EP3126064A2 - Surface functionalisation method - Google Patents
Surface functionalisation methodInfo
- Publication number
- EP3126064A2 EP3126064A2 EP15721851.2A EP15721851A EP3126064A2 EP 3126064 A2 EP3126064 A2 EP 3126064A2 EP 15721851 A EP15721851 A EP 15721851A EP 3126064 A2 EP3126064 A2 EP 3126064A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- paa
- solution
- typically
- metallization
- polymer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
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- 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
- C23C18/31—Coating with metals
- C23C18/38—Coating with copper
-
- 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
- C23C18/31—Coating with metals
- C23C18/38—Coating with copper
- C23C18/40—Coating with copper using reducing agents
Definitions
- the present invention relates to a method for functionalizing a surface of an organic or inorganic solid support with at least one layer of acrylic acid-based polymer, the substrates obtainable by this process, and their use for the preparation of implantable medical devices, for surface preparation of biosensors, for structural bonding, for the manufacture of composite materials, for printed electronics, for the complete or localized metallization of glass or plastic surfaces, for the production of hydrophilic glazings or hydrophobic, for the treatment of heavy metals liquid effiuents.
- the grafting of thiols on gold surface is based on the privileged chemical interaction of sulfur atoms on a gold surface. This process makes it possible to produce self-organized organic monolayers [Chem. Rev., 2005, 105 (4), pp 103-170]. The method is generally reserved for fundamental studies and is not of significant stability since the thiol layer can be desorbed. It is not strictly covalent interfacial links.
- silane layer on glass or oxide is based on the privileged interaction of the silicon atoms with the oxygen atoms. This process is widely used in microelectronics [Silanes and Other Coupling Agents, Volume 4, KL Mittal, CC Press 2007]. Covalent siloxane bonds can under certain conditions be created but they will remain sensitive to hydrolysis.
- cathodic electrografting makes it possible to create a real covalent bond between the organic layer and the substrate.
- electrografting of vinyl monomers [ChemPhysChem 2004, 5, 1469-1481]
- electrografting of diazonium salts [WO 1998044172]
- electrografting of a mixture of vinyl monomers and diazonium salts [WO 2007/048894]
- these methods require the implementation of a conductive or semiconductor substrate of electricity.
- the Graftfast® process is a process for the surface coating of conductive, semiconducting and insulating substrates by a thin layer of organic polymer, via the redox activation of aryldiazonium salts in the presence of vinyl monomers, in an aqueous acidic medium (Mevellec et al. Chem., 2007, 19, 6323-6330, EP 2,121,814 B1).
- the aryldiazonium salts are reduced with an iron powder to form surface-reactive aryl radicals, leading to (i) the formation of polyphenylene type films on the surface of the substrate and (ii) initiating the polymerization of the vinyl monomer in solution.
- the radical-terminated macromolecular chains formed in solution are then capable of reacting with the polyphenylene-based primer to form a very thin and homogeneous organic film on the surface.
- an adhesion primer especially via cleavable aryl salts, especially aryldiazonium salts.
- the layer of polymer immobilized on the surface of the solid support constitutes in itself an adhesion layer, capable of reacting with other molecules present in its environment, via the carboxylic acid and / or anhydride functions of the polymer based on acrylic acid.
- the acrylic acid polymer is a biocompatible polymer, which makes it particularly suitable for functionalizing supports intended for a biological or medical application.
- this method makes it possible to very easily control the thickness of the acrylic acid polymer-based adhesion layer, either through the mass concentration of the acrylic acid-based polymer in the solvent, or taking advantage of the polyelectrolytic properties of the acrylic acid polymer that allow it to strongly adsorb onto substrates that exhibit surface electrostatic charges (such as, for example, oxides, metals, or surface oxidation-treated materials). Under these conditions, it is then possible to obtain, in a reproducible and conformal manner (ie, the layer perfectly follows the topography of the surface of the material), a thin layer (in particular ⁇ 20 nm thick) of residual polymer of acrylic acid.
- This faculty is particularly interesting when it comes to coating substrates with a complex geometry, for example substrates having a spherical geometry, or edges such as cubic or parallelepipedal geometries, or having a high form factor: this is particularly the case for substrates having a groove or a deep hole whose opening diameter is narrow, such as vias in microelectronics.
- the Conformity of the acrylic acid-based polymer layer obtained by this method makes it possible to obtain, during the subsequent metalization of the substrate, a metallic coating of very good optical quality ("mirror-polished" appearance).
- the method of the invention also advantageously makes it possible to modulate the swelling of the adhesion layer via, in particular, the crosslinking of the polymer based on acrylic acid during the heat or radiative treatment.
- this process makes it possible to functionalize organic or inorganic solid supports of varied nature, in particular glass and stainless steel, or polymers known to be very difficult to modify, such as, for example, polytetrafluoroethylene (PTFE) whose metalization according to the process. of the invention offers important advantages in the field of high frequency electronics.
- PTFE polytetrafluoroethylene
- the subject of the invention is a process for functionalizing a surface of a solid support with at least one acrylic acid-based polymer layer, said process comprising the steps of:
- Said solution not comprising an adhesion primer based on curable aryl salts, especially aryldiazonium salts;
- the solid support implemented in step i) may be an organic or inorganic support, in particular a conducting, semiconducting or insulating support. It can be chosen in particular from metals such as copper, nickel, stainless steel, aluminum, iron, titanium, or their oxides, such as titanium dioxide (TiO 2 ), iron oxides, or aluminum oxides; mineral oxides, especially those based on silicon oxide commonly called glasses; plastics; cellulosic papers, synthetic papers such as Teslin®, carbon fibers, especially woven or non-woven fibers, and composite materials such as fiberglass-reinforced epoxy resins, carbon fibers or natural fibers.
- metals such as copper, nickel, stainless steel, aluminum, iron, titanium, or their oxides, such as titanium dioxide (TiO 2 ), iron oxides, or aluminum oxides
- mineral oxides especially those based on silicon oxide commonly called glasses
- plastics cellulosic papers, synthetic papers such as Teslin®, carbon fibers, especially woven or non-woven fibers, and composite materials such as
- the method comprises a step o), prior to step i), of subjecting the solid support to a surface pretreatment of the oxidative type, in particular chemical and / or radiative, so as to increase the affinity of the solid support with the solution containing the acrylic acid-based polymer.
- This treatment may comprise an oxygen or argon plasma exposure step, a UV-Ozone activation or a chemical oxidation with acids.
- the method comprises a step o '), prior to step i), of subjecting the solid support to an oxidative type surface pretreatment followed by a deposition of a thin film (in particular ⁇ 5 nm thick) of a cationic polymer, typically polyethylene imine (PEI) or polyallyl amine so as to increase the affinity of the solid support with the solution containing the acrylic acid-based polymer, by developing the electrostatic interactions.
- a cationic polymer typically polyethylene imine (PEI) or polyallyl amine
- polymer based on acrylic acid means a polymer comprising the following repeating unit: - (CH 2 -CX (COOH)) n - where X is H, or an alkyl group C 1 -C 6 , especially C3 ⁇ 4 or C 2 H 5 .
- copolymer mention may be made of the copolymer of acrylic acid and maleic acid.
- the molecular weight of the polymer based on polyacrylic acid can vary to a large extent, especially g.mof 2000 * 1 000 000 g.mol "1.
- the molecular weight of the polymer based on polyacrylic acid is between 50,000 g.mol -1 and 300,000 g mol -1 .
- the polymer is a homopolymer of acrylic acid, also designated PAA hereinafter, having in particular a molecular weight of 130 000 g-mof 1.
- the solution implemented in step i) may further comprise a second or more homopolymers of acrylic acid of different molecular weight.
- the solvent may be selected from water, alcohols, or a mixture thereof.
- the alcohols may in particular be chosen from C1-C6 alcohols, especially ethanol.
- the solvent is a hydroalcoholic mixture, especially a water-ethanol mixture.
- the water-alcohol action can vary to a large extent, especially as a function of the surface energies of the materials to be functionalized.
- the solution implemented in step i) may further comprise a second polymer based on acrylic acid of a different nature from the first.
- This solution may also comprise adjuvants such as wetting agents, fluidifiers, emulsifiers or pigments, complexing agents, fluorophores. It may also comprise crosslinking agents such as polyallylamine hydrochloride, hexamethylenediamine hydrochloride, polyethylene glycol or polyethylene glycol-diamine.
- the solution implemented in step i) does not comprise an adhesion primer based on cleavable aryl salts, in particular aryldiazonium salts. According to one embodiment, the solution implemented in step i) does not comprise an adhesion primer other than the acrylic acid-based polymer.
- adhesion primer is intended to mean any organic molecule capable, under certain conditions, of adhering, in particular of chemisorbing on the surface of a solid support, in particular by radical reaction such as a radical chemical grafting. Such molecules comprise at least one functional group capable of forming a radical.
- adhesion primers include cleavable aryl salts such as aryldiazonium salts.
- cleavable aryl salts means aryl salts (ArX n + , Y n- ) capable of generating an aryl radical (Ar * ), in particular by homolytic cleavage of the linkage. Ar-X.
- cleavable aryl salts include aryldiazonium salts, ammonium aryl salts, aryl phosphonium salts, aryl iodonium salts, and aryl sulfonium salts. These molecules are thus capable of forming a crosslinked film adhering to the surface of the solid support via these radical reactions.
- the solution can be applied to the surface of the solid support according to various methods, including dipping (immersion-emersion), centrifugation (spinning), spraying (spray), projection (inkjet, spraying), transfer (brush, brush) felt, pad).
- the thickness of the acrylic acid-based polymer layer obtained in step iii) is easily adjustable via the concentration of the acrylic acid-based polymer in the solution of step i) and / or via the deposit successive layers of polymers based on acrylic acid on the surface of the support, that is to say via the repetition of steps i) to iii), step iii) being optional between two successive deposits.
- a concentration of PAA in ethanol of 2% by weight makes it possible to obtain a layer of PAA with a thickness of 1000 nm. .
- Step ii) consists in removing the solvent from the solution of step i) deposited on the surface of the solid support, generally in the form of a homogeneous film.
- the removal of the solvent can be carried out by any suitable technique well known to those skilled in the art such as simple air drying, in particular for solutions based on alcoholic solvents, for example with ethanol, evaporation under reduced pressure, in particular for solutions based on hydroalcoholic solvents.
- the method further comprises two steps subsequent to step ii) of:
- Step iii) eliminates the polyacrylic acid-based polymer not specifically adsorbed and / or chemically on the surface of the solid support at the end of steps i) and ii).
- This step may comprise several successive rinsing with water, until a conformal layer is obtained, that is to say a layer of residual polymer, of constant thickness, on the surface of the solid support. .
- steps iij) and ii 2 ) advantageously make it possible to control the thickness of the acrylic acid-based polymer layer attached to the surface of the W
- the acrylic acid-based polymer behaves like a polyelectrolyte which can be adsorbed by electrostatic interactions on certain surfaces such as oxides, metals, or materials having undergone superficial oxidation (chemical and / or radiative), thus creating electrostatic charges favorable to the expression of the adsorption phenomena.
- electrostatic interactions are exerted over a distance that is dependent on the nature of the polymer and the substrate. The equilibrium of these different forces leads to the deposition of a thin layer, of perfectly defined thickness after several successive rinses.
- LBL Layer By Layer
- Step iii) is a step for fixing the acrylic acid-based polymer to the surface of the solid support by heat or radiative treatment of the surface obtained in step ii).
- fixing is meant, in particular, a covalent or non-covalent grafting, especially via polyelectrolytic interactions, of the polymer on the surface of the solid support.
- the deposit obtained in step ii) undergoes a heat treatment or radiative, especially via light or electronic irradiation, to make it adherent to this surface.
- This treatment in fact creates chemical hardening mechanisms, in particular through homo-crosslinking of the acrylic acid-based polymer, which render the polymer layer insoluble, difficult to dissolve and mechanically difficult to tear off.
- this process makes it possible to obtain adhesion of the acrylic acid-based polymer layer on any type of material.
- This adhesion would result from different physicochemical phenomena that can vary depending on the nature of the support and / or the nature of the treatment in step iii), that is to say thermal or radiative.
- the heat or radiative treatment would notably make it possible to generate reactive radical species which will confer cohesive properties, by the crosslinking between the polymer chains between them, and / or adhesive properties, by the reaction of the radical species with the solid support.
- the adhesion of the acrylic acid-based polymer layer to solid supports could result from covalent grafting via thermal decarboxylation of the polymer to Acrylic acid base.
- the adhesion could result from a polyelectrolyte adhesion, that is to say the interaction between the calcium or aluminum ions of the glass and the carboxylate functions of the polymer based on acrylic acid via the formation of saline bridges (U. Lohbauer, Materials 2010, 3, 76-96).
- the adhesion and hence adhesion of the acrylic acid-based polymer results from a number of factors or a combination of these including viscoelastic dissipation capabilities of the polymer, the polyelectrolyte character of the latter and / or the crosslinking induced by a heat treatment or radiative via the decarboxylation of anhydride functions.
- step (iii) is carried out by heat treatment, especially at a temperature between 150 ° C and 300 ° C, more particularly at a temperature of about 200 ° C.
- this treatment is performed on materials that can withstand such temperatures for a period of up to 60 minutes, typically 2 to 30 minutes.
- the heat treatment may in particular be applied to substrates such as metals (stainless steel, aluminum, copper, titanium), glasses, silicon and certain thermo stable polymers such as polyimide or polytetrafluoroethylene.
- substrates such as metals (stainless steel, aluminum, copper, titanium), glasses, silicon and certain thermo stable polymers such as polyimide or polytetrafluoroethylene.
- Scheme 3 Schematic diagram of grafting by heat treatment.
- the polymer layer has a very high concentration of residual anhydride groups that can be spontaneously engaged in chemical reactions, for example and without limitation with amine, alcohol, acid or thiol functions.
- anhydride functions can also be hydrolysed in a basic medium to generate carboxylate functions, which can then be acidified to carboxylic acid functions, which can also be reacted according to usual coupling chemical methods.
- the acidic or basic chemical forms of the PAA can be easily restored by a simple pH control of the solution in which the film is immersed.
- the acid-base conversion is usually fast. If the PAA film is returned to its acid form, it is possible to repeat a complete transformation cycle: acid-anhydride-carboxylate-acid, and so on.
- the annealed film retains its swelling character vis-à-vis solvents, including aqueous; essential property for some applications such as metallization for example.
- step iii) is carried out by radiative treatment.
- This treatment consists in subjecting the polymer to ultraviolet radiation (Vacuum UV, or VUV), that is to say at a wavelength of between 100 and 200 nm. It is particularly suitable for flat or shaped surfaces allowing exposure to light, in particular to solid supports selected from gold layers, polyvinyl chloride (PVC), polyethylene terephthalate (PET), polyvinylidene fluoride (PVDF) ), and polytetrafluoroethylene (PTFE).
- PVC polyvinyl chloride
- PET polyethylene terephthalate
- PVDF polyvinylidene fluoride
- PTFE polytetrafluoroethylene
- the radiative route advantageously makes it possible to immobilize thin films of polymer based on acrylic acid on thermally fragile substrates.
- the radiation of 172 nm of the excimer lamp OSRAM brand XERADEX® type breaks the bonds of the acrylic acid-based polymer and create excited species, including radicals and / or ions.
- Figure 4 shows that at 172 nm, many chemical bonds of the polymers can absorb light and be excited.
- the radicals are notably capable of recombining by interchain mechanisms which make it possible to crosslink the film in its volume but also to recombine with the surface when they are formed nearby.
- the substrate is itself organic (such as PVC, PET, PVDF, PTFE) and reached by radiation, it can be, in the same way, excited and recombine with the polymer that covers it.
- the radiative treatment thus makes it possible to confer cohesive properties (crosslinking) and adhesive properties (surface grafting). (See figure 5 below).
- the adhesion of the acrylic acid-based polymer layer to the surface implies that the radiation reaches the film-substrate interface.
- the thickness of the layer can thus be adjusted according to the radiation absorption decay rules, the duration and / or the irradiation power.
- films of 1 to 150 nm can be immobilized with irradiation times of between 2 and 15 minutes for an irradiation power of the order of 140W.
- the polymer layer still has a very high concentration of carboxylic groups which can be spontaneously engaged in chemical reactions, for example and without limitation with amine, alcohol, acid or thiol functions.
- the irradiated film retains its swelling character vis-à-vis solvents, aqueous in particular; essential property for some applications such as metallization for example.
- the process according to the invention comprises a step subsequent to step iii) of covalent grafting of molecules of interest on the polymer layer obtained, in particular a biological molecule or a resin, that is to say say a natural or synthetic polymer, especially thermoplastic or thermosetting, more particularly the two-component resins.
- Two-component resins are resins obtained from two components: the resin on the one hand, which may be a first monomer or a prepolymer, and the hardener on the other hand, which may be a second monomer or prepolymer, also called agent crosslinking.
- the resin on the one hand which may be a first monomer or a prepolymer
- the hardener on the other hand which may be a second monomer or prepolymer, also called agent crosslinking.
- agent crosslinking also called agent crosslinking
- Formaldehyde amino -NH2 groups formaldehyde or urea-formaldehyde (VF)
- Aminoplasts melamine-melamine resins and sometimes formaldehyde or melamine-formaldehyde
- thermosets PIRP
- the biological molecule can be grafted by a bioconjugation reaction between the carboxylic acid groups of the surface (obtained after VUV treatment or after hydrolysis of the anhydride functions) and the amino functions of the proteins, as is conventionally done with peptide couplings employing a combination of activating agents such as N-hydroxysuccinimide and ⁇ , ⁇ dicyclohexylcarbodiimide (NHS / DCC) in an organic medium or sulfo-N-hydroxysuccinimide and ethyl-3- hydrochloride ( 3-dimethylaminopropyl, carbodiiride (sulfo-NHS / EDC) in an aqueous medium.
- activating agents such as N-hydroxysuccinimide and ⁇ , ⁇ dicyclohexylcarbodiimide (NHS / DCC) in an organic medium or sulfo-N-hydroxysuccinimide and ethyl-3- hydrochloride
- the covalent grafting step subsequent to step iii) comprises:
- the activated esters formed react with the neighboring acid groups to reform, this time chemically, anhydride functions, even at room temperature.
- this embodiment makes it possible to obtain a coating having anhydride functions without resorting to heat treatment. This is particularly interesting for thermally fragile substrates and therefore unable to withstand the treatment at a temperature between 150 ° C and 300 ° C, required to obtain the anhydride functions directly.
- bicomponent resins for example example with the amino groups of the bicomponent epoxy resins (polyepoxy resins (EP)) 5 polyimides (thermosetting polyimide resins PIRP) and melamine-formaldehyde (melamine-formaldehyde aminoplast resins (MF)) or with alcohol groups of two-component polyurethane resins (cross-linked polyurethane resins (PUR)).
- EP polyepoxy resins
- PIRP thermosetting polyimide resins
- MF melamine-formaldehyde aminoplast resins
- PUR cross-linked polyurethane resins
- the polymer solution in step (i) comprises metal salts.
- the process then comprises a step subsequent to step iii) of reducing the metal salts, whereby a metallization of the surface of the solid support is obtained.
- the subject of the invention is the substrates that can be obtained by the process as defined above.
- the acrylic acid-based polymer layer immobilized on the surface of the solid support generally has a thickness of between 3 nm and 5000 nm, especially between 10 nm and 1000 nm, more particularly between 20 nm and 500 nm, especially between 10 and 100 nm, for example between 20 nm and 70 nm. More particularly for the radiative treatments, the acrylic acid-based polymer layer immobilized on the surface of the solid support has a thickness of between 3 nm and 300 nm, in particular between 10 nm and 100 nm, for example between 20 nm and 70 nm. nm.
- Resistance to prolonged washings means that the intensity of the infrared absorption signal of the characteristic bands of the immobilized PAA (intensity directly related to the thickness of the PAA layer), in particular the absorption bands characteristic of the acid functions.
- carboxylic at 1721 cm “1 etc carboxylates to 1576 cm” varies by less than 20%, preferably less than 10%, prefer! less than 5% ,.
- the degree of crosslinking obtained following the heat treatment or radiative the removal of uncrosslinked chains is possible (cavities can thus advantageously be formed). It is then important to observe the stabilization of the quantity of material with respect to washes.
- the intensity of the absorption peak of the COOH carboxylic function (1721 201 201
- the subject of the invention is the use of the substrates that can be obtained according to the process of the invention, and / or the use of the process according to the invention for the treatment of liquid effluents by capture of the heavy metals, the preparation of stents, prostheses, implantable medical devices, for the realization of electrical circuits on glass, plastic, optical resin (cyclic olefins polymer-based resins (Cyclo Olef Method or COP) for example) or paper (Teslin® type for example) such as RFID antenna circuits, or for producing reflective surfaces, for grafting biological molecules on paper, glass, plastic or metal, for structural bonding applications , for the manufacture of composite materials with carbon fiber reinforcement (or Carbon Fiber Reinforced Polymer, in English).
- optical resin cyclic olefins polymer-based resins (Cyclo Olef. Polymer or COP) for example
- paper Teslin® type for example
- RFID antenna circuits or for producing reflective surfaces, for grafting biological molecules on paper,
- the invention relates to the use of the method according to the invention for depositing a metalization primer on a substrate electroless way, especially on glass, polymers, especially composites such as polymers with fiber reinforcement. carbon or fiberglass.
- electroless metalization refers to a process of metalization by chemical means that is to say without electricity or electrolytic bath, via a controlled autocatalytic reduction process of metal ions leading to the formation of a uniform metal layer.
- Silanes are compounds that are simultaneously capable of grafting onto glass and capturing catalytic metals from electroless processes.
- Their disadvantages are, on the one hand, the hydrolyzable nature of the deposited layers. Indeed, the Si-O-Si siloxane bond is very polar, therefore highly hydrolyzable.
- the leaching of a glazing facade is ⁇ ⁇ ⁇ ⁇ per year that is to say several nanometers per day.
- silane solutions used to make the coatings are not chemically stable over time. The solution is prepared and condensation mechanisms occur. We must constantly redo the solutions before application.
- the method according to the invention advantageously makes it possible to overcome these disadvantages.
- aircraft fuselage or wing elements are generally made of electrically conductive materials.
- the aeronautical industry is increasingly tending to substitute these conductive materials with carbon composites, which have an insulating character and it is therefore necessary to metallize.
- This metallization is currently done by adding copper fabrics or adding copper wires into the carbon composites.
- this metallization is very expensive and cumbersome to implement.
- Another method is to project metal particles onto the composite material so as to physically embed these particles in the material.
- the continuity of the layer and the resulting conduction properties are however not satisfactory.
- the metallization method according to the invention makes it possible to metallize at lower cost, superficially, in continuous and thin layers, such composites, in particular composites of carbon fibers-epoxy resin, to render them conductive.
- this method is easy to implement, and allows to metallize elements directly on site.
- the method is thus particularly useful for metallizing the constituents of the cell of an aircraft, in particular the fuselage or the wing, made of polymer composite materials, in particular reinforced with carbon fiber.
- the process according to the invention is also particularly useful for metallizing heat-resistant polymers which are difficult to treat superficially.
- the method makes it possible to metallize keviar, in particular in the form of a fabric for intelligent textile applications, or else polyimide for applications of printed flexible electronics.
- the method according to the invention is also particularly useful for metallizing semiconductor materials. Indeed, a recurrent problem of microelectronics is the realization of barrier layers to the diffusion of copper atoms (realizing the conductive parts) to silicon (semiconducting part) to prevent the copper from poisoning the semiconducting properties of silicon. .
- the metallization of titanium nitride is currently carried out via physical metallization processes under vacuum, particularly heavy and complex to implement.
- the method according to the invention allows the formation of barrier layers, for example nickel, having an electrical continuity between the copper on the one hand, and the titanium nitride on the other hand.
- the process according to the invention is also useful for the preparation of depollution coatings, for example for the manufacture of a liquid effiuents filtration material contaminated with dissolved metal salts.
- the film is at the end of heat treatment grafted chemically on the substrate and crosslinked. It is in a totally anhydride chemical form for functions that have not undergone decarboxylation.
- the PAA film is then treated in a basic aqueous solution in order to rehydrate the anhydrides and to restore the polyacrylic acid form.
- This chemical form of polyacrylic acid can advantageously capture metal salts effectively and is therefore particularly useful for depollution or metallization applications.
- the method is also useful for the preparation of self-adhesive adhesion reinforcement via the anhydride functions.
- the method according to the invention thus makes it possible to deposit, over a wide range of substrates, thin coatings in an anhydride form capable of spontaneously and very easily reacting at room temperature with resins or two-component paints such as epoxy resins or paints. or polyurethane.
- resins or two-component paints such as epoxy resins or paints. or polyurethane.
- the anhydride forms react very efficiently with the amino groups of the resin before it is crosslinked.
- This graft coating is particularly advantageous when the substrates to be bonded or coated have very smooth surfaces, that is to say very polished surfaces. Indeed, in these cases, it is not possible in the adhesion phenomena to use the mechanical anchoring which is very often involved in the overall adhesion.
- the process according to the invention advantageously makes it possible to obtain an excellent chemical adhesion on these very smooth surfaces, in particular chemically weakly reactive surfaces where mechanical anchoring is not present.
- the method is particularly useful for improving the adhesion of gems to mirror polished precious metal surfaces.
- the invention relates to the use of the method according to the invention for metallizing plastics, or metal or mineral oxides such as silica (SiO 2 ) or indium titanium oxide (ITO). 201
- the invention relates to the use of the method according to the invention for functionalizing a surface of a solid support with biological molecules.
- the invention relates to the use of the method according to the invention for functionalizing a surface of a solid support with an adhesion primer comprising or consisting of a polymer layer based on acrylic acid.
- Figure 2 Photograph of a glass slide immersed in a palladium activation bath and then in a nickel plating bath in the presence of a PAA film locally deposited on the surface with the aid of an adhesive stencil. Metallization occurred only at locations where AAP was deposited.
- Figure 4 Photograph of a locally metallized PVC surface using PAA solution as an ink deposited by a fountain pen.
- FIG. 5 IR Transmittance as a Function of the Wavelength of a Polyimide Support (PI) Functionalized by PAA
- FIG. 6 IR Transmittance as a Function of the Wavelength of a PAA Functional Polyethylene Terephthalate (PET) Backing
- FIG. 7 IR Transmittance as a Function of the Wavelength of a Polyethylene (PE) Support Functionalized with PAA
- Figure 9 (a) chemical mechanism responsible for the adhesion of the amine hardener of the resin to the anhydride groups of the support.
- Figure 10 Increased surface energy of hydrophobic PVC. Measurement of contact angles before (left - 70 °) and after (right - 30 °) treatment.
- Figure 1 1 Decrease of the surface energy of a golden surface. Hydrophilic gold layer turned hydrophobic by grafting a long alkyl layer. High: IR transmittance as a function of the wavelength of a gold-plated support (glass-evaporated gold layer) functionalized with PAA, and grafted with a Ci-1 alkylamine. Bottom: measure contact angles. (Left) Gold alone, (center) Gold + PAA, (right) Gold + PAA + amine Cl l.
- FIG. 12 IR transmittance as a function of the wavelength of a gold support functionalized by an adsorbed residual layer of PAA.
- Figure 13 IR transmittance as a function of the wavelength tracing the different steps of protein grafting with activation of the surface in organic medium.
- Figure 14 IR transmittance as a function of the wavelength tracing the various steps of protein grafting with activation of the surface in an aqueous medium.
- Figure 15 Photographs a) virgin carbon fiber fibers before coating, b) and c) carbon fiber fibers coated with PAA film
- Figure 16 Treated carbon felt and column treatment device.
- Figure 17 Metallization of a carbon-epoxy composite plate used in aeronautics.
- Example 1 Metallization of the surfaces.
- Example 1-a Full surface metallization of a glass surface. (Heat treatment)
- a solution of PAA (M n 130 000) with a concentration of 50 mg in 10 ml of ethanol is prepared by dissolution.
- a microscope-type glass slide (7.5x2.5 cm) is degreased (washing with a surfactant and then typically an alcohol rinse) and then dried (with a dry gas blower of nitrogen and then a passage to the oven at 100 ° C for 15 minutes).
- the application of the PAA solution is made by soaking-withdrawal (immersion-emersion) in order to obtain, after evaporation of the ethanol, a film of PAA covering and homogeneous thickness of 50 to 70 nm.
- the PAA deposit then occurs on both sides of the glass slide.
- the glass slides coated with PAA are then typically heated at 200 ° C. for 30 min in a single oven at atmospheric pressure and without any particular precaution.
- the solution can be prepared in advance.
- the activated glass slide is immersed in an electroless bath (i.e., an electrolytic bath) regulated at a temperature of 34 ° C.
- an electroless bath i.e., an electrolytic bath
- the bath is typically a Niposit TM PM 988 commercial bath. Its pH is 9.4.
- the reducing agent is sodium hypophosphite (NaH 2 PO 2 , H 2 O).
- the activated glass slides are left for 10 minutes in order to have a complete and homogeneous metallization.
- the thickness of the nickel film is typically 500 nm.
- Adhesion / adhesion of the metal coating to the substrate The adhesion / adhesion of the metal layer is determined by applying the ASTM D3359 standardized scotch test.
- a glass slide which has not been covered with a PAA layer has been metallized by immersion in the activation solution. of palladium acetate described above. Due to the hydrophilic nature of the glass substrate, the palladium ions adsorb on this surface. This is then transferred to the electroless bath and the process of methanol is developed. Rinsing with water and drying with a dry gas gun is sufficient. The thickness of the nickel film is typically 200 nm.
- Figure 1 shows:
- Example 1-b Full-surface metallization of a glass surface with a PAA film of residual thickness in conformity. (Heat treatment)
- Example 1-b Full-surface metallization of a glass surface with a PAA film of residual thickness in conformity. (Heat treatment)
- a solution of PAA (M n 130 000) with a concentration of 5 mg in 10 ml of ethanol is prepared by dissolution.
- a microscope-type glass slide (7.5x2.5 cm) is degreased (washing with a surfactant and then typically an alcohol rinse) and then dried by a heat gun at a temperature exceeding 200 ° C without exceeding 300 ° C for 1 minute.
- the application of the PAA solution is made by soaking-withdrawal (immersion-emersion) in order to obtain, after evaporation of the ethanol, a film of PAA covering and homogeneous with a thickness of 10 nm .
- the PAA deposit then occurs on both sides of the glass slide.
- the PAA coated glass slides are then typically rinsed with deionized water to remove unadsorbed PAA chains.
- the polyelectrolytic interactions govern the persistence of a residual thin film of a few nanometers (less than 5 nm). This residual film is then heat-treated with a heat gun for 90 seconds at a temperature exceeding 200 ° C and not exceeding 300 ° C.
- the solution can be prepared in advance.
- the activated glass slide is immersed in an electroless bath (i.e. an electrolytic bath) regulated at a temperature of 34 ° C.
- an electroless bath i.e. an electrolytic bath
- the bath is typically a Niposit TM PM 988 commercial bath. Its pH is 9.4.
- the reducing agent is sodium hypophosphite (NaH 2 PO 2 , H 2 O).
- the activated glass slides are left for 10 minutes in order to have a complete and homogeneous metallization.
- the thickness of the nickel film is typically 500 nm.
- Figure 1-e shows that a PAA film of residual thickness (less than 5 nm), thanks to its perfectly compliant character, makes it possible to obtain a high quality metallic layer of mirror polished type. In addition, an adhesive tape test was performed and no detachment was observed.
- Example 1-c Localized metallization of a glass surface. (Heat treatment)
- a solution of PAA (M n 130 000) with a concentration of 50 mg in 10 ml of ethanol is prepared by dissolution.
- a microscope-type glass slide (7.5x2.5 cm) is defatted (washing with a surfactant and then an alcohol rinse) and then dried (with a dry gas blower of nitrogen and then a passage to the oven at 100 ° C for 15 minutes).
- the application of the PAA solution is made with a stencil (masking) and a sprayer.
- the pattern of the adhesive stencil here is drops of water. ( Figure 2).
- the adhesive stencil is removed after drying the PAA layer.
- the glass slides coated with PAA are then typically heated at 200 ° C. for 30 min in a single oven at atmospheric pressure and without any particular precaution.
- the solution can be prepared in advance.
- the activated glass slide is immersed in the regulated electroless bath at a temperature of 34 ° C.
- the bath is typically a Niposit TM PM 988 commercial bath. Its pH is 9.4.
- the reducing agent is sodium hypophosphite (NaH 2 PC 3 L 2 O).
- the activated glass slides are left for 10 minutes in order to have a complete and homogeneous methalation.
- the thickness of the nickel film is typically 500 nm.
- Figure 2 shows that only areas initially coated with PAA were metallized.
- Example 1-d Full surface metallization of a PVC surface. (VUV radiative treatment)
- a solution of PAA typically of 50 mg in 10 ml of ethanol is prepared by dissolution.
- the PVC flexible plate (format and manufacture for credit card) is degreased (typically washing with a surfactant and then typically an alcohol rinse) and then dried (typically by a blowgun of dry nitrogen gas).
- the application of the PAA solution is typically done by soaking-withdrawal (immersion-emersion) in order to obtain, after evaporation of the ethanol, a film of PAA covering and homogeneous with a thickness typically of 50. at 70 nm.
- the PAA deposition will then occur on both sides of the PVC plate ( Figure 3).
- the PVC plates are typically insolated by VUV (Vacuum Ultraviolet) radiation for 2 minutes at a distance of 15 cm in a purged air atmosphere by dry nitrogen sweep.
- VUV Vauum Ultraviolet
- the characteristics of the VUV lamp are: Excimer lamp of the brand OSRAM model XERADEX. Power of 140 W. Radiation 150 to 190 nm with maximum at 172 nm.
- the solution can be prepared in advance. Typically:
- the PVC plates are placed at room temperature for 10 min in the activation solution. A rinsing with DI water is done.
- the activated PVC plate is immersed in the regulated electroless bath at a temperature of 34 ° C.
- the bath is typically a Niposit TM PM 988 commercial bath. Its pH is 9.4.
- the reducing agent is sodium hypophosphite (NaH 2 O 2 , H 2 0).
- the activated PVC is left for 10 minutes in order to have a complete and homogeneous metallization.
- the thickness of the nickel film is typically 500 nm.
- a 10-minute argon plasma treatment allows the surface of the PTFE substrate to be homogeneously wetted by the PAA solution and thus deposit a PAA film of uniform thickness. On the unexposed side of the plasma, the wettability was not sufficient to coat the PTFE with the PAA film.
- the application of the PAA solution is typically done by soaking-withdrawal (immersion-emersion) in order to obtain, after evaporation of the ethanol, a film of PAA covering and homogeneous with a thickness typically of 50. at 70 nm.
- PAFE-coated PTFE carriers are then typically heated at 200 ° C for 30 min in a single oven at atmospheric pressure and without special precautions.
- the PAA is in the form of anhydride functions. Immersion for 10 minutes in water allows to hydrolyze the anhydride functions and to restore the chemical form of the PAA.
- the solution can be prepared in advance.
- the PTFE supports are brought to ambient temperature for 10 min in the activation solution. A rinsing with DI water is done.
- the activated PTFE support is immersed in the controlled electroless bath at a temperature of 34 ° C.
- the bath is typically a Niposit TM PM 988 commercial bath. Its pH is 9.4.
- the reducing agent is sodium hypophosphite (NaH 2 PO 2 , H 2 O).
- the activated PTFE is left for 10 minutes in order to have a complete and homogeneous metallization.
- the thickness of the nickel film is typically 500 nm.
- PTFE carriers that have not been (FIG. 3c) or poorly coated with a PAA layer (FIG. 3-d) are immersed in the palladium acetate-based activator solution described. previously.
- Pd 2+ ions and / or PAA coating can not adsorb to the substrate and allow the development of the metallization process.
- Figure 3-e shows the metallized zone (activation and metallization) corresponding to the presence of PAA coating.
- Example 1-f Localized metallization of a PVC surface.
- a PAA solution (M n 130 000) of concentration typically 50 mg in 10 ml of ethanol is prepared by dissolution.
- the PVC flexible plate (format and manufacture for credit card) is degreased (washing with a surfactant and then typically an alcohol rinse) and then dried (typically with a dry nitrogen gas gun).
- the location of the deposit of the PAA solution is achieved in this example by using a writing pen previously soaked in the PAA solution (FIG. 4).
- the PVC plates are typically insolated by VUV radiation for 2 minutes at a distance of 15 cm in an air purged air by dry nitrogen sweep.
- the characteristics of the VUV lamp are: Excimer lamp of the brand OSRAM model XERADEX. Power of 140 W. Radiation 150 to 190 nm with maximum at 172 nm.
- Activation Preparation of the activation solution
- the solution can be prepared in advance.
- the PVC plates are put at ambient temperature for 10 min in the activation solution. A rinsing with DI water is done.
- the activated PVC plate is immersed in the regulated electroless bath at a temperature of 34 ° C.
- the bath is typically a commercial bath NipositTM PM 988. Its pH is 9.4.
- the reducing agent is sodium hypophosphite (NaH 2 PO 2 , H 2 O).
- the activated PVC is left for 10 minutes in order to have a complete and homogeneous metallization.
- the thickness of the nickel film is typically 500 nm.
- Figure 4 shows that a localized metallization of the PVC was obtained: the metallized parts were obtained using the PAA solution as an ink. The pattern was done with a writing pen.
- Example 2-a Thermal Immobilization of PAA on Polvimide i) Coating of the support.
- a solution of PAA (M n 130 000) of concentration of 100 mg in 10 ml of ethanol is prepared by dissolution.
- a flexible sheet of 50 ⁇ of polyimide (PI) is defatted (washing with a surfactant and then an alcohol rinse) and then dried (with a dry gas gun of nitrogen and then an oven passage at 100 ° C for 15 min. ).
- the application of the PAA solution is typically done by soaking-withdrawal (immersion-emersion) to obtain after evaporation of ethanol a PAA film covering and homogeneous thickness typically 150 to 250 nm. The PAA deposition will then occur on both sides of the polyimide sheet. ( Figure 5)
- the polyimide flexible sheets coated with PAA are then typically heated at 200 ° C. for 30 min in a simple oven at atmospheric pressure and without any particular precaution.
- the PAA is in the form of anhydride functions that can be used to couple with other complementary functions of materials of interest.
- Figure 5 shows that the peaks associated with the presence of a 200 nm PAA film on the PI persist after a 120 h wash in water.
- Example 2-bl Immobilization by VUV insolation of a PAA film on a flexible sheet of polyethylene terephthalate (PET.
- a solution of PAA typically of 50 mg in 10 ml of ethanol is prepared by dissolution.
- a flexible sheet of 50 ⁇ of polyethylene terephthalate (PET) is degreased (typically washing with a surfactant and then typically an alcohol rinse) and then dried (typically with a dry nitrogen gas gun).
- PET polyethylene terephthalate
- the application of the PAA solution is typically done by soaking-withdrawal (immersion-emersion) in order to obtain, after evaporation of the ethanol, a film of PAA covering and homogeneous with a thickness typically of 50 to 70 nm.
- the PAA deposition will then occur on both sides of the PET sheet ( Figure 6).
- the flexible sheets of PET coated with the PAA are then typically irradiated with VUV (Vacuum Ultraviolet) radiation for 2 minutes. at a distance of 15 cm in an air purged air by dry nitrogen sweep.
- VUV Vauum Ultraviolet
- the characteristics of the VUV lamp are: Excimer lamp of the brand OSRAM model XERADEX. Power of 140 W. Radiation 150 to 190 nm with maximum at 172 nm.
- FIG. 6c and 6d shows the persistence of the PAA film in its carboxylate form due to irradiated water rinsing and the removal of PAA on the non-irradiated side.
- a solution of PAA (M n 130 000) with a concentration of 50 mg in 10 ml of ethanol is prepared by dissolution.
- a flexible sheet of 50 ⁇ of polyethylene (PE) is degreased (washing with a surfactant and then an alcohol rinse) and then dried (with a dry gas gun of nitrogen).
- the application of the PAA solution is made by dipping-withdrawal (immersion-emersion) in order to obtain, after evaporation of the ethanol, a film of PAA covering and homogeneous with a thickness typically of 50. at 70 nm. PAA deposition will then occur on both sides of the PE sheet.
- Oxidative pretreatment of the surface by UV-ozone, or oxygen plasma may be done prior to coating to improve wetting of the PAA solution.
- the PE PA-coated flexible sheets are then irradiated with VUV (Vacuum Ultraviolet) radiation for 2 minutes at a distance of 15 cm in a purged air atmosphere by dry nitrogen sweep.
- VUV Vauum Ultraviolet
- the characteristics of the VUV lamp are: Excimer lamp of the brand OSRAM model XERADEX. Power of 140 W. Radiation 150 to 190 nm with maximum at 12 nm.
- FIG. 7c and 7d show the persistence of the PAA film in its acid and carboxylate form due to irradiated water rinsing and the removal of non-irradiated PAA on the side.
- EXAMPLE 3 Immobilization and Structuring by VUV Insolation of a Thin Film of PAA on Gold
- This example demonstrates the possibility of immobilizing and structuring a thin film of PAA on any surface at sub-millimeter scales by photolithographic methods.
- a solution of PAA (M n 130 000) of concentration of 100 mg in 10 ml of ethanol is prepared by dissolution.
- a gold surface (gold glass slide) is cleaned by UV-ozone treatment for 5 minutes to remove surface organic contaminants.
- the application of the PAA solution is made by soaking-withdrawal (immersion-emersion) in order to obtain, after evaporation of the ethanol, a film of PAA covering and homogeneous with a thickness typically of 150. at 250 nm.
- a mask is deposited by direct contact on the gold surface coated with the PAA, then the whole is irradiated by VUV (Vacuum Ultraviolet) radiation for 15 minutes at a distance of 7 cm in an air purged air by means of a vacuum. dry nitrogen.
- VUV Vauum Ultraviolet
- the characteristics of the VUV lamp are: Excimer lamp of the brand OSRAM model XERADEX. Power of 140 W. Radiation 150 to 190 nm with maximum at 172 nm.
- the black line represents the line measured by profilometry (bottom left) and shows that the difference in thickness between the irradiated zone and the non-irradiated area is of the order of 200 nm, the same order of magnitude as the initial thickness of PAA film on the gold substrate.
- Example 4 Structural bonding via anhydride groups. (Heat treatment)
- Example 4-a Bonding an epoxy resin on a stainless steel surface. i) Coating the substrate
- a PAA solution (M n 130 000) with a concentration of 50 mg
- a mechanically polished stainless steel blade up to a roughness of 1 ⁇ is degreased (typically washing with a surfactant and then typically an alcohol rinse) and then dried (typically by a dry gas blower of nitrogen and then by a transition to the oven at 100 ° C for 15 min).
- the application of the PAA solution is typically done by soaking-withdrawal (immersion-emersion) in order to obtain, after evaporation of the ethanol, a film of PAA covering and homogeneous thickness typically of 70 to 100 nm.
- the stainless steel surfaces coated with PAA are then typically heated at 200 ° C. for 30 min in a single oven at atmospheric pressure and without particular precautions.
- the heating will make it possible to adhere the PAA on the stainless steel, to form reactive anhydride groups and to crosslink the film by decarboxylation.
- the mixture is made and applied in a thin layer of 300 ⁇ on stainless steel (use of a screen-printing stencil).
- the bubbles are eliminated naturally in 5 minutes and final drying at 100 ° C for 1 hour is done.
- the epoxy film is applied to a virgin stainless steel surface (comparative substrate) and under the same conditions on a stainless steel surface with a PAA-anhydride coating.
- Example S Control of the surface energy of a substrate
- Example 5-A / Hydrophilic Modified Hydrophobic Substrate (PVC) A solution of PAA (typically M n 130,000) typically of 50 mg in 10 ml of ethanol is prepared by dissolution.
- the PVC flexible plate (format and manufacture for credit card) is degreased (typically washing with a surfactant and then typically an alcohol rinse) and then dried (typically by a blowgun of dry nitrogen gas). At this stage, the PVC surface is very hydrophobic.
- the application of the PAA solution is typically done by dipping-withdrawal (immersion-emersion) in order to obtain, after evaporation of the ethanol, a film of PAA covering and homogeneous of thickness typically of 50 to 70 nm.
- PVC sheets are typically insolated by radiation
- VUV Ultraviolet Vacuum
- VUV are: Excimer lamp of the brand OSRAM model XERADEX. Power of 140 W. Radiation 150 to 190 nm with maximum at 172 nm.
- the surface energy of the substrate is determined by the measurement of the contact angle.
- the contact angle measurements were performed with an Apollo Instrument brand instrument, controlled via the Sca 20 software.
- Example 5-b A hydrophilic hydrophobic modified substrate (glass substrate coated with a gold layer)
- a solution of PAA typically of 50 mg in 10 ml of ethanol is prepared by dissolution.
- a microscope slide (7.5x2.5 cm) coated with a layer of gold (gold substrate) is directly treated with UV-Ozone for 5 min to remove traces of organic contamination. of atmospheric origin ..
- the application of the PAA solution is typically done by soaking-withdrawal (immersion-emersion) in order to obtain, after evaporation of the ethanol, a film of PAA covering and homogeneous thickness typically of 50 to 70 nm.
- the glass slides coated with PAA are then typically heated at 200 ° C. for 30 min in a single oven at atmospheric pressure and without any particular precaution.
- the heating will make it possible to adhere the PAA on the gold substrate, to form reactive anhydride groups and to crosslink the film by decarboxylation.
- a molecule comprising a hydrophobic part (C1-alkyl group) and a primary amine function is applied to the activated surface, in pure form (undiluted) by placing a drop and then spreading it by applying a coverslip of glass above, or in a form diluted in a solvent, for example hexane or cyclohexane, not interfering with the coupling reaction between the anhydrides and the amines (Figure 11). ⁇ Cf. diagram below).
- the contact angle of clean gold after UV-03 treatment is between 20 and 30 °.
- This PAA coated substrate has a contact angle typically between 30 and 50 °. Then, when the C 1 amine is grafted onto the PAA coated substrate, this contact angle reaches 100 °.
- IR spectroscopy makes it possible to demonstrate the chemical reaction between the acid surface of the PAA coated gold substrate and the amine by the presence of the amide bands (FIG. 11).
- Example 6 Production of PAA film of residual and constant thickness.
- Projection or transfer coating methods are limited in deposition quality by the application step and solvent evaporation, which are never perfectly homogeneous.
- PAA is a polyelectrolyte that can be adsorbed by electrostatic interactions on certain surfaces. These interactions develop over a distance that is dependent on the nature of the polymer and the substrate and can therefore be variable. The equilibrium of these different forces leads to the deposition of a thin layer of perfectly defined thickness after several successive rinses. The thickness asymptotically obtained after rinsing is then governed by the surface.
- One method of preparing these conformal PAA thin films is to apply a PAA coating of greater thickness than the desired thickness without particular precautions, and then rinse off the PAA polymer chains which do not physically interact with the PAA. area.
- a PAA film for example, on a gold support (deposition of a gold layer on a glass slide) is deposited a PAA film by dipping-withdrawal (immersion-emersion) to obtain after evaporation of ethanol a homogeneous, thick PAA film of typically 50 to 70 nm thickness.
- the residual films obtained on gold converge asymptotically to a constant thickness of 15 nm as shown by the IR intensities of FIG. 12. This residual thickness is controlled by the polyelectrolytic interactions in relation to the surface properties.
- Example 7 / coupling of biological molecules on a surface of
- Stable coupling of biological molecules on a surface is an important goal of many methods of analysis and medical diagnosis.
- the following example illustrates the possibility of chemically and covalently grafting proteins onto an activated adhesion primer itself covalently grafted onto a substrate.
- activated surfaces are created and then these activated surfaces are used to perform the actual coupling with the proteins.
- Protein coupling is operated in a conventional manner for biologists through the activated form of the so-called activated ester acid.
- This activated ester preferentially reacts in a buffered medium with the amino groups of the proteins to create stable and hydrolysis resistant amide linkages.
- linkages see Greg T Hermanson, "Bioconjugate Techniques," 2nd Edition, Elsevier, 2008.
- N-hydroxy succinimide (NHS) 22 mg are dissolved in 13 ml of acetonitrile.
- Activation condition of the PAA surface A PAA slide grafted in its acid form is immersed in a solution containing 8 ml of acetonitrile, 1 ml of the solution of Dicyclohexyl carbodiimide (DCC), and 1 ml of the solution. N-hydroxysuccinimide (NHS). The PAA surface is allowed to react for 30 minutes.
- DCC Dicyclohexyl carbodiimide
- NHS N-hydroxysuccinimide
- FIG. 13 illustrates the formation of surface-activated esters of the PAA film (FIG. 13 -a) and the result of the coupling with the protein: appearance of a component bound to the protein (FIG. 13-b). Since the PAA film was not swollen with acetonitrile, the NHS and DCC reagents did not penetrate into the PAA layer and only the surface carboxylic acid (COOH) groups were modified.
- N-hydroxy succinimide 16 mg are dissolved in 10 ml of DI water.
- EDC 1-ethyl-3 - (- 3-dimethylaminopropyl) carbodiimide hydrochloride
- NHS N-hydroxy succinimide solution
- a solution of protein (calmodulin) at 1 mg / ml in DI water at a pH of 6 is prepared.
- the surface of PAA prepared according to the conditions described above is immersed in 2 ml of the protein solution. The whole is placed in an incubator at 37 ° C. and with gentle stirring for 1 h.
- Figure 14 illustrates the formation of anhydrides chemically in an aqueous medium, in the presence of NHS and EDC ( Figure 14-a), and the result of coupling with the protein ( Figure 14-b). It was previously verified that the anhydride functions persisted after immersion of the activated support for 15 minutes in DI water at a pH of 6 (FIG. 14-c). Thus the disappearance of the anhydride functions after coupling with the protein is the result of the reaction that took place between these functions and the protein.
- Example 8 Thermal immobilization of PAA on carbon felt for the production of filter elements of industrial heavy metals (Cu, Za, Ni, ...) for the treatment of liquid effluents. It is a question of collecting salts of metallic elements in solution on polyacrylic acid-coated carbon felt filters,
- a PAA solution of 130,000 Mn, typically 50 mg in 10 ml of ethanol is prepared by dissolution.
- a solution of Polyethylene imine (PEI), MW 25000, 5 mg in 10 ml of DI water is prepared by dissolution.
- a first impregnation is made with an aqueous solution of polyethylene imine (PEI) 5 mg / 10 ml.
- PEI polyethylene imine
- the felt is filled with a pasteur pipette until visual detection of complete impregnation.
- the felt is left to dry.
- the PEI (positive-charged polymer) coating enhances the polyelectrolytic properties of the PAA (negatively charged) and leads to a better subsequent coating of the fibers by the PAA.
- a second impregnation is made with a solution of PAA at 50 mg / 10 ml in ethanol until visual detection of the complete impregnation.
- the felt is left to dry.
- Baking is done at 200 ° C for 30 min.
- the process allows a coating covering individual fibers of the carbon felt.
- interferential hues are detected on all the fibers, whether on the surface of the felt or on the inside of the felt.
- the PAA is in the anhydride chemical form.
- the film thus manufactured is chemically stable on the fibers.
- the dry residue after drying is 16 mg and represents an average PAA film thickness coating the 70 nm fibers.
- 13 felts thus prepared (which represents 21 mg of PAA immobilized on the 13 felts) are placed in a column (100 ml plastic syringe), 2.4 l of a solution of 45 mg / l of Cu ++ in water tap are filtered slowly on the column.
- the copper concentration of recovered filtrate is 1 ⁇ / ⁇ which demonstrates the efficiency of capture.
- a solution of PAA (Mn 130,000) with a concentration of 50 mg in 10 ml of ethanol is prepared by dissolution.
- the application of the PAA solution is made by soaking-withdrawal (immersion-emersion) to obtain after evaporation of ethanol a PAA film covering and homogeneous thickness of 50 to 70 nm.
- the PAA deposit then occurs on all the fibers.
- the PAA-coated kevlar fiber fabric is then typically heated at 200 ° C for 30 minutes in a single oven at atmospheric pressure and without any particular precaution.
- the solution can be prepared in advance.
- the activated fiber fabric is immersed in an electroless bath (i.e., an electrolytic bath) regulated at a temperature of 34 ° C.
- an electroless bath i.e., an electrolytic bath
- the bath is typically a Niposit TM PM 988 commercial bath. Its pH is 9.4.
- the reducing agent is sodium hypophosphite (aH2PO2, H2O).
- the activated fiber fabric is left for 10 minutes in order to have a complete and homogeneous metallization.
- the thickness of the nickel film is typically 500 nm.
- Example 10 Carbon-epoxy composite metallization aeronautical type.
- a solution of PAA (Mn 130,000) with a concentration of 50 mg in 10 ml of ethanol is prepared by dissolution.
- a carbon-epoxy composite plate of the aeronautical type A carbon-epoxy composite plate of the aeronautical type.
- the application of the PAA solution is made by soaking-withdrawal (immersion-emersion) in order to obtain, after evaporation of the ethanol, a film of PAA covering and homogeneous thickness of 50 to 70 nm.
- the PAA deposit then occurs on the immersed plate fraction.
- the carbon-epoxy composite plate coated with PAA is then typically heated at 200 ° C. for 30 min in a simple oven at atmospheric pressure and without any particular precaution.
- the solution can be prepared in advance.
- the carbon-epoxy composite plate is immersed in an electroless bath (i.e. an electrolytic bath) regulated at a temperature of 34 ° C.
- an electroless bath i.e. an electrolytic bath
- the bath is typically a Niposit TM PM 988 commercial bath. Its pH is 9.4.
- the reducing agent is sodium hypophosphite (NaH2PO2, H2O).
- the carbon-epoxy composite plate is left for 10 minutes in order to have a complete and homogeneous metallization.
- the thickness of the nickel film is typically 500 nm.
- FIG. 17 it is observed that the lower part has been coated with grafted PAA and then metallized. Metallization was only done on the PAA treated part.
- Example 11 Metallization of polymeric substrates of ABS type. A / Coating and immobilizing the acrylic acid (PAA) coating.
- PAA acrylic acid
- a solution of PAA typically of 50 mg in 10 ml of ethanol is prepared by dissolution.
- ABS surfaces are mirror-quality convex surfaces. These are blank ABS parts used especially in sanitary such as, for example, bath caps. The parts are prepared with a simple degreasing with a surfactant and rinsing with water and then dried (typically with a dry nitrogen gas gun).
- the application of the PAA solution is typically made by soaking-removing (immersion-emersion) so to obtain, after evaporation of ethanol, a film of PAA covering and homogeneous with a thickness typically of 50 to 70 nm.
- the samples are typically exposed by VUV radiation for 2 minutes at a distance of 15 cm in a purged atmosphere of air by dry nitrogen sweep for 10 minutes.
- the characteristics of the VUV lamp are: Excimer lamp of the brand OSRAM model XERADEX. Power of 140 W. Radiation 150 to 190 nm with maximum at 172 nm. These characteristics remain the same for the following examples.
- PAA thin films The immobilization of PAA thin films is tested by washing with ethanol and with water, which are very good solvents for PAA. The resistance of the films is observed on all the substrates. The rinsing tests with alcohol or water before irradiation obviously show the complete elimination of the PAA.
- the solution can be prepared in advance.
- the ABS substrate is immersed in an electroless bath (i.e. an electrolytic bath) regulated at a temperature of 34 ° C.
- an electroless bath i.e. an electrolytic bath
- the bath is typically a commercial bath NiposiiTM PM 988. Its pH is 9.4.
- the reducing agent is sodium hypophosphite (NaH2PO2, H2O).
- ABS substrate is left for 10 minutes in order to have a complete and homogeneous metallization.
- the thickness of the nickel film is typically 500 nm.
- a solution of PAA typically of 50 mg in 10 ml of ethanol is prepared by dissolution.
- the surfaces of commercial COP (cyclic Olefin Polymer) by the company Zeon (Zeonex®) are prepared with a simple degreasing with a surfactant and rinsing with water and then dried (typically with a dry nitrogen gas gun).
- the application of the PAA solution is typically done by soaking-shrinking (immersion-emersion) in order to obtain, after evaporation of the ethanol, a film of PAA covering and homogeneous thickness typically from 50 to 70 nm.
- the samples are typically irradiated with VUV for 2 minutes at a distance of 4 cm in a purged atmosphere of air by dry nitrogen sweep for 10 minutes.
- PAA thin films The immobilization of PAA thin films is tested by washing with ethanol and with water, which are very good solvents for PAA. The resistance of the films is observed on all the substrates. The rinsing tests with alcohol or water before irradiation obviously show the complete elimination of the PAA.
- the solution can be prepared in advance.
- the COP substrate is immersed in an electroless bath (i.e., an electrolytic bath) regulated at a temperature of 34 ° C.
- an electroless bath i.e., an electrolytic bath
- the bath is typically a commercial bath NipositTM P 988. Its pH is 9.4.
- the reducing agent is sodium hypophosphite (NaH2PO2, H2O).
- the COP substrate is left for 10 minutes in order to have complete and homogeneous metallization.
- the thickness of the nickel film is typically 500 nm.
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- 2015-04-03 EP EP22167257.9A patent/EP4043110A1/en active Pending
- 2015-04-03 US US15/301,528 patent/US11014121B2/en active Active
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Also Published As
Publication number | Publication date |
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FR3019477B1 (en) | 2023-03-17 |
WO2015151070A2 (en) | 2015-10-08 |
WO2015151070A3 (en) | 2015-11-26 |
EP4043110A1 (en) | 2022-08-17 |
US11014121B2 (en) | 2021-05-25 |
FR3019477A1 (en) | 2015-10-09 |
US20170113249A1 (en) | 2017-04-27 |
EP3126064B1 (en) | 2022-05-04 |
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