickness, comprises at least a second layer called outer layer having a second thickness, the first and second plastic materials being free of metal charges or

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 catalyst.

 Still according to the invention the piece is such that the interface is formed on the second material from a plasma activation of at least this second material and then immersing the piece in an ionic palladium bath.

 To achieve the part according to the invention, the plasma activation is made on the two plastic materials for a duration activating only one of the plastic materials.

 According to one particular embodiment of the invention, the plasma activation activates the two materials, a step of deactivating one of the materials being placed between the activation and the immersion, the deactivation step possibly being a step of waiting or aging.

 In alternative mode, the plasma activation is done on the two materials, an oxygen supply being carried out for example by stirring the bath, bubbling, air blowing or bubbling during a chemical deposition step subsequent to the immersion of the piece. in the ionic palladium bath to form the initial layer on only one of the plastic materials.

 According to the invention, the first and second materials may be chosen from SPS, LCP, PBT and PPS materials and their various non-catalytically charged grades. The first and second plastic materials can form after treatment a non-metallizable / metallizable pair selected from LCP / SPS; PBT / LCP; PBT / SPS; PPS / LCP; PPS / SPS; PBT / SPS.

 The outer layer may in particular be made by electrochemical deposition of a metal such as copper or nickel.

 The thickness of the initial layer can start at 0.3 m and go up to 20 m but is advantageously between 0.3 m and 1.5 m, the outer layer preferably having a thickness of between 4 m and 30 m.

 The part according to the invention is such that the adhesive force of the deposit on the second plastic material is greater than 1 N / mm 2 and in particular the adhesion force of the deposit on the second plastic material may be greater than 2 N / mm2.

 Still according to the invention the surface of the second material after tearing off the deposit has an analysis spectrum provided with at least peaks

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 corresponding to the nitrogen species, peaks corresponding to the palladium species and has a shift of the peaks, corresponding to the palladium species, specific to PdNx bonds.

 The invention will be better understood on reading the description which follows and on examining the figures which accompany it. These are presented only as an indication and in no way limitative of the invention. The figures show: FIG. 1: the evolution of the energy position of the spin 3d doublet of palladium; - Figures 2a, 2b and 2c: an exemplary part according to the invention for the molding steps and activation; - Figure 3: view of a detail of the part according to Figures 2A, 2B, 2C after metallization; FIG. 4: representation of the XPS spectrum of the surface of the metal plastic interface of a part according to the invention; - Figure 5: A first detail of the representation of Figure 4; - Figure 6: A second detail of the representation of Figure 4; FIG. 7: statistical representation of a detail of the XPS spectrum of the surface of the interface of another type of part according to the invention; - Figure 8 is a schematic sectional view of a part comprising a single plastic material metallized according to the method of the invention.

 The plasma technique used in the context of the invention consisted in creating a high frequency potential difference in a gas under reduced pressure. Different species are then created, including: electrons, ions, atoms and molecules excited or not, free radicals, UV and visible photons.

 In practice, the three excitation frequencies used to create this plasma are in the range of low frequencies (<100 Hz) radio frequencies (13.56 MHz) and microwaves (430 MHz or 2.45 GHz).

 The plasma used is a nitrogenous plasma, for example of the N 2 or NH 3 or N 2 + H 2 type, which forms on the surface of the polymer C-N type groups.

Plasma is also a very reactive set which causes on the surface of the substrate many effects among which: - the cleaning of the surface, by the elimination of the organic contaminants, - the stripping, which removes the superficial layers by creating a

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 some roughness at the nanoscale of the substrate surface.

 In addition, the UV of the plasma breaks the C-C and C-H bonds of the polymer, thus leaving free radicals reacting with other radicals of the gas or with other macromolecular chains of the surface.

 An effect obtained in the context of the invention by the use of a nitrogenous plasma is the functionalization which is a grafting of chemical functions carried out with a reactive gas plasma: grafting of nitrogen functions (plasma N2, NH3) to the surface of the polymer. The nitrogenous plasmas N2 make it possible to obtain the following groups: amines H2N-C, imines N = C, nitriles N # C. The NH 3 plasmas lead to the formation of groups: amines H2N-C, amides N-C = O.

 A second step to obtain a metallized high temperature plastic in the context of the invention is Electroless metallization. Electroless metallization is a process of chemical deposition of metal layers on substrates from an aqueous solution, without the use of an external current source. This is a method that operates without an external power source. The baths or solutions used to obtain the metal deposits, are industrial solutions designed by specialized companies. The baths consist of several agents, including in particular: a salt of the metal to be deposited: Ni, Cu, Ag, Co; - a reducing agent: sodium hypophosphite, formaldehyde; a stabilizer; a pH regulator, and; a complexing agent

 The metal deposition reaction results from a redox reaction between a metal ion of the agent to be deposited and the reductant of the system. In order to obtain a deposit on the surface of any substrate, this active surface must be made catalytic for the redox reaction in order to allow an initiation of the reduction of the metal ions. If the substrate is non-conductive, in the case of polymers, it is necessary to produce nucleation sites on the surface of the latter. This is done by fixing a salt of a Group VIII metal (usually palladium), in order to initiate the deposition reaction. Consequently, such an approach has been implemented in the invention in order to modify the surface of the substrate by a treatment

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 plasma.

 Thus, according to the invention, by subjecting a substrate, in particular a connector element consisting of a polymer, to an N 2 or NH 3 or (N 2 + H 2) type plasma, C-N groups are formed on its surface. By then immersing this sample in a palladium salt bath: PdCl 2 or PdSO 4, covalent strong bonds are created between the nitrogen and palladium atoms: C-N-Pd; the surface is thus activated, which makes it possible to initiate the oxidation-reduction reaction described above. A first advantage of the process of the invention is that this simplified treatment eliminates the chemical surface conditioning treatments and the tin chloride sensitization treatment known in the prior art whose solution management is difficult and expensive.

 This simplified process which will be described below can be summarized by the following flowchart: solvent degreasing, plasma etching, activation, rinsing and metallization.

 As seen previously, in order to modify the surface of the polymers, we used so-called non-polymerizable gases: N2, NH3, allowing grafting of nitrogenous chemical functions. The plasma treatments were carried out, without limitation, using a 13.56 MHz radiofrequency RF reactor with parallel electrodes in aluminum, operating in capacitive mode.

The connector substrate to be treated is disposed on a lower electrode, the cathode, which is connected to the RF generator. The upper electrode, the anode, connected to the ground is pierced with holes, which allows a homogeneous flow of gases at the entrance to the reactor. A water circulation system continuously cools the two electrodes, thus limiting their temperature to 60 C maximum. Since the efficiency of the plasma treatments depends on different operating parameters, we have endeavored to vary these parameters in order to optimize the metallization conditions: - Pressure of the gas in the reactor: 0. 12 Pa at 35 Pa; - Gas flow: 10 to 1000 sccm; - Gases used: NH3, N2, (H2 + N2) as the main gas and in some cases we added rare gases such as Helium, Argon and Neon; - Treatment duration: 0.5 s to 10 minutes; - Power: a power density provided by the generator: 0. 1 to 1.1 W / cm2.

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 Electroless baths most commonly used industrially contain the salt of the metal to be deposited, a strong reducing agent, a complexing agent of the metal ion and a stabilizing compound to prevent the decomposition of the solution. In the card of the invention, we used two baths of Enthone-IMO. A first bath to make nickel deposits: Enplate Ni426, contains little phosphorus.

A second bath to make copper deposits: Enplate Cu872.

 For all materials that are non-conductive such as polymers, it is necessary to render the surface catalytically active by creating on it nucleation sites by grafting a noble metal, such as palladium capable of catalyzing the reaction. . We use palladium here because it has a very strong affinity with nitrogen, previously fixed by plasma treatment.

 We used, to metallize the samples, three solutions, namely: a bath of palladium chloride containing between 0.05 g / l and 0.5 g / l of PdCl 2 of 1 to 30 cm 3 / l of pure HCl, in order to achieve adsorption of the catalyst (immersion for 0.5 to 5 minutes and then rinsing with water for about 30 seconds); as a reducing bath, we used a bath of sodium hypophosphite operating between 50 and 85 ° C., or a bath of formaldehyde in sodium medium, or a bath of hydrosulphite in an alkaline medium in order to chemically reduce the grafted catalyst to the surface of the substrates (immersion for 1 min to 10 min). This step is optional and its use depends on the stability of industrial baths. Indeed, the reduction of Pd2 + species by the chemical reducer before the metallization step allows the latter to start quickly and obtain quality deposits; a metallization bath containing the nickel salt or the copper salt (immersion for a variable duration depending on the desired thickness of metal).

 The electroless metallization process used can be summarized as follows for a PBT + 30% glass fiber substrate by way of example: - Degreasing: isopropanol with ultrasonic or alkaline degreaser - RF plasma (0.5 to 10 min)

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 - Immersion in the PdCl2 bath - Rinsing: distilled water - Immersion in the hypophosphite bath or formaldehyde - Immersion in the plating bath - Rinsing.

 For the degreasing of parts, the parts, for example plastic connector housings, are placed in an ultrasonic isopropanol bath or in an alkaline degreasing bath containing a surfactant and sodium hydroxide.

 The baths containing hypophosphite and nickel are each brought to a temperature between 50 and 65 ° C. After the grafting of nitrogen functions on the polymer: C-N bonds, it is activated at PdCl 2 by attaching palladium seeds to it. Since palladium has a high affinity for nitrogen, C-N-Pd bonds are created, the palladium thus fixed being in the Pd (II) state.

To be active, the palladium must be in the Pd (0) state. This is accomplished by subjecting the grafted substrates to the direct action of a reducing agent (immersion in a hypophosphite bath) or to the action of the metallization bath itself (bath which contains hypophosphite).

 The surfaces thus prepared were then analyzed. To characterize the surface of the insulators, in particular the surface of the polymers, a possible technique is X-ray induced photoelectron spectroscopy: XPS. The interest of this method resides in its ability to demonstrate the presence of certain surface chemical bonds. . Another test method such as inorganic mass spectrometry analysis (English abbreviation SIMS) makes it possible to characterize the peaks corresponding to the chemical species existing on the surface of the material.

 The wettability of the items was also measured using a GBX Scientific Instruments Digidrop camera with a camera, image analysis and processing system, and software to perform automatic angle measurements. of contact.

 Adhesion testing has also been carried out by tearing off an adhesive tape, commonly referred to as Scotch test (Scotch is a registered trademark by 3M). The adhesive tape used is 3M Type 250. This test consists in making separate cross incisions ( grid) on the metallization deposit.

These incisions must be deep enough to reach the substrate. We do

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 then strongly adhere an adhesive tape to the incised surface. After waiting for 3 minutes, the adhesive tape is pulled off very quickly, without any downtime. In general, the test is carried out at an angle of 180. The notched portion of the coating under test is then examined.

A standard six-class classification is used to estimate the adhesion of the deposit on the substrate.

It is also possible to carry out a pull-out test. During this test, the adhesion is measured by the tensile force that it is necessary to exert on the deposit, perpendicularly to the plane of the interface, to tear it off its substrate. A cylindrical aluminum pad is adhered to the coating by means of a cyanoacrylate adhesive. The substrate being immobilized, the stud is torn off using a traction machine which records the maximum force necessary to detach a coating disc. The ratio between this maximum force and the surface of the stud is often used to characterize the adhesion:
It is necessary to wait 24 hours of drying at room temperature before carrying out the tensile test.

 The substrates studied are parts for use in connection or molded interconnect devices (molded interconnect devices). These are for example connector housings coated with a metal layer for example forming disjoint conductive tracks for the transport of electricity or constituting an electromagnetic shielding. This layer of metal must not deteriorate or peel off as a result of industrial or environmental constraints as encountered in the automobile for example. The metallized parts must in particular withstand significant electrical stresses without damaging the surface of the substrate. Resistance to electrical stresses is measured by thermal shock tests. These tests are of two types: conventional thermal shocks or cyclic thermal shocks. These thermal shocks make it possible to check the capacity of the deposit to withstand significant thermal variations and consequently electric shocks which cause a rise in the temperature at the level of the conductive metal. By checking the resistance of the metal deposit to the substrate following a thermal shock, it is possible to validate the resistance of the sample to electric shocks.

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 In the context of the manufacture of electronic components, the materials for connectors on which nickel and copper must be deposited to make conductive tracks, are for example the following: - PBT + 30% glass fibers (polybutylene terephthalate), called industrially Pocan; LCP (liquid crystal polymer), referred to industrially as Vectra; - SPS + 30% glass fibers, industrially called Questra; Polyphenylene sulphide + 40% glass fiber (for example the RYTON product from Chevron Phillips).

 We therefore studied each of the parameters of the plasma treatment: the treatment time, the power of the generator, the flow rate and the pressure of the gas. In order to optimize the plasma parameters, we characterized the surface of each of the treated samples by measuring the wetting angle and by XPS analysis.

PBT substrates loaded with 30% glass fibers
We studied the influence of the treatment time, the power, the flow and the pressure of the gas. We were also interested in the influence of the nature of the gas: NH3 or N2 and their mixtures with a rare gas which is neon.

 The wetting angle was measured for each processed connector. The results of these measurements allow us to define the evolution of the wetting angle according to the studied parameter.

 The value of the wetting angle for a PBT sample loaded with 30% untreated glass fiber is 83.6. A 180s to 240s processing has been ideal, and drops the angle value by about 10.

By way of example, the parameters of a treatment (T1) making it possible to initiate a metal deposit on the sample are for this type of polymer: Treatment time: 240 seconds Type of gas: N2 (95%) + Ne (5%) - Power 0. 2 to 0.3 W / cm2 - Flow rate: 350 sccm (ml / min) - Pressure: 25 Pa
A second treatment (T2) with another gas also allows

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the initiation of a metallic deposit: - Treatment time: 300 seconds - Type of gas: N2 (90%) + H2 (10%) - Power 0. 8 to 0.9 W / cm2 - Flow rate: 350 sccm (ml / min) - Pressure: 25 Pa
In conclusion, the parameters of the plasma treatment, pressure and flow rate, the treatment time and the power delivered by the generator are optimized according to the gas used (NH3 or N2) for the treatment, but also according to the rare gas used. A rare gas favors dissociation and therefore requires less power delivered. By cons use of a mixture of nitrogen and hydrogen require more power and more processing time to ensure grafting.

 The XPS analysis of the part samples shows how the surface of the polymer has been modified. For each plasma treatment we analyzed two representative samples of PBT connectors.

Each connector is immersed for 4 minutes in the bath of PdCl2 and rinsed with water. Knowing the affinity of palladium with respect to the nitrogen functions previously fixed on the surface of the polymer we should find by analyzing the surface of the sample by XPS traces of palladium. The proportions of each of the atoms present on the surface of the samples are calculated. We have grouped the results of the analyzes in the table below. The given values correspond to atomic percentages.

<Tb>
<Tb>

Samples <SEP>% C <SEP>% O <SEP>% N <SEP>% Pd <SEP>% CI
<tb> PBT <SEP> with <SEP> treatment <SEP> 67 <SEP> 23 <SEP> 5. <SEP> 8 <SEP> 3 <SEP> 1.2
<tb> T1
<tb> PBT <SEP> with <SEP> treatment <SEP> 67. <SEP> 9 <SEP> 23. <SEP> 0 <SEP> 3. <SEP> 6 <SEP> 3. <SEP> 2 <SEP > 0. <SEP> 5
<tb> T2
<Tb>

We note that the T1 treatment grafts more nitrogen than the T2 treatment but that the level of grafted palladium remains equivalent.

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LCP Substrates
In a second step, we carried out identical measurements on another polymer: the LCP, after various plasma treatments. the connectors manufactured with this plastic are intended for very high temperature applications (continuous operation at 190 C and soldering at 245 C).

We characterized the surfaces of the treated samples.

 We carried out surveys of the wetting angles for the different treatments carried out. This allowed us to evaluate the influence of the experimental parameters on the wettability of the substrate.

The value of the wetting angle for an untreated LCP sample is 78.8. After a treatment of 15 seconds, the wetting angle decreases significantly to 40.2. From 30s the wetting angle tends to a plateau, with mean wetting angles values of about 12. For treatment times greater than 240 seconds, the polymer may deteriorate
Since the LCP is sensitive to treatment, short times are necessary, unlike PBT.

 As a variant, the flow and pressure parameters, nature of the gas, treatment time and power, it is possible to perform the plasma treatment for the LCP.

By way of example, the parameters of a LCP treatment (T3) for initiating metal deposition on the adherent sample are for this type of polymer: - Treatment time: 20 seconds - Gas type: N2 (96) %) + Ar (4%) - Power 0. 15 to 0. 20 W / cm2 - Flow rate: 200 sccm (ml / min) - Pressure: 22 Pa
A second treatment for LCP (T4) with another gas also allows the initiation of a metallic deposit: - Treatment time: 35 seconds - Type of gas: NH3 - Power 0.2 to 0.25 W / cm2 - Flow rate: 50 sccm (ml / min) - Pressure: 25 Pa

<Desc / Clms Page number 19>

Surface analysis of these samples by XPS shows that after immersion of an ionic palladium bath, a formaldehyde-based reduction bath in sodium medium, we have the following atomic surface composition:

<Tb>
<tb> Samples <SEP>% C <SEP>% 0 <SEP>% N <SEP>% Pd <SEP>% CI
<tb> LCP <SEP> with <SEP> treatment <SEP> T3 <SEP> 66. <SEP> 5 <SEP> 21. <SEP> 7 <SEP> 7. <SEP> 2 <SEP> 3. <SEP > 4 <SEP> 1.2
<tb> LCP <SEP> with <SEP> treatment <SEP> T4 <SEP> 67.1 <SEP> 22.4 <SEP> 6.7 <SEP> 2.9 <SEP> 0.9
<Tb>

The T4 treatment grafts less nitrogen and less palladium than T3, but is sufficient to trigger adherent metal deposition on the LCP connectors.

 After having optimized the plasma parameters making it possible to obtain a modification of the surface state, it is important to validate that the modified substrate metallizes correctly and in a reproducible manner, in particular by a nickel electroless metallization. At first we used the nickel bath of the company Enthone. To optimize the metallization of the substrate with this bath we have carried out some preliminary studies. These studies were conducted with the aim of obtaining a homogeneous and reproducible metallization of the modified substrate. For this we studied the influence of: - the composition of the Enthone bath (proportions of the different constituents, pH of the solution at the start and during the deposition) - the cleaning of the substrates.

 treatment times of the different steps of the process.

Following these studies, we proceeded to tests of qualification and quantification of the adhesion of the metal on the substrate by using the scotch test and tearing tests then thermal shock tests on several samples, plasma treated. under the previously defined operating conditions (T1 to T4),
We have thus used two enthone metallization baths of different composition, ie not having the same proportions of solutions A, B to be mixed.

<Desc / Clms Page number 20>

<Tb>
<Tb>

Bath <SEP> Plastic <SEP> Bath <SEP> Standard
<tb> Solution <SEP> A <SEP> 50 <SEP> cm3 / l <SEP> 100 <SEP> cm3 / l
<tb> Solution <SEP> B <SEP> 50 <SEP> cm3 / l <SEP> 100 <SEP> cm3 / l
<tb> Water <SEP> Distilled <SEP> 900 <SEP> cm311 <SEP> 800 <SEP> cm3 / l
<Tb>

For each type of bath we realized solutions with different pH:

<Tb>
<tb> Bath <SEP> plastic <SEP> Bath <SEP> standard
<tb> 5. <SEP> 4 <SEP> 5.4
<tb> PH <SEP> 6.2 <SEP> 6.0
<tb> 6.4 <SEP> 6. <SEP> 2
<Tb>

Visually, all samples are metallized homogeneously over their entire surface, no blisters appeared.

 The standard bath allows a higher deposition rate than the plastic bath: The pH plays an important role on the deposition rate: When the pH goes from 5.4 to 6.2 in a standard bath, the deposition rate increases by 20%. The higher the pH, the higher the rate of deposition. By further increasing the pH to values greater than 8, it is possible to deposit up to 20 m of metal deposit in less than one hour. The adhesion of the deposit remains very good and no blisters appear. Several industrial baths have been tested, for example that of MacDermidFRAPPAZ Europlate Ni 810 containing a higher phosphorus content than that of Enthone, so having a better resistance to corrosion, similar results have been obtained.

 To further improve the process, several methods of cleaning the surface of the samples were tested: - Pickling by plasma treatment 02; - Alkaline cleaning in a concentrated solution of NaOH, followed by neutralization with an acidic solution (immersion in an acetic acid solution) then rinsing with water; - Classic cleaning with isopropanol and immersion in the bath with ultrasound.

 We conducted the 3 types of cleaning in parallel to compare their effectiveness on PBT and LCP.

 No significant difference in the quality of the deposits obtained with

<Desc / Clms Page number 21>

 the different surface treatments could not be highlighted.

 Priming the metallization in the Electroless bath is an optional step for the invention. It is possible to prime the baths so that the metallization of the treated substrate is initiated in the solution.

 According to some tests, several samples immersed in a non-primed bath have not been metallized correctly, a more or less important zone, which may in some cases represent 90% of the surface of the sample, exhibited an absence of nickel. this problem has been considered for the set of baths tested for chemical nickel or chemical copper.

A first resolution of this problem consisted in immersing in the solution a nickel strip freshly stripped in a solution of HCl. Under these conditions, the presence of a large catalytic surface in the bath allows the initiation of the oxidation-reduction reaction since the bath automatically switches to the redox potential suitable for the reaction. This is manifested by a gaseous release of hydrogen on the substrate. The metallizations carried out following a priming of the bath, made it possible to obtain a homogeneous metallization of the samples and a reproducibility of 100%.

 The importance of the immersion times in the different baths of the Electroless metallization process has been verified for the quality of the deposit.

 By carrying out tests for different immersion times in hypophosphite, and formaldehyde we have verified the influence of this treatment on the initiation time of nickel deposition. It was also found that the nature of the polymer had a very important influence on the final metallization of the substrate.

 for the LCP, the minimum immersion time is 20 seconds, for lower times the substrate is metallized in a non-homogeneous manner; - for PBT, the minimum immersion time is 60 seconds, below this time some samples have not been well metallized.

 This constraint may also be used for the selective metallization of two-component articles, by limiting, in addition possibly other choices, the metallization time to an intermediate duration between these two different durations.

 FIG. 1 shows the evolution of the energy position of the palladium 3d spin doublet as a function of the immersion time in the bath of

<Desc / Clms Page number 22>

 of hypophosphite parts of PBT connectors on which Pd2 + ions have been chemisorbed. At zero time, palladium is present in the form Pd2 + and the energy position of the peak Pd 3d 5/2 is 337.9eV. As the immersion time in H2PO2- increases, the energy position of this peak moves towards the lower binding energies which corresponds to a reduction of Pd2 + to Pd (0) metal. The energy position of the Pd 3d 5/2 peak of the metallic palladium is at 335.8eV, a value reached after 15 minutes immersion of the PBT in H2PO2 '. The following comparative table provides for Vectra and PBT the energy positions of the peak Pd 3d5 / 2 for different immersion times in H2PO2. It highlights the influence of the substrate on the reduction rate of Pd2 + and shows that Vectra is more active than PBT since after 3 minutes a large fraction of Pd2 + is reduced to Pd (0), the maximum of peak envelope being displaced by 0.9eV.

 If one respects the parameters below in a systematic way, one obtains a correct metallization and this with a reproducibility of 100%.

In conclusion, it is necessary to use a bath with a use temperature of the order of 60 C, ideally 62 C to 63 C, the priming should preferably be carried out, the immersion time in the PdCl 2 bath is 2 minutes minimum; in the H2PO2- bath for LCP: 20 s, for PBT: 60 s. This mode of differentiation also makes it possible, for example by choosing 40 sec, to separate the metallizations on various parts of the same article into different plastic materials.

We then made the adhesion of the metal deposits on the various high temperature plastic substrates. Deposits were carried out on PBT and LCP substrates, SPS and PPS on which we proceeded to a surface treatment according to the optimal conditions determined and already mentioned:
This treatment made it possible to carry out Electroless nickel metallization, taking into account the above indications. Several deposits have been made one after the other on the treated substrates so as to reproduce the structure of the electronic components. We made chemical deposits, Electroless, then electrochemical deposits. Deposits are made of nickel or copper; these are the metals used in connection technology for the manufacture of components

<Desc / Clms Page number 23>

 because they are very conductive.

 The samples thus metallized were subjected to the adhesion tests: Scotch test, tear test and thermal shocks.

 The peel test compares the adhesion stresses measured on each sample with the adhesion stress given by industry standards that require the deposit to withstand a minimum adhesion stress of 1.2 N / mm 2 for one application. in connection.

 To study the adhesion of metal layers to PBT we analyzed the influence of the type of gas used during plasma treatment, then the influence of the thickness of the chemical nickel deposited in the first layer, and also the influence of the type of copper layer.

Here are some examples of tests done on connector materials:

<Tb>
<tb> TYPE <SEP> TYPE <SEP> 2 <SEP> TYPE <SEP> 3
<tb> Ni <SEP> electro
<tb> Ni <SEP> chemical <SEP> Ni <SEP> electro <SEP> Ni <SEP> electro
<tb> Cu <SEP> chemical <SEP> Cu <SEP> electro <SEP> Cu <SEP> electro
<tb> Ni <SEP> Chemical <SEP> Ni <SEP> Chemical <SEP> Ni <SEP> Chemical
<tb> PBT <SEP> and <SEP> plasma <SEP> NH3 <SEP> PBT <SEP> and <SEP> plasma <SEP> N2 <SEP> PBT <SEP> and <SEP> plasma <SEP> NH3
<Tb>

Samples of the first type were prepared in the following manner: - 0.3m chemical nickel flash - 6.5m chemical copper plating - 0.25m chemical nickel plating (protection against copper oxidation ) - 5.2 m electrochemical nickel reloading to obtain a final thickness of 12.25 m.

 Samples of the second type were prepared in the following manner: - Chemical nickel deposition of 0.87p, m at 4.58m - Electrochemical copper deposition of 6m at 9m - 5.2m electrochemical nickel reloading to obtain a final thickness of between 12 m and 16 m.

 Samples of the third type were prepared in the manner

<Desc / Clms Page number 24>

 Chemical deposition of 0.3 μm to 4.6 m electrochemical copper deposit from 6 m to 15 m Electrochemical nickel reloading of 5.2 m to obtain a final thickness between 11 m and 20 m .

 We performed the tear test on all samples.

 All the samples showed satisfactory results on all the tests carried out, the tearing stresses being greater than the minimum constraint accepted for this kind of parts.

 The results grouped in the following tables, Table 1 first type, Table 2 second type, and Table 3 third type, show adhesion stress values higher than the standard regardless of the initial thickness of nickel and regardless of the thickness. thickness of electrochemical copper added. The lowest adhesion stresses are observed for the highest total thicknesses in effect the greater the thickness deposited, the greater the internal stresses and the greater the deposit is solicited with risks of cohesive failure.

Table 1

<Tb>
<tb> TYPE <SEP> 1 <SEP>
<tb> ISO <SEP> DIN
<tb> ASTM
<tb> Nickel <SEP> 2409 <SEP> 53496
<tb> Nickel <SEP> Copper <SEP> Nickel <SEP> Thickness <SEP> D <SEP> 5179
<tb> Plasma <SEP> Electro <SEP> Scotch <SEP> Test
<tb> Substrate <SEP> Chemical <SEP> Chemical <SEP> Chemical <SEP> Total <SEP> Test
<tb> NH3 <SEP> Chemical <SEP> is <SEP> Shock
<tb> (m) <SEP> (m) <SEP> (m) <SEP> (m) <SEP> Adherence
<tb> (m) <SEP> 2 <SEP> (Holding <SEP> Thermal
<tb> (N / mm2) <SEP> in <SEP>%) <SEP>
<tb> Resist
<tb> PBT <SEP> 200sccm, <SEP> 0. <SEP> 3 <SEP> 6.5 <SEP> 0.25 <SEP> 5. <SEP> 2 <SEP> 12. <SEP> 25 <SEP>><SEP> 3.1 <SEP> 100 <SEP> to <SEP> 100%
<Tb>

25 Pa, ########################################

25 Pa, ###############################################

<Tb>
<tb> Resist
<tb> LCP <SEP> 180W, <SEP> 0. <SEP> 3 <SEP> 6. <SEP> 5 <SEP> 0. <SEP> 25 <SEP> 5. <SEP> 2 <SEP> 12.25 <SEP>><SEP> 1.2 <SEP> 95
<tb> ~~~~~ <SEP> to <SEP> 100%
<tb> 90 <SEP>###############################################
<tb> Resist
<tb> SPS <SEP> seconds <SEP> 0.3 <SEP> 6.5 <SEP> 0.25 <SEP> 5.2 <SEP> 12.25 <SEP>><SEP> 1.8 <SEP> 100
<tb> to <SEP> 100%
<Tb>

<Desc / Clms Page number 25>

Table 2

<Tb>
<tb> TYPE <SEP> 2 <SEP>
<tb> TYPE <SEP> ISO <SEP> z ~~~~~
<tb> ASTM
<tb> Copper <SEP> Nickel <SEP> 2409 <SEP> DIN <SEP> 53496
<tb> Nickel <SEP> Thickness <SEP> D <SEP> 5179 <SEP>
<tb> Plasma <SEP> Electro <SEP> Electro <SEP> Scotch <SEP> Test
<tb> Substrate <SEP> Chemical <SEP> Total <SEP> Test
<tb> N2 + Ne <SEP> (m) <SEP> Chemical <SEP> Chemical <SEP> (m) <SEP> Adhesion <SEP> Test <SEP> Shock
<tb> (m) <SEP> (m) <SEP> 2 <SEP> (Holding <SEP> Thermal
<Tb>

(N/mm ) (N/mm ) ' en%)~~~~~~

(N / mm) (N / mm) 'in%) ~~~~~~

<Tb>
<tb> Resist
<tb> PBT <SEP> 0. <SEP> 87 <SEP> 9 <SEP> 5.2 <SEP> 15.07 <SEP>><SEP> 2.6 <SEP> 100 <SEP> 100%
<tb> 200sccm, <SEP> Resists
<tb> PBT <SEP> 25 <SEP> Pa, <SEP> 4. <SEP> 58 <SEP> 6 <SEP> 5. <SEP> 2 <SEP> 15.78 <SEP>><SEP> 2.4 <SEP> 100 <SEP> 100%
<tb> 180W, <SEP> Resists
<tb> LCP <SEP> 90 <SEP> 0. <SEP> 87 <SEP> 9 <SEP> 5. <SEP> 2 <SEP> 15.07 <SEP>><SEP> 1.2 <SEP> 100 <SEP> to <SEP> 100% <SEP>
<Tb>

######secondes 100% secondes

###### seconds 100% seconds

<Tb>
<tb> Resist
<tb> LCP <SEP> 4.58 <SEP> 6 <SEP> 5.2 <SEP> 15.78 <SEP>><SEP> 1.1 <SEP> 90 <SEP> to <SEP> 95%
<tb> Table <SEP> 3 <SEP>
<tb> TYPE <SEP> 3 <SEP>
<tb> ASTM <SEP> ISO <SEP> 2409 <SEP>
<tb> Copper <SEP> Nickel <SEP> DIN <SEP> 53496
<tb> Nickel <SEP> Thickness <SEP> D5179 <SEP> Scotch
<tb> Electro <SEP> Electro <SEP> Test
<tb> Substrate <SEP> Plasma <SEP> NH3 <SEP> chemical <SEP> total <SEP> test <SEP> test
<tb> Chemical <SEP> Chemical <SEP> Shock
<tb> (m) <SEP>~~><SEP> (m) <SEP> Adhesion <SEP> (Holding <SEP> en
<Tb>

(IJm) (IJm) 2\\ Thermique ~~~~~~~~~~~~~~~~~~~<'~~~~~~~~(N) %)~~~~""'

(IJm) (IJm) 2 \\ Thermal ~~~~~~~~~~~~~~~~~~~~~~~~~~~~ (N)%) ~~~~ ""'

<Tb>
<tb> Resist
<tb> PBT <SEP> 0. <SEP> 35 <SEP> 15 <SEP> 5. <SEP> 2 <SEP> 20.55 <SEP>><SEP> 2.1 <SEP> 100 <SEP> to <SEP> 100 % <SEP>
<tb> Resist
<Tb>

PBT 20 SCCm' 1.5 10 5.2 16.7 ~ > 2.3 100 à 100%

PBT 20 SCCm '1.5 10 5.2 16.7 ~> 2.3 100 to 100%

<Tb>
<tb> 200sccm, <SEP> Resists
<tb> PBT <SEP> 25 <SEP> Pa, <SEP> 4. <SEP> 6 <SEP> 6 <SEP> 5. <SEP> 2 <SEP> 15.8 <SEP>><SEP> 2.45 <SEP> 100 <SEP> to <SEP> 100%
<tb> 180W, <SEP> ~~~ <SEP> ~ <SEP> Resists
<tb> SPS <SEP> 90 <SEP> 0. <SEP> 35 <SEP> 15 <SEP> 5. <SEP> 2 <SEP> 20.55 <SEP>><SEP> 2.05 <SEP> 100 <SEP> to <SEP> 95%
<tb> seconds
<tb> Resist
<tb> SPS <SEP> 1. <SEP> 5 <SEP> 10 <SEP> 5. <SEP> 2 <SEP> 16.7 <SEP>><SEP> 1.9 <SEP> 100 <SEP> to <SEP> 100 % <SEP>
<tb> Resist
<tb> SPS <SEP> 4.57 <SEP> 6 <SEP> 5.2 <SEK> 15.77 <SEP>><SEP> 1.7 <SEP> 100 <SEP> to <SEP> 100% <SEP>
<Tb>

<Desc / Clms Page number 26>

For each sample, it is observed that the initial thickness of nickel does not influence the value of the maximum adhesion stress in significant proportions. The Scotch test and thermal shock tests have similar, positive results, which confirm the previous results and confirm that the method according to the invention creates a true grafting sites attachment for the metal on the plastic substrate.

 Similarly, if we consider an electrochemical copper thickness of 6 m, it is observed that the initial thickness of nickel does not influence the value of the maximum adhesion stress.

 It has even been carried out repeated activations, before metallization, in cycles, each cycle comprising a submission of the article for 60 seconds (or other duration) to a plasma selected from those described above, an ionic graft palladium immersion during 2 minutes (or other time), and immersion for 3 minutes (or other time) in a hypophosphite bath. Different results can then be obtained, depending on the nature of the following operations and on the materials to be metallized.

 On the other hand, for two-part parts made with an overmolding of a first plastic material by a second plastic material, and because the overmolding is done in two times, the influence of the waiting time after the activation and before grafting palladium was considered. Indeed, the molded parts are molded in a first workshop of a factory, activated in another workshop of the factory, and returned to the first workshop for overmolding.

 The effects of waiting before grafting which resulted from such an industrial process have been studied in the invention. It was established that after 15 days, LCP samples were completely deactivated, PBT samples were 50% deactivated, and SPS samples were successfully metallized. This loss of activation makes it possible to make bi-material products LCP - SPS for example, fully activated, to wait 15 days (or other duration), and to metallize all. This gives a selective metallization of the parts in SPS. The shape of the mechanical structure is sufficient to separate the SPS metallized zones from the non-metallized zones into LCP.

 Similarly, the influence of the metallization time and the stirring of the metallization bath makes it possible to differentiate a metallization, by comparing

<Desc / Clms Page number 27>

 PPS and LCP, at the time of metallization in a bath with stirring, it is noted that the PPS requires 120 seconds of metallization, while the LCP reacts to the plating bath after 5 to 10 seconds. Thus, according to one embodiment of the invention, mixed PPS LCP samples are activated, immersed in the plating bath for not more than 15 seconds, and removed from the bath so that in the end only the LCP is metallized. Here too, the mechanical structure is sufficient to separate the metallized zones from the non-metallized zones without using a material provided with catalytic charges or having metallization precursor.

 In the case where the stirring of a metallization bath is stopped, the metallizations of the PPS and the LCP are immediate. In practice, stirring of the bath slows the metallization of the PPS if the speed of the stirrer is greater than 500 revolutions per minute. This is due to the fact that stirring introduces oxygen into the metallization solution. Or oxygen is a poison for the catalytic nuclei on the surface of the plastic article. An excess of oxygen deactivates the metallization of the plastic, the palladium being then poisoned or oxidized. This occurs for PPS, and less for LCP with an excess of catalytic sites.

 Excess air can, however, slow down the metallization of the LCP. By replacing the oxygen with nitrogen, the metallization of the two articles then occurs without difficulties.

 The metallization bath used is, for example, an ENPLATE NI 426 bath from Enthone OMI.

 So in addition to the duration, in this case we have a parameter relating to the stirring speed and or the bath temperature to promote selective metallization.

 Consequently, by using different high temperature polymer materials, for example PBT or PPS as non-metallizable material in common with SPS or LCP as metallizable materials, the invention makes it possible to form Molded Interconnect Devices (or devices interconnect molded). The surface shapes of the parts of the articles in these different materials respectively represent the areas not to be metallized and to metallize.

 The selectivity parameters of the differential metallization are, taken some together in combination, or separately:

<Desc / Clms Page number 28>

 the nature of the activation plasma, the carrying out of one or more activation cycles before grafting, the waiting time after activation and before grafting, the duration of metallization, the stirring rate of the metallisation bath, - the temperature of the metallisation bath, - the nature of the metal of the metallization (nickel, or copper).

 All these parameters can be adapted according to the nature of the two-component high-temperature polymer materials selected and the type of metallization required. These methods are furthermore compatible, under the same conditions as above, with overmolding techniques followed by subsequent metallization.

 An exemplary embodiment of a metallized bi-material article is schematically represented in FIGS. 2A, 2B, 2C, the first material 1 to be metallized is molded in the first place, the second material 2 which must not react to the metallization is overmolded on the first leaving areas 3 of the first apparent material. The whole is then activated by the nitrogenous plasma creating a surface provided with activated sites.

 FIG. 3 shows a partial section of a selective metallization zone with two metal layers 5, 6, some zones of which have been removed so as to allow analysis of the metal plastic interface 4.

 FIG. 4 shows the general spectrum curve by electron photometry spectrometry (ESCA or XPS analysis method) after Plasma NH3, 200 Sccm, 20Pa, 200W, 40s plating of a LCP substrate. This general spectrum has several peaks whose peak 8 representative of the presence of nitrogenous species, the peaks 7 and 9 being respectively representative of carbon species and oxygen.

 A detail of the curve in FIG. 5 centered on the peak 8 makes it possible to characterize three subpeakers 10, 11, 12 which result from the nitrogenous plasma activation.

 FIG. 6 shows a detail centered on the palladium energy zone of a curve obtained on a PPS substrate by the metallization method according to the invention. This detail makes it possible to determine two peaks 13, 14 common to palladium which according to a statistical analysis represented in FIG.

<Desc / Clms Page number 29>

 FIG. 7 shows a representative shift of Palladium / Nitrogen bonds obtained by the process according to the invention.

 Figure 8 shows a schematic view of a part made by the method according to the invention for which a plastic material 20 has been metallized. This part 20 is for example a half-housing comprising a strip 26, an outer turn 27, one or more attachment studs 28 an inner wall 29, an outer surface 30, an inner surface 31.

 This housing comprises metallized zones 21, 22, 23a to 23c, 24, 25, 32, the zone 21 forming a shielding part, the zones 24 of the metallized connecting tracks, the zones 23a to 23c of the internal connection pads connected to the shielding 21 by metallized through-holes 22, these internal connection pads making it possible to produce ground points or heat-dissipating pads, while the zone 25 extends the zone 21 to form an external mass connection point. .

 To achieve this part, the housing, for example molded in a material such as PBT, is pre-coated, on areas not to be metallized such as the strip 26 and the outer tower 27, with one or more masking elements known in the prior art and then disposed in the plasma activation chamber. Thanks to the method according to the invention, even hidden zones such as through-holes are activated and can, during immersion in the palladium bath, undergo grafting of palladium and the formation of palladium-nitrogen bonds and constitute hooking for metallization.

 The part is then immersed in the bath or successive baths metallization itself to obtain the metallized layers as described above in thicknesses compatible with the shielding function or the desired current conduction function.

 In order to limit the complexity of the masking operation, it is possible to metallize the inner face 31 uniformly, an additional laser structuring step then makes it possible to make the tracks 24 and to separate the pads 23a to 23c on this internal face. 31.

 Thus, the process and the parts obtained by this process can be performed flexibly and in a time less than the processes of the prior art and in so-called high temperature materials suitable for industrial use with a high technical content.

Claims (13)

1 - Method of metallizing a high-temperature polymer plastic article comprising cleaning steps, etching by plasma, grafting and metallization by immersion in a plating bath, characterized in that the plating bath is worn at a temperature between 50 C and 70 C.  2 - Process according to claim 1, characterized in that the bath is heated to a temperature of 55 C to 65 C.  3 - metallization process of a high-temperature polymer plastic article comprising cleaning steps, etching by plasma, grafting and metallization by immersion in a metallization bath, characterized in that the attack step by plasma uses a nitrogenous plasma type N2, or NH3, or N2 + H2.  4 - Process according to one of claims 1 to 3, characterized in that the gas used for the plasma comprises an inert rare gas such as neon, helium or argon, the inert gas being added in a proportion of 0.1 to 6% to increase the dissociation of nitrogen into reactive compounds of 7 to 8% free radicals.  5 - Process according to one of claims 1 to 4, characterized in that the activation time by plasma is of the order of 5 seconds to 5 minutes.  6 - Process according to one of claims 1 to 5, characterized in that the power density of the plasma is of the order of 0.1W / cm2 to 1.1W / cm2.  7 - Method according to one of claims 1 to 6, characterized in that the grafting is carried out by a dive of the article in an ionic solution comprising palladium salts, including chlorinated salts of PdCl2 + HCl, and comprises a grafting of palladium ions.  8 - Process according to one of claims 1 to 7, characterized in that the polymers are PBT, LCP, PPS or SPS.  9 - Process according to one of claims 1 to 8, characterized in that the immersion metallization is completed to give a thick metallization by electrochemical or galvanic deposition, a characteristic of the resulting product being found there by analysis of nitrogen compounds at the metal-polymer interface, the metallized layer having a thickness of between 0.2 m and 20 m. <Desc / Clms Page number 31>  10 - Method of metallizing a high-temperature polymer plastic article comprising the steps of cleaning, etching by plasma, grafting and metallization by immersion in a plating bath, characterized in that the article comprises parts in different plastics, and in that the operating conditions of these steps are set such that the metallization is effective on one of these parts and not on the other.  11 - Method according to one of claims 1 to 10, characterized in that the operating conditions set of these steps are at least one of the following taken some together in combination, or separately, - the nature of the activation plasma the production of one or more activation cycles before grafting, the waiting time after activation and before grafting, the duration of metallization, the stirring rate of the metallization bath, the temperature of the metallization bath, - the nature of the metal of the metallization (nickel, or copper) .: 12 - Method according to one of claims 1 to 11, characterized in that the duration of action of the plasma is less than or equal to 15 seconds.  13 - Method according to one of claims 1 to 12, characterized in that the metallization bath is a copper bath.