Method for preparing an organic film at the surface of a solid support under non-electrochemical conditions, solid support thus obtained and preparation kit

Abstract

This invention relates to a method for preparing an organic film at the surface of a solid support, with a step of contacting said surface with a liquid solution including (i) at least one solvent, (ii) at least one adhesion primer, under non-electrochemical conditions, and allowing the formation of radical entities based on the adhesion primer. The liquid solution can also include (iii) at least one monomer different from the adhesion primer and radically polymerizable. This invention also relates to a non-electrically-conductive solid support on which an organic film according to said method is grafted, and a kit for preparing an essentially polymeric organic film at the surface of a solid support.

Claims

1. A method for preparing an organic film at the surface of a solid support, wherein it includes a step of contacting said surface with a liquid solution including: at least one aprotic solvent, at least one cleavable aryl salt and at least one radically polymerisable monomer different from said cleavable aryl salt, said organic film being polymeric or copolymeric and having a monomer unit sequence in which the first unit is constituted by a derivative of the cleavable aryl salt and the other units are derived from said cleavable aryl salt and from polymerizable monomers, wherein said contacting is under non-electrochemical conditions enabling formation of radical entities based on the cleavable aryl salt, wherein the cleavable aryl salts generate said radical entities without reacting with the surface on which said radical entities are intended to be grafted.

2. The preparation method of claim 1, wherein said aprotic solvent is chosen from the group constituted by dimethylformamide (DMF), acetone and dimethyl sulfoxide (DMSO).

3. The preparation method of claim 1, wherein said cleavable aryl salt is chosen from the group constituted by aryl diazonium salts, aryl ammonium salts, aryl phosphonium salts and aryl sulfonium salts.

4. The preparation method of claim 1, wherein said cleavable aryl salt is chosen from the group constituted by aryl diazonium salts, aryl ammonium salts, aryl phosphonium salts and aryl sulfonium salts and wherein said aryl group is chosen from the aromatic or heteroaromatic carbon structures, possibly mono- or polysubstituted, constituted by one or more aromatic or heteroaromatic cycles each comprising 3 to 8 atoms, the heteroatom(s) being capable of being N, O, P or S, and the substituent(s) possibly containing one or more heteroatoms or alkyl groups in C.sub.1 to C.sub.6.

5. The preparation method of claim 1, wherein said cleavable aryl salt has the following formula (I):
R—N.sub.2.sup.+,A.sup.−  (I) in which: A represents a monovalent anion and R represents an aryl group.

6. The preparation method of claim 1, wherein said cleavable aryl salt has the following formula (I):
R—N.sub.2.sup.+,A.sup.−  (I) in which: A represents a monovalent anion and R represents an aryl group chosen from the aromatic or heteroaromatic carbon structures, possibly mono- or polysubstituted, constituted by one or more aromatic or heteroaromatic cycles each comprising 3 to 8 atoms, the heteroatom(s) being capable of being N, O, P or S, and the substituent(s) possibly containing one or more heteroatoms or alkyl groups in C.sub.1 to C.sub.6.

7. The preparation method of claim 1, wherein said cleavable aryl salt has the following formula (I):
R—N.sub.2.sup.+,A.sup.−  (I) in which: A represents a monovalent anion chosen from the inorganic anions, the halogenborates and the organic anions and R represents an aryl group.

8. The preparation method of claim 1, wherein said cleavable aryl salt is chosen from the group constituted by phenyldiazonium tetrafluoroborate, 4-nitrophenyldiazonium tetrafluoroborate, 4-bromophenyldiazonium tetrafluoroborate, 4-aminophenyldiazonium chloride, 2-methyl-4-chlorophenyldiazonium chloride, 4-benzoylbenzenediazonium tetrafluoroborate, 4-cyanophenyldiazonium tetrafluoroborate, 4-carboxyphenyldiazonium tetrafluoroborate, 4-acetamidophenyldiazonium tetrafluoroborate, 4-phenylacetic acid diazonium tetrafluoroborate, 2-methyl-4-[(2-methylphenyl)diazenyl]benzenediazonium sulphate, 9,10-dioxo-9,10-dihydro-1-anthracenediazonium chloride, 4-nitronaphthalenediazonium tetrafluoroborate and naphthalenediazonium tetrafluoroborate.

9. The preparation method of claim 1, wherein said cleavable aryl salt concentration in said liquid solution is between around 10.sup.−6 and 5 M.

10. The preparation method of claim 1, wherein said cleavable aryl salt is prepared in situ in said liquid solution.

11. The preparation method of claim 1, wherein said liquid solution also contains at least one surfactant.

12. The preparation method of claim 1, wherein the non-electrochemical conditions allowing for the formation of radical entities are chosen from the group constituted by thermal, kinetic, chemical, photochemical or radiochemical conditions and a combination thereof, to which the cleavable aryl salt is subjected.

13. The preparation method of claim 1, wherein the non-electrochemical conditions allowing for the formation of radical entities are chemical conditions.

14. The preparation method of claim 1, wherein said liquid solution also includes one or more chemical initiator(s).

15. The preparation method of claim 1, wherein said liquid solution also includes one or more chemical initiator(s) chosen from: a reducing metal in a finely divided form, a metallocene, an organic or inorganic base in proportions sufficient for the pH of the liquid solution to be greater than or equal to 4, a pre-irradiated polymeric matrix.

16. The preparation method of claim 1, wherein the surface of said solid support has at least one atom capable of being involved in a radical reaction.

17. The preparation method of claim 1, wherein said solid support and/or the surface of said solid support are made of a material chosen from the group constituted by metals, wood, paper, cotton, felt, silicon, carbon nanotubes, fluoro-polymers and diamond.

18. The preparation method of claim 1, wherein the surface of the solid support contacted with said liquid solution comprises at least one area covered with a mask.

19. The preparation method of claim 1, wherein the surface of the solid support contacted with said liquid solution comprises at least one area covered with a mask and wherein the mask is not soluble in the solvent of said liquid solution.

20. The preparation method of claim 1, wherein the surface of the solid support contacted with said liquid solution comprises at least one area covered with a mask composed of alkylthiols.

21. The preparation method of claim 1, wherein said radically polymerisable monomer is a molecule comprising at least one ethylene-type bond.

22. The preparation method of claim 1, wherein said radically polymerisable monomer is a molecule with the following formula (II): ##STR00003## in which the R.sub.1 to R.sub.4 groups, identical or different, represent a non-metallic monovalent atom, a hydrogen atom, a saturated or unsaturated chemical group, a —COOR.sub.5 group in which R.sub.5 represents a hydrogen atom or an alkyl group in C.sub.1-C.sub.12, a nitrile, a carbonyl, an amine or an amide.

23. The preparation method of claim 1, wherein said radically polymerisable monomer is chosen from the group constituted by vinyl acetate, acrylonitrile, methacrylonitrile, methyl methacrylate, ethyl methacrylate, butyl methacrylate, propyl methacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, glycidyl methacrylate and their derivatives; the acrylamides, aminoethyl, propyl, butyl, pentyl and hexyl methacrylamides, the cyanoacrylates, the di-acrylates and di-methacrylates, the tri-acrylates and tri-methacrylates, the tetra-acrylates and tetra-methacrylates tetramethacrylate pentaerythritol, styrene and its derivatives, parachloro-styrene, pentafluoro-styrene, N-vinyl pyrrolidone, 4-vinyl pyridine, 2-vinyl pyridine, the vinyl halides, acryloyl or methacryloyl, di-vinylbenzene (DVB), and vinyl cross-linking agents based on acrylate, methacrylate and derivatives thereof.

24. The preparation method of claim 1, wherein the amount of said radically polymerisable monomer represents between 18 and 40 times the solubility of said monomer at room temperature or at the reaction temperature.

25. The preparation method of claim 1, wherein said method includes a preliminary step during which said at least one radically polymerisable monomer different from the cleavable aryl salt is dispersed or emulsified in the presence of at least one surfactant, or by ultrasound, before it is mixed with the liquid solution including at least one aprotic solvent and at least one cleavable aryl salt.

26. The preparation method of claim 1, wherein said method includes the following steps, consisting of: a) adding said at least one radically polymerisable monomer to a solution containing said at least one cleavable aryl salt different from said monomer in the presence of said at least one aprotic solvent and optionally at least one chemical initiator, b) placing the solution obtained in step (a) under said non-electrochemical conditions allowing for the formation of radical entities based on said cleavable aryl salt and possibly based on said chemical initiator, c) placing the surface of the solid support in contact with the solution of step (b).

27. The preparation method of claim 1, wherein said method includes the following steps, consisting of: a′) placing the surface of the solid support in contact with a solution containing said at least one cleavable aryl salt in the presence of said at least one aprotic solvent, and at least one radically polymerisable monomer different from said cleavable aryl salt and possibly at least one chemical initiator, b′) placing the surface of the solid support in contact with the solution of step (a′) under non-electrochemical conditions allowing for the formation of radical entities based on said cleavable aryl salt and possibly based on said chemical initiator, c′) possibly adding at least one radically polymerisable monomer different from said cleavable aryl salt to the solution obtained in step (b′).

28. The preparation method of claim 1, wherein said method includes an additional step, prior to the grafting, of cleaning the surface on which the organic film is to be formed.

29. The preparation method of claim 1, wherein the method has an additional step of functionalising said organic film.

30. The preparation method of claim 1, wherein the method has an additional step of functionalising said organic film and wherein the functionalisation is performed by placing said organic film in contact with a functionalisation solution comprising at least one functionalizing compound.

31. The preparation method of claim 1, wherein the method has an additional step of functionalising said organic film and wherein the functionalisation is performed by placing said organic film in contact with a functionalisation solution comprising at least one functionalizing compound which has a chelating structure.

32. The preparation method of claim 1, wherein the method has an additional step of functionalising said organic film and wherein the functionalisation is performed by placing said organic film in contact with a functionalisation solution comprising at least one functionalizing compound which is a derivative of a biomolecule.

33. The preparation method of claim 1, wherein the surface of the support is placed in contact with a suspension of at least one nano-object (NB) in a suspension solvent and in that the film and the nano-object have a physicochemical affinity.

34. The preparation method of claim 1, wherein the surface of the support is placed in contact with a suspension of nano-objects (NBs) which are nanoparticles (NPs) or nanocrystals (NCs) in a suspension solvent and in that the film and the nano-objects have a physicochemical affinity.

35. The preparation method of claim 1, wherein the surface of the support is placed in contact with a suspension of nano-objects (NBs) which are metal or metal alloy nanoparticles (NPs) or nanocrystals (NCs) in a suspension solvent and in that the film and the nano-objects have a physicochemical affinity.

36. The preparation method of claim 1, wherein the surface of the support is placed in contact with a suspension of nano-objects (NBs) in a suspension solvent, wherein the film and the nano-objects have a physicochemical affinity and wherein said NBs are capable of coalescing under the action of a coalescence agent and at least one zone of the surface of the support, coated with the film comprising the NBs, is exposed to a coalescence agent.

37. The preparation method of claim 1, wherein the surface of the support is placed in contact with a suspension of nano-objects (NBs) in a suspension solvent, wherein the film and the nano-object have a physicochemical affinity and wherein said NBs are capable of coalescing under the action of a coalescence agent which is a modification of the temperature or irradiation and at least one zone of the surface of the support, coated with the film comprising the NBs, is exposed to a modification of the temperature or irradiation.

38. A method for metallizing an organic film prepared at the surface of a solid support including the steps consisting of: (1) preparing, at the surface of a solid support, an organic film by contacting said surface with a liquid solution including: at least one solvent, at least one cleavable aryl salt, and at least one radically polymerisable monomer different from said cleavable aryl salt, under non-electrochemical conditions enabling the formation of radical entities based on the cleavable aryl salt, wherein the cleavable aryl salts generate said radical entities without reacting with the surface on which said radical entities are intended to be grafted, (2) placing the surface of the support in contact with a suspension of at least one nano-object (NB) in a suspension solvent, the film and the nano-object having a physicochemical affinity, so an organic film comprising nano-objects (NBs) is obtained at the surface of the solid; (3) placing the film obtained in step (2) in contact with a solution containing at least one metal salt capable of being reduced by said NBs, said organic film being polymeric or copolymeric and having a monomer unit sequence in which the first unit is constituted by a derivative of the cleavable aryl salt and the other units are derived from said cleavable aryl salt and from polymerizable monomers.

39. The metallization method of claim 38, wherein the nano-objects (NBs) in the suspension are nanoparticles (NPs) or nanocrystals (NCs) in a suspension solvent.

40. The metallization method of claim 38, wherein the nano-objects (NBs) in the suspension are metal or metal alloy nanoparticles (NPs) or nanocrystals (NCs) in a suspension solvent.

41. The metallization method of claim 38, wherein the solvent in said liquid solution is an aprotic solvent preferably chosen from the group constituted by dimethylformamide (DMF), acetone and dimethyl sulfoxide (DMSO).

42. The metallization method of claim 38, wherein the solvent in said liquid solution is a protic solvent preferably chosen from the group constituted by water, deionised water, distilled water, acidified or not, acetic acid, hydroxylated solvents, low-molecular-weight liquid glycols such as ethyleneglycol, and mixtures thereof.

43. The metallization method of claim 38, wherein said cleavable aryl salt is chosen from the group constituted by aryl diazonium salts, aryl ammonium salts, aryl phosphonium salts and aryl sulfonium salts.

44. The metallization method of claim 38, wherein said cleavable aryl salt is chosen from the group constituted by aryl diazonium salts, aryl ammonium salts, aryl phosphonium salts and aryl sulfonium salts and wherein said aryl group is chosen from the aromatic or heteroaromatic carbon structures, possibly mono- or polysubstituted, constituted by one or more aromatic or heteroaromatic cycles each comprising 3 to 8 atoms, the heteroatom(s) being capable of being N, O, P or S, and the substituent(s) possibly containing one or more heteroatoms or alkyl groups in C.sub.1 to C.sub.6.

45. The metallization method of claim 38, wherein said cleavable aryl salt has the following formula (I):
R—N.sub.2.sup.+,A.sup.−  (I) in which: A represents a monovalent anion and R represents an aryl group.

46. The metallization method of claim 38, wherein said cleavable aryl salt has the following formula (I):
R—N.sub.2.sup.+,A.sup.−  (I) in which: A represents a monovalent anion and R represents an aryl group chosen from the aromatic or heteroaromatic carbon structures, possibly mono- or polysubstituted, constituted by one or more aromatic or heteroaromatic cycles each comprising 3 to 8 atoms, the heteroatom(s) being capable of being N, O, P or S, and the substituent(s) possibly containing one or more heteroatoms or alkyl groups in C.sub.1 to C.sub.6.

47. The metallization method of claim 38, wherein said cleavable aryl salt has the following formula (I):
R—N.sub.2.sup.+,A.sup.−  (I) in which: A represents a monovalent anion chosen from the inorganic anions, the halogenborates and the organic anions and R represents an aryl group.

48. The metallization method of claim 38, wherein said cleavable aryl salt is chosen from the group constituted by phenyldiazonium tetrafluoroborate, 4-nitrophenyldiazonium tetrafluoroborate, 4-bromophenyldiazonium tetrafluoroborate, 4-aminophenyldiazonium chloride, 2-methyl-4-chlorophenyldiazonium chloride, 4-benzoylbenzenediazonium tetrafluoroborate, 4-cyanophenyldiazonium tetrafluoroborate, 4-carboxyphenyldiazonium tetrafluoroborate, 4-acetamidophenyldiazonium tetrafluoroborate, 4-phenylacetic acid diazonium tetrafluoroborate, 2-methyl-4-[(2-methylphenyl)diazenyl]benzenediazonium sulphate, 9,10-dioxo-9,10-dihydro-1-anthracenediazonium chloride, 4-nitronaphthalenediazonium tetrafluoroborate and naphthalenediazonium tetrafluoroborate.

49. The metallization method of claim 38, wherein said cleavable aryl salt concentration in said liquid solution is between around 10.sup.−6 and 5 M.

50. The metallization method of claim 38, wherein said cleavable aryl salt is prepared in situ in said liquid solution.

51. The metallization method of claim 38, wherein said liquid solution also contains at least one surfactant.

52. The metallization method of claim 38, wherein the non-electrochemical conditions allowing for the formation of radical entities are chosen from the group constituted by thermal, kinetic, chemical, photochemical or radiochemical conditions and a combination thereof, to which the cleavable aryl salt is subjected.

53. The metallization method of claim 38, wherein the non-electrochemical conditions allowing for the formation of radical entities are chemical conditions.

54. The metallization method of claim 38, wherein said liquid solution also includes one or more chemical initiator(s).

55. The metallization method of claim 38, wherein said liquid solution also includes one or more chemical initiator(s) chosen from: a reducing metal in a finely divided form, a metallocene, an organic or inorganic base in proportions sufficient for the pH of the liquid solution to be greater than or equal to 4, a pre-irradiated polymeric matrix.

56. The metallization method of claim 38, wherein the surface of said solid support has at least one atom capable of being involved in a radical reaction.

57. The metallization method of claim 38, wherein said solid support and/or the surface of said solid support are made of a material chosen from the group constituted by metals, wood, paper, cotton, felt, silicon, carbon nanotubes, fluoro-polymers and diamond.

58. The metallization method of claim 38, wherein the surface of the solid support contacted with said liquid solution comprises at least one area covered with a mask.

59. The metallization method of claim 38, wherein the surface of the solid support contacted with said liquid solution comprises at least one area covered with a mask and wherein the mask is not soluble in the solvent of said liquid solution.

60. The metallization method of claim 38, wherein the surface of the solid support contacted with said liquid solution comprises at least one area covered with a mask composed of alkylthiols.

61. The metallization method of claim 38, wherein said radically polymerisable monomer is a molecule comprising at least one ethylene-type bond.

62. The metallization method of claim 38, wherein said radically polymerisable monomer is a molecule with the following formula (II): ##STR00004## in which the R.sub.1 to R.sub.4 groups, identical or different, represent a non-metallic monovalent atom, a hydrogen atom, a saturated or unsaturated chemical group, a COOR.sub.5 group in which R.sub.5 represents a hydrogen atom or an alkyl group in C.sub.1-C.sub.12, a nitrile, a carbonyl, an amine or an amide.

63. The metallization method of claim 38, wherein said radically polymerisable monomer is chosen from the group constituted by vinyl acetate, acrylonitrile, methacrylonitrile, methyl methacrylate, ethyl methacrylate, butyl methacrylate, propyl methacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, glycidyl methacrylate and their derivatives; the acrylamides, aminoethyl, propyl, butyl, pentyl and hexyl methacrylamides, the cyanoacrylates, the di-acrylates and di-methacrylates, the tri-acrylates and tri-methacrylates, the tetra-acrylates and tetra-methacrylates tetramethacrylate pentaerythritol, styrene and its derivatives, parachloro-styrene, pentafluoro-styrene, N-vinyl pyrrolidone, 4-vinyl pyridine, 2-vinyl pyridine, the vinyl halides, acryloyl or methacryloyl, di-vinylbenzene (DVB), and vinyl cross-linking agents based on acrylate, methacrylate and derivatives thereof.

64. The metallization method of claim 38, wherein the amount of said radically polymerisable monomer represents between 18 and 40 times the solubility of said monomer at room temperature or at the reaction temperature.

65. The metallization method of claim 38, wherein said method includes a preliminary step during which said at least one radically polymerisable monomer different from the cleavable aryl salt is dispersed or emulsified in the presence of at least one surfactant, or by ultrasound, before it is mixed with the liquid solution including at least one solvent and at least one cleavable aryl salt.

66. The metallization method of claim 38, wherein said method includes the following steps, consisting in: a) adding said at least one radically polymerisable monomer to a solution containing said at least one cleavable aryl salt different from said monomer in the presence of said at least one solvent and optionally at least one chemical initiator, b) placing the solution obtained in step (a) under said non-electrochemical conditions allowing for the formation of radical entities based on said cleavable aryl salt and possibly based on said chemical initiator, c) placing the surface of the solid support in contact with the solution of step (b).

67. The metallization method of claim 38, wherein said method includes the following steps, consisting of: a′) placing the surface of the solid support in contact with a solution containing said at least one cleavable aryl salt in the presence of said at least one solvent, and at least one radically polymerisable monomer different from said cleavable aryl salt and possibly at least one chemical initiator, b′) placing the surface of the solid support in contact with the solution of step (a′) under non-electrochemical conditions allowing for the formation of radical entities based on said cleavable aryl salt and possibly based on said chemical initiator, c′) possibly adding at least one radically polymerisable monomer different from said cleavable aryl salt to the solution obtained in step (b′).

68. The metallization method of claim 38, wherein said method includes an additional step, prior to the grafting, of cleaning the surface on which the organic film is to be formed.

69. The metallization method of claim 38, wherein the method has an additional step of functionalising said organic film.

70. The metallization method of claim 38, wherein the method has an additional step of functionalising said organic film and wherein the functionalisation is performed by placing said organic film in contact with a functionalisation solution comprising at least one functionalizing compound.

71. The metallization method of claim 38, wherein the method has an additional step of functionalising said organic film and wherein the functionalisation is performed by placing said organic film in contact with a functionalisation solution comprising at least one functionalizing compound which has a chelating structure.

72. The metallization method of claim 38, wherein the method has an additional step of functionalising said organic film and wherein the functionalisation is performed by placing said organic film in contact with a functionalisation solution comprising at least one functionalizing compound which is a derivative of a biomolecule.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1 shows the IR spectrum of a gold plate according to an alternative of the method of this invention with a solution of which the diazonium salt was prepared in situ from p-benzylamine.

(2) FIG. 2 shows the IR spectrum of a gold plate treated according to an alternative of the method of this invention, i.e. with a solution of which the diazonium salt has been prepared in situ from p-phenyldiamine.

(3) FIG. 3 shows the IR spectrum of a gold plate treated according to an alternative of the method of this invention, i.e. with a diazonium solution, after 5, 10, and 15 minutes of exposure of the plate (respectively (a), (b) and (c)).

(4) FIG. 4 shows the IR spectrum of a nickel plate treated according to an alternative of the method of this invention with a solution of which the diazonium salt was prepared in situ from p-benzylamine.

(5) FIG. 5 shows the IR spectrum of a steel plate (AISI 316L) treated according to an alternative of the method of this invention with a solution of which the diazonium salt was prepared in situ from p-benzylamine.

(6) FIG. 6 shows an AFM image of a diamond surface coated with a primer film (FIG. 6a) and a profilometric curve (length X (nm)/height Z(Å)) of this surface indicated by a double arrow on the AFM image (FIG. 6b).

(7) FIG. 7 provides a diagrammatic representation of a sequential film (FIG. 7a) and a statistical film (FIG. 7b) prepared according to this invention.

(8) FIG. 8 provides a diagrammatic representation of the grafting methods of the prior art (FIG. 8a) and the method according to this invention (FIG. 8b).

(9) FIG. 9 shows the IR spectrum of a gold plate treated according to an alternative of the method of this invention, i.e. with a solution of which the diazonium salt was prepared in situ using a monomer.

(10) FIG. 10 shows, for a gold plate treated according to this invention, with a primer and a monomer, on the one hand, the IR spectrum of said gold plate treated at different exposure times (FIG. 10a) and, on the other hand, the IR spectrum of said gold plate treated according to the amount of iron filings (FIG. 10b).

(11) FIG. 11 shows the XPS spectrometry (X photoelectron spectroscopy) analyses of a conductive carbon felt (FIG. 11a) and of the same carbon felt on which an organic film is grafted, which film is prepared according to the method of this invention, i.e. from a diazonium salt created in situ and acrylic acid, in the presence of iron filings (AAP for acrylic acid polymer) (FIG. 11b).

(12) FIG. 12 shows the IR spectrum of a gold plate treated according to the method of this invention for forming a sequential film.

(13) FIG. 13 shows the IR spectrum of a gold plate treated according to the method of this invention for forming a statistical film.

(14) FIG. 14 shows the IR spectrum of a gold plate treated according to the method of this invention for forming a film based on a monomer that is insoluble in the reaction solvent.

(15) FIG. 15 shows the IR spectrum of a glass plate treated according to the method of this invention with a primer and a monomer.

(16) FIG. 16 shows a photograph of carbon nanotubes (FIG. 16a) and a photograph of carbon nanotubes after a treatment according to the invention with a primer and a monomer (FIG. 16b).

(17) FIG. 17 shows the IR spectrum of a PTFE plate treated according to the method of this invention with a primer and a monomer.

(18) FIG. 18 shows the IR spectra obtained for a gold plate (FIG. 18a) and a titanium plate (FIG. 18b) treated identically according to the method of this invention, i.e. based on 2-hydroxyethylmethacrylate and a diazonium salt prepared in situ, in the presence of iron filings.

(19) FIG. 19 shows the photograph of a water drop on a pristine glass plate (FIG. 19a) and the photograph of a water drop on the same glass plate coated with p-butylmethacrylate (p-BuMA) according to the method of the invention (FIG. 19b).

(20) FIG. 20 shows the IR/AFM mapping obtained for gold plates coated with a commercial ink mask after treatment by the process in the presence of hydroxyethylmethacrylate (FIG. 20a) or acrylic acid (FIG. 20b) and removal of the mask.

(21) FIG. 21 shows the IR/AFM mapping obtained for a gold plate coated with a thiol mask after treatment by the process in the presence of acrylic acid and removal of the mask.

(22) FIG. 22 shows the IR/AFM mapping obtained for a gold plate coated with a thiol mask after treatment by the process in the presence of hydroxyethylmethacrylate and removal of the mask with different patterns (FIG. 22a and FIG. 22b).

(23) FIG. 23 shows the IRRAS spectrum of a gold plate coated with a film comprising PHEMA and a cyclodextrin derivative.

(24) FIG. 24 shows the IRRAS spectrum of a gold plate coated with a film comprising PHEMA and a calixarene derivative.

(25) FIG. 25 shows the XPS spectra C.sub.1s (25a) and N.sub.1s (25b) of a gold plate coated with a film developed from a single primer and comprising a porphyrin derivative.

(26) FIG. 26 shows an XPS spectrum (global) of a film comprising PAA, grafted on a gold plate, before incorporation of the Pt nanoparticles.

(27) FIG. 27 shows an XPS spectrum (global) of a film comprising PAA, grafted on a gold plate, after incorporation of the Pt nanoparticles.

(28) FIG. 28 shows an XPS spectrum (global) of a film comprising PAA, grafted on carbon nanotubes, after incorporation of the Pt nanoparticles.

DETAILED DESCRIPTION OF SPECIFIC EMBODIMENTS

(29) The following examples were performed in a glass cell. Unless otherwise indicated, they were conducted under normal conditions of temperature and pressure (around 25° C. under around 1 atm) in ambient air. Unless otherwise indicated, the reagents used were obtained directly on the market without any additional purification. The glass plates used had a surface of 1 cm.sup.2.

(30) No precaution was taken with regard to the composition of the atmosphere, and the solutions were not degassed. When the reaction time is not specified, the exposure of the surface to be treated with the reagent solution lasted for 1 to 15 minutes.

(31) Four series of examples illustrate the embodiments of the invention. The first concerns films prepared with an adhesion primer, the second concerns films prepared with an adhesion primer and a monomer, the third concerns functionalisable films, and the fourth concerns films comprising nano-objects.

I—Adhesion Primer Alone

Example I-1—Preparation of a Film on a Gold Plate Using a Diazonium Salt from Para-Benzylamine, Prepared In Situ in the Presence of Iron Filings

(32) 4 ml of a solution of NaNO.sub.2 at 0.1 M in water were added to 4 ml of a solution of para-benzylamine at 0.1 M in HCl (0.5 M), in order to form the diazonium salt. A gold plate was then added to the reaction medium for 15 min. The plate was then rinsed in water with acetone, and subjected to ultrasound in DMF and then a basic soda solution with a pH=9.5 so as to deprotonate the primary amine, before being dried.

(33) The XPS spectrometry (X photoelectron spectroscopy) and IR analyses confirm the presence of the film expected, of which the thickness increases with the reaction time. The specific poly-benzylamine bands at 1476 cm.sup.−1 (Deformation C═C), 1582 cm.sup.1 (Deformation N—H) and 3362 cm.sup.−1 (Elongation N—H) are visible on the IR spectrum of a plate after the treatment (FIG. 1).

Example I-2—Preparation of a Film on a Gold Plate Using a Diazonium Salt from p-Phenyldiamine, Prepared In Situ in the Presence of Iron Filings

(34) 4 ml of a solution of NaNO.sub.2 at 0.1 M in water were added to 4 ml of a solution of p-phenyldiamine at 0.1 M in HCl (0.5 M), in order to form the diazonium salt. 200 mg of iron filings were added to this diazonium salt solution. A gold plate was then added to the reaction medium for 15 min. The plate was then rinsed in water with acetone, and subjected to ultrasound in DMF and then rinsed in water before being dried.

(35) The XPS spectrometry (X photoelectron spectroscopy) and IR analyses confirm the presence of the film expected, of which the thickness increases with the reaction time. The specific p-phenylamine bands at 1514 cm.sup.−1 (Deformation C═C), 1619 cm.sup.−1 (Deformation N—H) and 3373 cm.sup.−1 (Elongation N—H) are visible on the IR spectrum of a plate after the treatment (FIG. 2).

Example I-3—Test of the Film Thickness

(36) To show the influence of various parameters on the thickness of the organic film, the method was applied to a gold plate, placed in the presence of a solution containing 4-aminobenzyldiazonium, under non-electrochemical conditions allowing for the formation of radical entities. This choice was in particular motivated by the presence of characteristic absorption bands of the film obtained at 1504 cm.sup.−1 (Deformation C═C), 1605 cm.sup.1 (Deformation N—H) and 1656 cm.sup.−1 (Elongation N—H).

(37) A solution of diazonium salt in water was prepared by adding 4 ml of a solution of NaNO.sub.2 at 0.1 M (4.10.sup.−4 moles) to 4 ml of a solution at 0.1 M (4.10.sup.−4 moles) of p-4-aminobenzylamine in HCl (0.5 M), under agitation. A gold plate was added to this solution.

(38) To study the influence of the reaction time, the solution was then placed under non-electrochemical conditions allowing for the formation of radicals on the adhesion primer by adding 200 mg of iron filings. The plate was then removed from the reaction medium and immediately rinsed with water then acetone and dimethylformamide (DMF) under ultrasound, and finally dried under an argon current.

(39) As shown by the IR spectrum in FIG. 3, the time of exposure of the sample to the reaction medium has an influence on the thickness of the film obtained. Exposure times of 5, 10 and 15 minutes were tested. It appears that a prolonged exposure increases the thickness of the film. Indeed, the increase in the intensity of the absorption bands of the poly-p-4-aminobenzylamine at 1504 cm.sup.−1, 1605 cm.sup.−1 and 1656 cm.sup.−1 indicates an increase in the thickness of the film over time.

Example I-4—Preparation of a Film on a Gold Plate Using Commercial p-Nitrophenyldiazonium in the Presence of Iron Filings

(40) The experiment was conducted according to the protocol described in example I-2, using commercial p-nitrophenyldiazonium (Aldrich®) solubilised at 0.05 M in an HCl solution (0.5 M). The gold plate was then immersed in the solution for around 15 min. The plate was then rinsed with water and acetone, and subjected to ultrasound in DMF and then in water before being dried.

(41) As above, the XPS spectrometry (X photoelectron spectroscopy) and IR analyses confirmed the presence of the film expected, of which the thickness increases with the reaction time.

Example I-5—Preparation of a Film on a Gold Plate Using a Diazonium Salt Created In Situ in the Presence of Steel Wool

(42) The procedure is identical to that of example I-1. The iron filings were replaced by around 5.10 mg of steel wool fibers (supplier CASTORAMA®), successively fine (0), extra fine (00) and super fine (000), which makes it possible not to have solid iron residue in the solution.

(43) The XPS and IR analyses confirm the presence of the film expected, of which the thickness increases with the reaction time.

Example I-6—Preparation of a Film on a Gold Plate Using a Diazonium Salt Created In Situ in a Basic Medium

(44) The procedure is identical to that of example I-1. 0.3 ml of a soda solution at 2.5×10.sup.−3 M were substituted for the iron filings in order to allow for a slight increase in the pH to above 4.

(45) The XPS and IR analyses confirm the presence of the film expected, of which the thickness increases with the reaction time.

Example I-7—Preparation of a Film on a Gold Plate Using a Diazonium Salt Created In Situ, Primed by an Irradiated PVDF Membrane

(46) The protocol is identical to that of example I-1. An irradiated PVDF membrane (2 cm.sup.2, thickness 9 μm, electron irradiation dose: 100 kGy) was substituted for iron filings.

(47) The IR analyses confirmed the presence of the expected film, the thickness of which increased with the reaction time.

Example I-8—Preparation of a Film on a Gold Plate Using a Diazonium Salt Created In Situ in the Presence of Iron Filings

(48) The protocol is identical to that of example I-1. A glass plate was used in this case. The IR spectrum confirms the presence of the expected film, of which the thickness increases with the reaction time.

Example I-9—Preparation of a Film on a Nickel Plate Using a Diazonium Salt Prepared In Situ in the Presence of Iron Filings

(49) The protocol is identical to that of example I-1. A nickel plate was used in this case with a reaction temperature of 40° C. The IR spectrum obtained (FIG. 4) confirms the presence of the expected film, of which the thickness increases with the reaction time.

Example I-10—Preparation of a Film on a Steel Plate (AISI 316L) Using a Diazonium Salt Prepared In Situ in the Presence of Iron Filings

(50) The protocol is identical to that of example I-1. A steel plate AISI 316L was used in this case. The IR spectrum obtained (FIG. 5) confirms the presence of the expected film, of which the thickness increases with the reaction time.

Example I-11—Preparation of a Film on a Diamond Using a Diazonium Salt Prepared In Situ in the Presence of Iron Filings

(51) The protocol is identical to that of example I-1. A piece of diamond was used in this case. An AFM image (FIG. 6) confirms the presence of the expected film, of which the thickness increases with the reaction time. The profilometric analysis shows the presence of the film at the surface.

II—Adhesion Primer and Monomer

Example II-1—Preparation of a Film on a Gold Plate Using a Diazonium Salt Prepared In Situ and 2-Hydroxyethylmethacrylate (HEMA) in the Presence of Iron Filings

(52) 4 ml of a solution of NaNO.sub.2 at 0.1 M in water were added to 4 ml of a solution of p-phenylenediamine at 0.1 M in HCl (0.5 M), in order to form the aminophenyl mono diazonium salt. 1 ml of HEMA, then 200 mg of iron filings were added to this diazonium salt solution. A gold plate was then added to the reaction medium for 15 min. The plate was then rinsed in water with acetone, and subjected to ultrasound in DMF and then in water before being dried.

(53) The XPS spectrometry (X photoelectron spectroscopy) and IR analyses confirm the presence of the film expected, of which the thickness increases with the reaction time. FIG. 9 shows the IR spectrum of a plate after the treatment.

(54) Table 3 provided below combines a set of thickness values obtained for the same reagents when their concentrations, the exposure time or the amount of filings were varied.

(55) TABLE-US-00003 TABLE 3 HEMA Diazonium Thickness (mol .Math. l.sup.−1) (mol .Math. l.sup.−1) Time (min) Iron (mg) (nm) 0.9 0.05 1 200 10 0.9 0.05 3 200 50 0.9 0.05 5 200 90 0.9 0.05 10 200 140 0.9 0.05 15 200 200 0.45 0.025 1 200 <10 0.45 0.025 3 200 20 0.45 0.025 5 200 40 0.45 0.025 10 200 90 0.45 0.025 15 200 120 0.9 0.05 10 5 <10 0.9 0.05 10 50 30 0.9 0.05 10 100 70 0.9 0.05 10 150 100 0.9 0.05 10 200 150

(56) The increase in the exposure time, the primer and the monomer concentrations, and the amount of filings, enables the thickness of the film formed to be increased.

Example II-2—Test of the Film Thickness

(57) To show the influence of various parameters on the thickness of the organic film, the method was applied to a gold plate, placed in the presence of a solution containing an adhesion primer, 4-aminophenyldiazonium, and a monomer, HEMA, under non-electrochemical conditions allowing for the formation of a radical entity based on the adhesion primer. This choice was motivated in particular by the presence of characteristic absorption bands at 1726, 1454 and 1166 nm of the poly-HEMA.

(58) A solution of adhesion primer in water was prepared by adding 4 ml of a solution of NaNO.sub.2 at 0.1 M (4.10.sup.−4 moles) to 4 ml of a solution at 0.1 M (4.10.sup.−4 moles) of p-phenylenediamine in HCl (0.5 M), under agitation. 1 ml (8.24 mmoles) of HEMA and a gold plate were added to this solution.

(59) 2-1 Influence of the Reaction Time

(60) The solution was then placed under non-electrochemical conditions allowing for the formation of radicals on the adhesion primer by adding 200 mg of iron filings. The plate was then removed from the reaction medium and immediately rinsed with water then acetone and dimethylformamide (DMF) under ultrasound, and finally dried under an argon current.

(61) As shown by the IR spectrum in FIG. 10a, the time of exposure of the sample to the reaction medium has an influence on the thickness of the film obtained. Indeed, the increase in the intensity of the absorption bands of the HEMA at 1726, 1454 and 1166 nm indicates an increase in the thickness of the film over time.

(62) The thickness of the films was measured using a profilometer: it ranged from 12 nm to 200 nm for an exposure time ranging from 1 to 15 minutes.

(63) 2-2 Influence of Non-Electrochemical Conditions Allowing for the Formation of Radicals on the Adhesion Primer

(64) Given that the amount of radicals present in the solution has a notable influence on the reaction, the method was carried out with a variable amount of iron filings for a reaction time set at 10 min.

(65) As shown by the IR spectrum in FIG. 10b, the amount of iron filings present in the reaction medium has an influence on the thickness of the film obtained. A minimum amount of filings is necessary in order to generate enough radicals in the reaction medium and make it possible to obtain a grafted film of an IR-detectable thickness. Beyond a certain maximum amount of filings, the variations in thickness of the film obtained are negligible.

Example II-3—Preparation of a Film on a Gold Plate Using Commercial p-Nitrophenyldiazonium and HEMA in the Presence of Iron Filings

(66) The experiment was conducted according to the protocol described in example II-2, using commercial p-nitrophenyldiazonium (Aldrich®) solubilised at 0.05 M in an HCl solution (0.5 M). The gold plate was then immersed in the solution for around 15 min. The plate was then rinsed with water and acetone, and subjected to ultrasound in DMF and then in water before being dried.

(67) As above, the XPS spectrometry (X photoelectron spectroscopy) and IR analyses confirmed the presence of the film expected, of which the thickness increases with the reaction time.

Example II-4—Preparation of a Film on a Gold Plate Using a Diazonium Salt Created In Situ and HEMA in a Basic Medium

(68) The procedure is identical to that of example II-2. 0.3 ml of a NaOH solution at 2.5×10.sup.−3 M were substituted for the iron filings in order to allow for a slight increase in the pH to above 4.

(69) The XPS and IR analyses confirm the presence of the film expected, of which the thickness increases with the reaction time.

Example II-5—Preparation of a Film on a Conductive Carbon Felt Using a Diazonium Salt Created In Situ and Acrylic Acid (AA) in the Presence of Iron Filings

(70) The example was performed according to the procedure described in example II-2. The monomer used in this case was acrylic acid (1 ml) and the sample was constituted by carbon felt.

(71) The XPS analysis, as shown by the spectrum of FIG. 11, confirms the presence of the expected film.

Example II-6—Preparation of a Sequential Film on a Gold Plate Using a Diazonium Salt Prepared In Situ, HEMA and AA in the Presence of Iron Filings

(72) First, a plate was prepared and cleaned according to the procedure of example II-2.

(73) A new solution of the same diazonium salt was then prepared and, to it, 1 ml of acrylic acid, then 200 mg of iron filings were added. The plate previously prepared according to example II-2 was then placed in the reaction medium for a variable time, at the end of which it was cleaned and dried as described above.

(74) FIG. 12 shows the IR spectrum obtained for such a plate after 15 minutes of reaction. The characteristic bands of the AAP (acrylic acid polymer) at 1590 and 1253 nm appear on the spectrum of example 2.

Example II-7—Preparation of a Statistical Film on a Gold Plate Using a Diazonium Salt Prepared In Situ, HEMA and AA in the Presence of Iron Filings

(75) The procedure used is identical to that of example II-2, except that 0.5 ml of acrylic acid and 0.5 ml of HEMA were added to the diazonium salt solution.

(76) The IR spectrum obtained is shown in FIG. 13: it confirms the presence of the expected statistical film constituted in particular by the two monomers.

Example II-8—Preparation of a Film on a Gold Plate Using a Diazonium Salt Prepared In Situ and 4-Vinyl-Pyridine (4VP) in the Presence of Iron Filings

(77) 200 mg of iron filings, then a dispersion of 1 ml of 4 vinyl-pyridine in 10 ml of water, prepared by an ultrasound treatment, were added to a diazonium salt solution prepared according to example II-2, containing a gold plate. After a variable reaction time, the plate is then cleaned and dried according to the procedures described above.

(78) The IR spectrum obtained for the plate is shown in FIG. 14. The characteristic bands at 1602, 1554 and 1419 nm validate the presence of the expected film.

Example II-9—Preparation of a Film on a Glass Plate Using a Diazonium Salt Prepared In Situ and HEMA in the Presence of Iron Filings

(79) The protocol is identical to that of example II-2, except that a glass plate is used in this case.

(80) The IR spectrum shown in FIG. 15 confirms the presence of the expected film, the thickness of which increases with the reaction time.

Example II-10—Preparation of a Film on Carbon Nanotubes Using a Diazonium Salt Prepared In Situ and HEMA in the Presence of Iron Filings

(81) 200 mg of iron filings and 1 ml of HEMA were added to a diazonium salt solution prepared as indicated in example II-2. Then, 100 mg of multiwall carbon nanotubes in the form of a carpet were added to this solution. The layer, after reaction, was cleaned according to the protocol described in example 2 before being dried.

(82) The photographs obtained by scanning electron microscopy (SEM), shown in FIG. 16, correspond to nanotubes before (FIG. 16a) and after (FIG. 16b) treatment.

Example II-11—Preparation of a Film on a PTFE (Teflon®) Surface Using a Diazonium Salt Prepared In Situ and HEMA in the Presence of Iron Filings

(83) 4 ml of a solution of NaNO.sub.2 at 0.1 M in water were added to 4 ml of a solution of p-phenylenediamine at 0.1 M in HCl (0.5 M) so as to form the diazonium salt. 1 ml of HEMA, then 200 mg of iron filings were added to this diazonium salt solution. A Teflon® part measuring 4 cm.sup.2 was then introduced to the reaction medium for 15 min, the plate was then rinsed in water and acetone and exposed to ultrasound in DMF, then water, before being dried.

(84) The spectrometry and IR analyses (FIG. 17) confirm the presence of the expected film, the thickness of which increases with the reaction time.

Example II-12—Application of the Method to Different Samples

(85) The method was successfully applied to a large number of samples of various types, and different monomers were used. The diazonium salt used in this example was prepared in situ using p-phenylenediamine.

(86) The results obtained for each type of sample according to the monomer are shown in table 4 below. For each of the samples tested, the presence of the organic film was verified using IR spectra.

(87) TABLE-US-00004 TABLE 4 Support Monomer Time (min) Film Gold HEMA 15 yes Gold Acrylic acid 15 yes Gold Acrylonitrile 15 yes Silicon wafer HEMA 20 yes Silicon wafer Acrylic acid 20 yes Silicon wafer Acrylonitrile 20 yes Aluminum HEMA 30 yes Aluminum Acrylic acid 30 yes Aluminum Acrylonitrile 30 yes Nanotubes(c) HEMA 15 yes Nanotubes (c) Acrylic acid 15 yes Felt HEMA 15 yes Felt Acrylic acid 15 yes Felt Acrylonitrile 15 yes Platinum HEMA 15 yes Platinum Acrylic acid 15 yes Platinum Acrylonitrile 15 yes Stainless HEMA 15 yes steel Stainless Acrylic acid 15 yes steel Stainless Acrylonitrile 15 yes steel Zinc HEMA 15 yes Zinc Acrylic acid 15 yes Zinc Acrylonitrile 15 yes Titanium HEMA 15 yes Titanium Acrylic acid 15 yes Titanium Acrylonitrile 15 yes Nickel HEMA 15 yes Nickel Acrylic acid 15 yes Nickel Acrylonitrile 15 yes Wood HEMA 45 yes Paper HEMA 45 yes Cotton HEMA 45 yes Teflon ® HEMA 30 yes

Example II-13—Preparation of a Film on Surfaces of Different Types (Gold Plate and Titanium Plate) for the Same Solution

(88) 4 ml of a solution of NaNO.sub.2 at 0.1 M in water were added to a solution of p-phenylenediamine at 0.1 M in HCl (0.5 M). 1 ml of HEMA, then 200 mg of iron filings were added to this diazonium salt solution. A gold plate and simultaneously a titanium plate measuring 4 cm.sup.2 were then placed in the reaction medium for 15 min. The plates were then rinsed with water and acetone, and subjected to ultrasound in DMF, then water, before being dried.

(89) The spectrometry and IR analyses (FIG. 18) confirm the presence of the expected film for the two substrates.

Example II-14—Preparation of a Film on a Glass Plate Using a Diazonium Salt Prepared In Situ and Butylmethacrylate in the Presence of Iron Filings

(90) 200 mg of iron filings, then a dispersion of 1 ml of butylmethacrylate (BUMA) in 10 ml of water prepared by ultrasound were added to a diazonium salt solution prepared according to example II-2 and containing a glass plate that has been pre-cleaned by a “piranha” solution treatment (i.e. a mixture of 60/40 by volume of concentrated sulfuric acid and water oxygenated at 110 volumes). After a reaction time of 10 minutes, the plate is then cleaned and dried according to the procedures described above.

(91) A spot test was then performed on the glass plate thus coated (FIG. 19b) and on a pristine glass plate used as a control (FIG. 19a). A change in the physical property of the glass plate thus coated, which becomes water-repellent, can be observed by the variation in the surface angle between the drop and the surface.

Example II-15—Preparation of a Film on a Gold Plate Having a Commercial Ink Mask Based on a Diazonium Salt Prepared In Situ and Hydroxyethylmethacrylate (HEMA) or Acrylic Acid (AA) in the Presence of Iron Fillings

(92) The protocol used is identical to that of example II-2 for HEMA and 5 for AA. Prior to its introduction to the reaction medium, the plate was coated with a mask: different patterns were produced on the gold plate using a black-colored ink felt pen (Staedtler®-Lumocolor®).

(93) After reaction, the plate was washed with water, DMF and acetone in order to remove the reaction products, then washed more vigorously with ultrasound with the same solvents. The surface was then rinsed again with acetone, then dried before being analyzed by Infrared spectroscopy (IR) (C═O bands for each of the polymers) and by Atomic Force Microscopy (AFM).

(94) The different mappings (IR/AFM) obtained are shown in FIG. 20. FIG. 20A shows the presence of a cross-shaped pattern and FIG. 20B shows another pattern, which are not covered by the organic film (it is a transmittance measurement, also, the areas in relief correspond to non-grafted areas).

Example II-16—Preparation of a Film on a Gold Plate Having a Thiol Mask Based on a Diazonium Salt Prepared in Situ and Acrylic Acid (AA) in the Presence of Iron Fillings

(95) The protocol used is identical to that of example II-15. Prior to its introduction into the reaction medium, a drop of long-chain (C18) ethanolic thiol solution was deposited on the plate, and the plate was treated after evaporation of the ethanol.

(96) After the treatment, the plate was then cleaned and analyzed as in example II-15.

(97) The IR/AFM mapping is shown in FIGS. 21a and 21b, which respectively show a three-dimensional view (a transmittance measurement, also, the areas in relief correspond to the non-grafted areas) and a planar view of the plate (the light area corresponding to the non-grafted area). It can be noted in these figures that the areas that were covered with the mask do not have a grafted film.

Example II-17—Preparation of a Film on a Gold Surface Having a Thiol Microprinted Mask Based on a Diazonium Salt Prepared In Situ and Hydroxyethylmethacrylate (HEMA) in the Presence of Iron Fillings

(98) The protocol used is identical to that of example II-15. Prior to its introduction into the reaction medium, the plate is covered with a thiol mask using a PDMS (polydimethylsiloxane) buffer having micrometric patterns and previously impregnated with a long-chain (C18) ethanolic thiol solution. The plate was treated after evaporation of the ethanol.

(99) After the treatment, the plate was cleaned and analyzed as in example II-15.

(100) The AFM mapping is shown in FIG. 22a, which shows that the grafted surface corresponds to the reverse of the triangular micrometric patterns appearing on the buffer and in FIG. 22b, which shows micrometric patterns corresponding to lines (a transmittance measurement, also, the areas in relief correspond to the non-grafted areas).

Example II-18—Preparation of a Film on a Gold Plate Using a Diazonium Salt from Para-Benzylamine, Prepared In Situ in the Presence of Non Porous Electron Irradiated PVDF Membrane and with Acetonitrile (ACN)

(101) 4 ml of a solution of NaNO.sub.2 at 0.1 M in water were added to 4 ml of a solution of para-benzylamine at 0.1 M in HCl (0.5 M), in order to form the diazonium salt.

(102) To 4 ml of this solution, were added to 4 ml of acetonitrile (ACN). An electron irradiated PVDF membrane (2 cm.sup.2, thickness 9 μm, electron irradiation dose: 100 kGy) was substituted for iron filings presented in the former examples. A gold plate was then added to the reaction medium for 15 min. The plate was then rinsed in water with acetone, and subjected to ultrasound in DMF and then a basic soda solution with a pH=9.5 so as to deprotonate the primary amine, before being dried.

(103) The IR analyses confirmed the presence of the expected film, of which the thickness increased with the reaction time.

Example II-19—Preparation of a Film on a Gold Plate Using a Diazonium Salt from Para-Benzylamine, Prepared In Situ in the Presence of Nanoporous Electron Irradiated PVDF Membrane and with Acetonitrile (ACN)

(104) 4 ml of a solution of NaNO.sub.2 at 0.1 M in water were added to 4 ml of a solution of para-benzylamine at 0.1 M in HCl (0.5 M), in order to form the diazonium salt.

(105) A nanoporous electron irradiated PVDF membrane (2 cm.sup.2, thickness 9 μm, electron irradiation dose: 100 kGy, fluence: 10.sup.10 pores/cm.sup.2, pore diameter: 50 nm) was substituted for iron filings presented in the former examples. A gold plate was then added to the reaction medium for 15 min. The plate was then rinsed in water with acetone, and subjected to ultrasound in DMF and then a basic soda solution with a pH=9.5 so as to deprotonate the primary amine, before being dried.

(106) The IR analyses confirmed the presence of the expected film, of which the thickness increased with the reaction time.

Example II-20—Preparation of a Film on a Gold Plate Using a Diazonium Salt from Para-Benzylamine, Prepared In Situ in the Presence of Non Porous Electron Irradiated PVDF Membrane and With Acrylic Acid (AA)

(107) 6.5 ml of a solution of NaNO.sub.2 at 0.1 M in water were added to 6.5 ml of a solution of para-benzylamine at 0.1 M in HCl (0.5 M), in order to form the diazonium salt.

(108) To this solution, were added to 2 ml of acrylic acid (AA) and the resulting solution was bubbled with Ar for 15 min.

(109) An electron irradiated PVDF membrane (2 cm.sup.2, thickness 9 μm, electron irradiation dose: 100 kGy) was substituted for iron filings presented in the former examples. A gold plate was then added to the reaction medium for 15 min under inert atmosphere (Ar). The plate was then rinsed in water with acetone, and subjected to ultrasound before being dried.

(110) The IR analyses confirmed the presence of the expected film, of which the thickness increased with the reaction time.

Example II-21—Preparation of a Film on a Gold Plate Using a Diazonium Salt from Para-Benzylamine, Prepared In Situ in the Presence of Nanoporous Electron Irradiated PVDF Membrane and With Acrylic Acid (AA)

(111) 6.5 ml of a solution of NaNO.sub.2 at 0.1 M in water were added to 6.5 ml of a solution of para-benzylamine at 0.1 M in HCl (0.5 M), in order to form the diazonium salt.

(112) To this solution, were added to 2 ml of acrylic acid (AA) and the resulting solution was bubbled with Ar for 15 min.

(113) A nanoporous electron irradiated PVDF membrane (2 cm.sup.2, thickness 9 μm, electron irradiation dose: 100 kGy, fluence: 10.sup.10 pores/cm.sup.2, pore diameter: 50 nm) was substituted for iron filings presented in the former examples. A gold plate was then added to the reaction medium for 15 min under inert atmosphere (Ar). The plate was then rinsed in water with acetone, and subjected to ultrasound before being dried.

(114) The IR analyses confirmed the presence of the expected film, of which the thickness increased with the reaction time.

Example II-22—Preparation of a Film on a Gold Plate Using a Diazonium Salt from Para-Benzylamine, Prepared In Situ in the Presence of Non Porous Electron Irradiated PVDF Membrane and with Acrylic Acid (AA) and Acetonitrile (ACN)

(115) 4 ml of a solution of NaNO.sub.2 at 0.1 M in water were added to 4 ml of a solution of para-benzylamine at 0.1 M in HCl (0.5 M), in order to form the diazonium salt.

(116) To 4 ml of this solution, were added to 11 ml of acetonitrile (ACN) and 2 ml of acrylic acid (AA), the resulting solution was then bubbled with Ar for 15 min.

(117) An electron irradiated PVDF membrane (2 cm.sup.2, thickness 9 μm, electron irradiation dose: 100 kGy) was substituted for iron filings presented in the former examples. A gold plate was then added to the reaction medium for 15 min under inert atmosphere (Ar). The plate was then rinsed in water with acetone, and subjected to ultrasound before being dried.

(118) The IR analyses confirmed the presence of the expected film, of which the thickness increased with the reaction time.

Example II-23—Preparation of a Film on a Gold Plate Using a Diazonium Salt from Para-Benzylamine, Prepared In Situ in the Presence of Nanoporous Electron Irradiated PVDF Membrane and with Acrylic Acid (AA) and Acetonitrile (ACN)

(119) 4 ml of a solution of NaNO.sub.2 at 0.1 M in water were added to 4 ml of a solution of para-benzylamine at 0.1 M in HCl (0.5 M), in order to form the diazonium salt.

(120) To 4 ml of this solution, were added to 11 ml of acetonitrile (ACN) and 2 ml of acrylic acid (AA), the resulting solution was then bubbled with Ar for 15 min.

(121) A nanoporous electron irradiated PVDF membrane (2 cm.sup.2, thickness 9 μm, electron irradiation dose: 100 kGy, fluence: 10.sup.10 pores/cm.sup.2, pore diameter: 50 nm) was substituted for iron filings presented in the former examples. A gold plate was then added to the reaction medium for 15 min under inert atmosphere (Ar). The plate was then rinsed in water with acetone, and subjected to ultrasound before being dried.

(122) The IR analyses confirmed the presence of the expected film, of which the thickness increased with the reaction time.

Example II-24—Preparation of a Film on a Gold Plate Using Commercial p-Nitophenyldiazonium and 2-Hydroxyethylmethacrylate (HEMA) in the Presence of Ferrocene

(123) At 2 ml of dimethylformamid (DMF) were added 0.04 mole of ferrocene and 1 ml of HEMA (3 10.sup.−3 M). At this solution were added 2 ml of 0.015 mole p-nitrophenyldiazonium tetrafluoroborate solution in DMF. A gold plate was then added to the reaction medium for 30 minutes. The plate was then rinsed with DMF, acetone, and subjected to ultrasounds in DMF (3 minutes) and then rinsed in acetone before being dried.

(124) The IR analyses confirm the presence of the film expected, of which the thickness increases with the reaction time. The specific poly-HEMA bands at 1726, 1454 and 1166 cm.sup.−1 are visible on the IR spectrum of a plate after the treatment.

Example II-25—Preparation of a Film on the Surface of Multiwall Carbon Nanotubes (MWCNTs) Using Commercial p-Nitophenyldiazonium and Butylmethacrylate (BUMA) in the Presence of Ferrocene

(125) 10.2 mg of MWCNTs were subjected to ultrasounds in 8 ml of DMF. At this solution was added 5 ml of a solution of BUMA and 0.04 mole of ferrocene. The resulting mixture was stirred during 3 minutes and then 0.015 mole of p-nitrophenyldiazonium tetrafluoroborate were added. After a 2 hours reaction, the nanotubes were filtered and washed several times with DMF and acetone. Finally, the MWCNTs were dried in a vacuum oven (100° C., 10.sup.−2 Torr).

(126) The XPS spectrometry (X photoelectron spectroscopy) and scanning electrons microscopy (SEM) analyses confirm the presence of the film expected, of which the thickness increases with the reaction time.

Example II-26—Preparation of a Film on the Surface of a Carpet of Multiwall Carbon Nanotubes (MWCNTs) Using Commercial p-Nitophenyldiazonium and 2-Hydroxyethylmethacrylate (HEMA) in the Presence of Ferrocene

(127) At 12 ml of DMF were added 0.04 mole of ferrocene, 5 ml of HEMA and the carpet of MWCTs supported by a silicon substrate (1 cm.sup.2 area, length of the tubes 275 μm). At this solution was added 103.9 mg (0.015 mole) of p-nitrophenyldiazonium tetrafluoroborate. After 2 hours reaction, the nanotubes were rinsed several times with DMF and acetone. Finally, the MWCNTs were dried in a vacuum oven (100° C., 10.sup.−2 Torr).

(128) The XPS spectrometry (X photoelectron spectroscopy) and scanning electrons microscopy (SEM) analyses confirm the presence of the film expected, of which the thickness increases with the reaction time.

III—Functionalisable Films

Example III-1—Film Comprising PHEMA and CD Functionalization on a Gold Plate

(129) Per-(3,6)-anhydro-β-cyclodextrine (PaCD) (M=1008 g/mol) was first prepared according to the protocol described in Gadelle, A.; Defaye, J. Angew. Chem., Int. Ed. Engl. 1991, 30, 78. The carboxylic acid function of PaCD (10 mg) was then activated by forming an activated ester using N,N′-diisopropylcarbodiimide (DIC) (6 eq.) in DMF (5 ml) under agitation for 6 hours in the presence of catalytic amounts (0.05 eq.) of dimethyl amino pyridine (DMAP).

(130) A gold plate with a surface of 2 cm.sup.2 coated with a film, around 10 nm in thickness, comprising poly(2-hydroxyethyl)methacrylate (PHEMA) and produced according to the modalities of example II-3, was placed in a closed test tube containing 6 ml of DMF as well as the activated PaCD.

(131) The reaction mixture was left under agitation for 72 hours at room temperature, then the plate was removed and rinsed in DMF and acetone before being dried.

(132) An XPS and IRRAS analysis confirms that the film comprises a cyclodextrin functionalization.

(133) The capture of lead by a film comprising CD functionalization such as those of this example was demonstrated using a quartz scale (QCM 922 SEIKO®). A quartz with a gold deposit (supplied by SEIKO) comprising a film as produced above was immersed in a solution of PbNO.sub.3 (10.sup.−4 M) for 130 s. The variation in the resonance frequency of the quartz demonstrates the complexing.

Example III-2—Film Comprising PAA and CD Functionalization, Comprising a Linking Group, on a Gold Plate

(134) The PaCD was prepared according to example II-1. A propanol spacer was added to the PaCD to form a functionalizing compound comprising a linking group (LG).

(135) NaH (350 mg; 28 eq.) and 3-bromo-1-propanol (0.6 ml; 28 eq.) were added to a solution of PaCD (250 mg) in DMF (10 ml). After 24 hours, methanol (5 ml) is added to the reaction medium, then the solution is evaporated and the solid obtained is solubilised in water (0.5 ml) before being precipitated in acetone (300 ml). After filtration, the beige solid obtained is filtered on a Büchner funnel and dried. A mixture of propanol spacer PaCDs in various degrees, from 4 to 14 propanols, is obtained.

(136) A gold plate with a surface of 2 cm.sup.2 with a PAA film of around 100 nm, prepared according to the modalities of example II-2 from acrylic acid, was placed in a test tube containing the mixture of propanol spacer PaCDs (10 mg) solubilised in DMF (6 ml).

(137) The reaction medium was left under agitation for 72 hours at room temperature, then the plate was removed and rinsed in DMF and acetone before being dried.

(138) The XPS analysis confirmed the presence of cyclodextrin. Indeed, the peak of 01, at 534 eV that appears is typical of the ester bonds of cyclodextrin. Similarly, on the spectrum of C.sub.1, the peak centered at 289 eV corresponds to C═O bonds.

(139) On the IRRAS spectrum, an intense band at 1740 cm.sup.−1 appears, typical of the valence band C═O (ester), which confirms the formation of an ester. In addition, the bands appearing at 1250 cm.sup.−1 typical of C—O bonds (valence band) demonstrate the presence of cyclodextrin on the substrate.

(140) The capture of lead by a film comprising CD functionalization such as those of this example was demonstrated using a quartz scale (QCM 922 SEIKO®). A quartz with a gold deposit (supplied by SEIKO) comprising a film as produced above was immersed in a solution of PbNO.sub.3 (10.sup.−4 M) for 180 s. The variation in the resonance frequency of the quartz demonstrates the complexing.

Example III-3—Film Comprising PHEMA and Calixarene Functionalization on a Gold Plate

(141) In this example, the derivative of calixarene shown below, which was produced according to the literature (Bulletin of the Korean Chemical Society (2001), 22(3), 321-324), was used.

(142) ##STR00002##

(143) A gold plate with a surface of 2 cm.sup.2 coated with a film, around 5 nm in thickness, comprising poly(2-hydroxyethyl)methacrylate (PHEMA) and produced according to the modalities of example II-3, was placed in a closed test tube containing 10 ml of dichloromethane as well as 10 mg of K.sub.2CO.sub.3. 20 mg of a calix[4]arene derivative were added to this solution, and the reaction medium was brought to reflux under agitation for 72 h. The plate was then rinsed with acetone, water and dichloromethane.

(144) On the IRRAS spectrum, shown in FIG. 24, a band at 1600 cm.sup.−1 appears, which is typical of the C═C band (aromatic) (valence band), demonstrating the presence of calixarene grafted on the film.

Example III-4—Film Comprising Polybenzyl Amine and Porphyrin Functionalization on a Gold Plate

(145) A porphyrin of which the carboxylic acid function was activated by the formation of an activated ester was used. The activated ester was formed by a reaction of tetrakis(benzoic acid)-4,4′,4″4′″-(Porphyrin-5,10,15,20-tetrayl) (10 mg; 1.26 10.sup.−5 mol) with N,N′-diisopropylcarbodiimide (6 eq.) in DMF in the presence of a catalytic amount of DMAP (0.05 eq).

(146) A gold plate with a surface of 2 cm.sup.2 comprising a polybenzyl amine film, with a thickness of 0.6 nm and prepared according to the modalities of example I-1, was placed in a round-bottom flask containing the activated porphyrin.

(147) The reaction medium was left under agitation for 72 h at room temperature, then the plate was removed and rinsed in DMF and acetone before being dried.

(148) The XPS analysis confirmed the presence of porphyrin on the film. Indeed, the peak centered at 189.5 eV on the spectrum of C.sub.1, shown in FIG. 25a, corresponds to the C═C bond of the amide that is formed with the surface as well as the porphyrin acids not attached to the film. Similarly, the spectrum N.sub.1S, shown in FIG. 25b, is composed of two peaks of which one, centered at 399.5 eV, is typical of the nitrogens included in an aromatic cycle and corresponds to that of the porphyrin nitrogens.

IV—Films Comprising Nano-Objects

Example IV-1—Incorporation of Platinum Nanoparticles in a Film Comprising Polyacrylic Acid Grafted on Au

(149) An organic copolymer film derived from acrylic acid (AA) and a diazonium salt prepared in situ, grafted on a gold plate and comprising platinum nanoparticles was prepared.

(150) 1-1. Synthesis of the Stabilizer: HEA-16-Cl

(151) In a 50-ml round-bottom flask equipped with a coolant, 29.2 mmol of N—N-dimethyl ethanolamine and 35 mmol (1.2 eq) of hexadecyl chloride were dissolved in 15 ml of absolute ethanol. The mixture was then brought to reflux for 24 h. The ethanol was then evaporated and the reaction mixture cooled at room temperature. The white solid that formed was recrystallised in an acetone/ethanol mixture to yield the N,N-dimethyl-N-hexadecyl-N-(2-hydroxyethyl)ammonium chloride denoted HEA-16-Cl.

(152) 1-2. Preparation of the Colloidal Suspension of Platinum (0): Pt-HEA-16-Cl

(153) The colloidal suspension was prepared at 20° C. 3.6 mg of sodium borohydride (NaBH.sub.4) were added to 300 mg of HEA-16-Cl dissolved in 5 ml of ultra pure water. This solution was then rapidly added under vigorous agitation to 5 ml of ultra pure water containing 12 mg of platinum tetrachloride (PtCl.sub.4). The reduction of the Pt(IV) into Pt(0) is characterized by a change in coloring from pale yellow to black/brown. The suspension was left for one hour under mechanical agitation before use. This suspension is stable for a number of weeks.

(154) 1-3. Grafting of a Film Comprising Polyacrylic Acid on Au

(155) In a 50-ml beaker, the following were added, in order: 2 ml of 1-4 diaminophenyl (0.1 M), 2 ml of sodium nitrite (NaNO.sub.2, 0.1 M) and 1 ml of acrylic acid (AA). 50 mg of iron powder were then added to the solution and a 5 cm.sup.2 gold plate was placed in the medium. After 45 minutes, the plate was removed from the reaction medium, then rinsed (water/ethanol/acetone) and dried.

(156) An XPS analysis confirmed the presence of the PAA film.

(157) 1-4. Incorporation of Pt Nanoparticles in the Film Comprising PAA

(158) First, the gold plate coated with the organic film was immersed in a soda solution 0.5 M for 5 minutes, then dried without additional rinsing. This step made it possible to convert the carboxylic acid groupings, precursor of the affinity group, of the PAA into carboxylate groupings, which have an affinity for the particles. 1 ml of a colloidal suspension of Pt(0) was then deposited on the gold plate coated with the film. After 15 minutes, the plate was rinsed (water/ethanol/acetone) before being dried and then analyzed by XPS.

(159) The XPS analysis showed the presence of platinum (0) in a significant amount after the treatment, as shown in FIG. 27, which corresponds to an XPS spectrum of the film after integration of the particles, by comparison with FIG. 26, which corresponds to the film before incorporation of the particles.

Example IV-2—Incorporation of Gold Nanoparticles in a Film Comprising Polyacrylic Acid Grafted on Steel (AISI 316L)

(160) An organic copolymer film derived from acrylic acid (AA) and a diazonium salt prepared in situ, grafted on a steel plate (AISI 316L) and comprising gold nanoparticles was prepared.

(161) 2-1. Synthesis of the Stabilizer: HEA-16-Cl

(162) The stabilizer was prepared according to example I-1.

(163) 2-2. Preparation of the Colloidal Suspension of Gold (0): Au-HEA-16-Cl

(164) The colloidal suspension was prepared at 20° C. 3.6 mg of sodium borohydride (NaBH.sub.4) were added to 300 mg of HEA-16-Cl dissolved in 5 ml of ultra pure water. This solution was then rapidly added under vigorous agitation to 5 ml of ultra pure water containing 12 mg of gold salt (AuHCl.sub.4). The reduction of the Au(IV) into Au(0) is characterized by a change in coloring from pale yellow to brick red. The suspension was left for one hour under mechanical agitation before use. This suspension is stable for a number of weeks.

(165) 2-3. Grafting of a Film Comprising Polyacrylic Acid on Steel (AISI 316L)

(166) In a 50-ml beaker, the following were added, in order: 2 ml of 1-4 diaminophenyl (0.1 M), 2 ml of sodium nitrite (NaNO.sub.2, 0.1 M) and 1 ml of acrylic acid (AA). 50 mg of iron powder were then added to the solution and a 5 cm.sup.2 gold plate was placed in the medium. After 45 minutes, the plate was removed from the reaction medium, then rinsed (water/ethanol/acetone) and dried.

(167) An XPS analysis confirmed the presence of the PAA film.

(168) 2-4. Incorporation of Au Nanoparticles in the Film Comprising PAA

(169) First, the steel plate (AISI 316L) coated with the organic film was immersed in a soda solution 0.5 M for 5 minutes, then dried without additional rinsing. This step made it possible to convert the carboxylic acid groupings, precursor of the affinity group, of the PAA into carboxylate groupings, which have an affinity for the particles. 1 ml of a colloidal suspension of Au(0) was then deposited on the steel plate (AISI 316L) coated with the film. After 15 minutes, the plate was rinsed (water/ethanol/acetone) before being dried and then analyzed by XPS.

(170) The XPS analysis showed the presence of gold (0) in a significant amount because the steel (AISI 316L) is no longer visible.

Example IV-3—Incorporation of Platinum Nanoparticles in a Film Comprising Polyacrylic Acid Grafted on Carbon Nanotubes

(171) An organic copolymer film derived from acrylic acid (AA) and a diazonium salt prepared in situ, grafted on a carbon nanotube carpet and comprising platinum nanoparticles was prepared.

(172) 3-1. Synthesis of the Stabilizer: HEA-16-Cl

(173) The stabilizer was prepared according to the protocol described in example IV-1.

(174) 3-2. Preparation of the Colloidal Suspension of Platinum (0): Pt-HEA-16-Cl

(175) The suspension was produced as described in example IV-1.

(176) 3-3. Grafting of a Film Comprising Polyacrylic Acid on the Nanotube Carpet

(177) 200 mg of iron filings and 1 ml of acrylic acid were added to a diazonium salt solution prepared as indicated in example II-2. Then, 100 mg of carbon nanotubes in carpet form were added. The carpet, after reaction, was cleaned according to the protocol described in example IV-2 before being dried.

(178) 3-4. Incorporation of Pt Nanoparticles in the Film Comprising PAA

(179) First, the nanotube carpet coated with the organic film was immersed in a soda solution 0.5 M for 5 minutes, then dried without additional rinsing. This step made it possible to convert the carboxylic acid groupings, precursor of the affinity group, of the PAA into carboxylic groupings, which have an affinity for the particles. 1 ml of a colloidal suspension of Pt(0) was then deposited on the nanotube carpet coated with the film. After 15 minutes, the nanotube carpet was rinsed (water/ethanol/acetone) before being dried and then analyzed by XPS.

(180) The XPS analysis showed the presence of platinum (0) as indicated on the spectrum shown in FIG. 28.

Example IV-4—Incorporation of Platinum Nanoparticles in a Polybenzyl Amine Film Grafted on Au

(181) An organic film derived from a diazonium salt prepared in situ, grafted on a gold plate and comprising platinum nanoparticles was prepared.

(182) 4-1. Synthesis of the Stabilizer: HEA-16-Cl

(183) The stabilizer was prepared as indicated in example IV-1.

(184) 4-2. Preparation of the Colloidal Suspension of Platinum (0): Pt-HEA-16-Cl

(185) The procedure is identical to that of example IV-1.

(186) 4-3. Grafting of a Polybenzyl Amine Film on Au

(187) In a 50-ml beaker, the following were added, in order: 2 ml of p-amino-benzyl amine (0.1 M), 2 ml of sodium nitrite (NaNO.sub.2, 0.1 M) then, 50 mg of iron powder were then added to the solution and 5 cm.sup.2 gold plate was placed in the medium. After 45 minutes, the plate was removed from the reaction medium, then rinsed (water/ethanol/acetone) and dried.

(188) The XPS analysis confirmed the presence of the organic polybenzyl amine film.

(189) 4-4. Incorporation of Pt Nanoparticles in the Polybenzyl Amine Film

(190) First, the gold plate coated with the organic film was immersed in a soda solution 0.5 M for 5 minutes, then dried without additional rinsing. This step made it possible to transform the ammonium groupings, precursors of the affinity group, into amino groupings that have an affinity for the particles. 1 ml of a colloidal suspension of Pt(0) was then deposited on the gold plate coated with the film. After 15 minutes, the plate was rinsed (water/ethanol/acetone) before being dried and then analyzed by XPS.

(191) The XPS analysis showed the presence of platinum (0) in a significant amount.

Example IV-5—Incorporation of Silica Nanoparticles in a Film Comprising Polyacrylic Acid Grafted on Au

(192) An organic copolymer film derived from acrylic acid (AA) and a diazonium salt prepared in situ, grafted on a gold plate and comprising silica nanoparticles was prepared.

(193) Small (around 12 nm in diameter), non-porous and finely divided commercial silica particles (supplied by DEGUSA®) were used.

(194) Each particle is substantially spherical and has a specific surface of around 200 m.sup.2.Math.g.sup.−1 and contains around 1 mmol.Math.g.sup.−1 of silanol groupings.

(195) The colloidal solution of silica particles was obtained by mixing 10 mg of silica in 10 ml of distilled water.

(196) 5-1. Grafting of a Film Comprising Polyacrylic Acid on Au

(197) The grafting was performed as indicated in example IV-1.

(198) 5-2. Incorporation of Silica Particles in the Film Comprising PAA

(199) The incorporation of particles was performed according to the protocol of example IV-1.

(200) The infrared analysis confirmed the presence of particles in the film.

Example IV-6—Incorporation of Platinum Nanoparticles in a Film Comprising Polyacrylic Acid Grafted on Glass and Plastic

(201) Organic copolymer films derived from acrylic acid (AA) and a diazonium salt prepared in situ, grafted on a plastic (polyethylene) and glass plate and comprising platinum nanoparticles were prepared.

(202) The preparation of the organic films and the incorporation of the particles were performed according to the protocols presented in example IV-1.

(203) The XPS analysis showed the incorporation of particles in each of the films.

Example IV-7—Coalescence of Nanoparticles Present in the Films

(204) The surfaces of the glass and gold supports of the preceding examples, coated with an organic film comprising Au or Pt nanoparticles, were treated for 5 min with a heat gun at around 500° C. A modification in the surface appearance was observed during the treatment and the initial iridescent appearance disappeared, with a resulting uniformity due to the coalescence of the particles.

Example IV-8—Metallization of the Film by Chemical Reduction of a Metal Salt Solution Using Nanoparticles Present in the Film

(205) A metallization bath was prepared with two solutions, the first containing 3 g of copper sulfate, 14 g of potassium sodium tartrate and 4 g of sodium hydroxide in 100 ml of distilled water. The second solution is an aqueous formaldehyde solution with a weight percent of 37.02. The two solutions were mixed in a ratio of 10/1, and 20 ml of the resulting mixture were taken for immersion for 5 min of the supports, glass or gold, coated with an organic film comprising Au or Pt nanoparticles, obtained according to examples IV-1, IV-4 and IV-6. The surfaces of the supports were then rinsed in water and acetone, and dried under an argon flux. A change in the appearance of the surface was noted, and a metal film was obtained.

Example IV-9—Metallization of the Film by Chemical Reduction of a Metal Salt Solution Using Palladium Nanoparticles Present in the Film

(206) 9-1 Preparation of Colloïdale Tetraoctadecylammonium Bromide Stabilized Palladium Colloid (Pd/[C.sub.18H.sub.37]4N.sup.+Br.sup.−)

(207) The tetraoctadecylammonium bromide stabilized palladium colloid (Pd/[C.sub.18H.sub.37]4N.sup.+Br.sup.−) was synthesized as follows: Palladium(II) acetate (Fluka, 4 g, 17.8 mmol) and tetraoctadecylammonium bromide (Fluka, 5 g, 4.5 mmol) were suspended in 200 mL of a 5:1 (v/v) mixture of toluene and THF at 30° C. After addition of 25 mL of absolute ethanol, the mixture was refluxed at 65° C. for 12 h. The color of the solution turned to deep brown-black.

(208) To initiate the precipitation of the colloids, an excess (100 mL) of absolute ethanol was added slowly with vigorous shaking. The solution was allowed to stand for 5 h at room temperature to complete the precipitation.

(209) The slightly colored supernatant solution was decanted, and the precipitate was dried under reduced pressure. A gray-black powder (2.1 g, 88% yield based on palladium) containing 79 wt % of palladium was isolated. The powder was readily re-suspended in toluene.

(210) 9-2. Grafting of Polyacrylic Acid Film on Poly-Ethylene and Poly-Propylene Plastic

(211) The grafting was performed as indicated in example IV-1. Copolymeric films derived from AA or HEMA and from an in-situ synthetized diazonium salt have been grafted on plastic supports (poly-ethylene and poly-propylene). Films derived from diazonium alone have also been synthetized. Such films have been obtained according to the protocols depicted above.

(212) 9-3 Incorporation of Colloïdal Paladium Pd/[C.sub.18H.sub.37].sub.4N.sup.+Br.sup.− in PAA Film and Metallization of this Film

(213) The incorporation of particles was performed by immersion of the coated poly-ethylene and poly-propylene supports in the toluene solution containing Pd/[C.sub.18H.sub.37]4N.sup.+Br.sup.− for 30 seconds, the support being then rinsed with toluene and dried. Metallization has been performed as indicated in Example IV-8.