ES2224898A1 - Method of modifying the surfaces of metals, semiconductors and carbon, surface-modified products thus obtained and applications thereof - Google Patents

Abstract

The modification of metal, semiconductor and carbon surfaces comprises application of a solution in aprotic medium of a primary amine of formula RNH2, to give a 10 Angstrom to 1 millimeter coating. Also claimed is a process using the modified products. CLAIMED PROCESS - The process is employed to protect, lubricate and bond metal surfaces, e.g. relative to biomaterials.

Description

Procedure for surface modification of metals, semiconductors and carbon, modified products superficially thus obtained and its applications.

Technical Field of the Invention

The present invention fits within the technical field of metal surface modification, of semiconductors and carbon to contribute to these materials physical and chemical surface properties other than originals and / or to functionalize them.

More specifically, the present invention provides a new procedure for the modification of surfaces of certain metals, semiconductors and carbon with primary amines, the modified products resulting from said procedure and the multiple applications thereof in Different industrial sectors.

State of the art prior to the invention

The modification of metal surfaces, of semiconductors and / or carbon to impart properties different physiochemicals or to functionalize them has great industrial interest due to its various applications in different sectors.

Proof of this is the existence of multiple patents and related scientific papers in terms general with this technical field; for example, worth as illustration, the following patents located by the applicant:

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European Patent No. Pub. 0672467 (BASF AKT.) By "Procedure for modification of metal surfaces ",

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European Patent No. Pub. 0951581 (HENKEL CORP.) By "Coated Metal Surfaces of phenolic formaldehyde resin and procedure related",

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European Patent No. Pub. 0770429 (ELF ATOCHEM S.A.) by "Metallic surfaces polymer coated ",

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European Patent No. Pub. 0858579 (UNIVERSITY OF SURREY) by "Modification of metal surfaces ", and, specifying the modification of metal and carbon surfaces with amines, the background more relevant that the applicant considers appropriate to mention and comment more widely are the following:

(one)

(a) Barbier , B .; Pinson , J .; Désarmot , G .; Sánchez , M.; J. Electrochem. Soc . 1990 , 137, 175;

(b)

Deinhammer , RS; Ho, M .; Anderegg , JW; Porter , MD; Langmuir , 1994 , 10, 1306;

(C)

Downard , AJ; Electroanalysis , 2000 , 12, 1085.

(2)

Adenier , A .; Chehimi , MM; Gallardo , I .; Pinson , J .; Vilá , N .; Langmuir , 2004 , 20, 8243

(3)

Buttry , DA; Peng , JCM; Donnet , JB .; Rebouillat , S. Carbon 1999 , 37, 1929.

(4)

(a) Bouchet , J .; Roche , A.; The Journal of Adhesion 2002 , 78, 799-830.

(The numerical references used previously to identify the different articles, are the same that will be used in the following scientific explanation of current state of the art)

The modification of carbon surfaces with primary and secondary aliphatic amines through training of covalent bonds has been possible through the use of techniques electrochemical 1a-b The process is schematized as follows:

one

The formation of covalent bonds with carbon surfaces through the amino group has been shown observing the electrochemical signal of electroactive groups, such as nitro groups, present in the molecule used for 1a-c modification Others have also been used electroactive groups such as anthracene or anthraquinone with the same goal. The coating has also been demonstrated by surface characterization techniques such as XPS. The surface concentration of amino groups is lower in the case of secondary aliphatic amines with respect to alkyl amines primary while no coating has been observed for the case of tertiary amines. Covalent bond formation to through the N of the amino group was initially attributed to the cation 1b radical formed after the oxidation stage but a most recent study indicates that the species responsible for the modification is the radical obtained after deprotonation of the radical cation 2.

2

Later, it was demonstrated that the modification of carbon surfaces could be achieved without using of electrochemical techniques and the existence of Michael-like reactions between the amino groups that acted as nucleophiles and the C sp 2 present on the surface as shows in the following scheme:

3

(z electro electroactive groups present in the carbon fibers such as carbonyls or carboxyls)

A recent publication 4 shows a study on the mechanisms of interface formation epoxy / metal. As a result of this study, the authors have shown that when a prepolymer system is applied epoxy / diamine to metal substrates, interfaces are created between the part of the coating and the metal surface. The properties Chemical, physical and mechanical interface formed depend both the substrate and the nature of the diamine used As hardener. The use of an appropriate curing cycle for the prepolymers allows to achieve both the maximum conversion of the polymer as the complete formation of the interface. When apply the DGEBA monomer (diglycidyl ether of bisphenol A) to the metal surfaces, or when monomers of pure diamine to gold-coated substrates, no observed chemical reaction. On the contrary, when monomers of pure diamine on titanium or aluminum metal surfaces, chemical reaction takes place. After the portion of the amine chemical on oxidized or hydroxylated metal surfaces, it observe a partial dissolution of the oxide and / or surface hydroxide on the metal substrate according to the basic behavior of the diamine monomers [3-aminomethyl-3,5,5-trimethylcyclohexylamine and poly (oxopropylenediamine)]. So, metal ions diffuse into the liquid monomer mixture (epoxy / diamine) and react by coordination with the amino groups of the monomers diamine to form organometallic complexes (or chelates). It has been proven that the general properties of the coatings, including those of the interface, depend on the duration of time of contact between the metal surfaces and the liquid mixture of prepolymers In addition, the results obtained indicate that the Epoxy / metal interface significantly affects adhesion initial coating practice. However, the formation of organo-metal complexes greatly improves the practical adhesion after aging, and complexes created act as corrosion inhibitors.

Therefore, from the previous exhibition it is observed that the authors show how Ti and Al are capable of experience a spontaneous reaction with diamines 3-aminomethyl-3,5,5-trimethylcyclohexylamine and poly (oxopropylenediamine) in epoxy / diamine systems, in that diamine is used as a curing agent while forming the interface

While theoretical studies carried out by these authors to establish the mechanisms of formation of said interface and its role in the adhesion of the polymeric coating to the metal surface, have revealed the possibility of that there is such a spontaneous reaction, what is clear is that said method cannot be considered by experts a method general treatment of metal surfaces with amines, at the level industrial. In fact, the diamines used are products complex, very expensive, which in this publication have application as hardeners in the polymerization process, but they lack totally of industrial interest within the technical context that You are dealing with this description.

On the other hand, it is not possible to carry out the modification of metal surfaces such as platinum, gold, iron, copper or zinc, with primary or secondary alkylamines by electrochemical techniques, since the oxidation of the metal itself at potential values lower than of oxidation of said amines. Since platinum and gold are metals with higher oxidation potentials, allow work with wider margins and in certain cases they can be treated superficially with secondary amines via electrochemistry.

Given the existing industrial interest by the modification of metal surfaces due to its multiple applications in various sectors, the applicant has directed his research efforts in the search for a process for such type of modification within the group known as "methods of spontaneous oxidation "that can optimize existing or apply to substrates that have not been able to date Modify with certain amines. Studies have been culminated with the process of the present invention and the products obtained by him, which are described with everything detail in the following sections of this report descriptive

Detailed description of the invention

The present invention, as described in its statement refers to a procedure for the modification of metal, semiconductor and carbon surfaces, to superficially modified products thus obtained and their Applications.

The process object of the present invention is aimed at the modification of certain surfaces of metals, semiconductor materials and carbon with amines primary to provide physical and chemical properties different from those originally owned and / or for functionalize them with a view to certain industrial applications of interest.

More specifically, the present invention provides a procedure to modify metal surfaces, of semiconductors and carbon, characterized in that it comprises contacting said metal, semiconductor or surface of carbon with a solution of a primary amine of formula (I):

(1) RNH2

where R is selected from an alkyl group C3-C6 straight or branched chain, a group C3-C6 cycloalkyl, and an aryl group, preferably a benzyl group, said groups being able to be without replace or substitute with one or more substituents that do not affect adversely to the reaction between the amine and the surface to Modify.

The process of the present invention is applies to both carbon surfaces and metal surfaces selected from the group consisting of gold, platinum, copper, iron, zinc, nickel, cobalt, aluminum and titanium mainly, as well as also to steel and certain titanium alloys and chrome-cobalt. It also applies to surfaces of semiconductor materials such as Si (100), Si (111) and silicon hydrogenated

As for the amine, the procedure of the The present invention can be carried out with any amine encompassed within the scope of formula (I). Refering to optional presence of substituent groups in any of the R groups defined above, there is no limitation within of the scope of the present invention, provided that said groups do not adversely affect the main reaction intended by the procedure of the present invention, that is, the reaction between the primary amino group of said amine of formula (I) and said surface.

According to the experiments carried out by the present inventors, it has been established that said reaction leads to the formation of stable covalent bonds between said metal, semiconductor and / or carbon surface and the primary amino groups of said amine of formula (I). As well,  said substituents can be chosen within the broad group of conventional substituents in the field well known to those experts, as long as it does not adversely affect the formation of said covalent bonds. Among such substituents, they can Mention groups methyl, ethyl, nitro, halogen, vinyl, hydroxyl, carboxyl, etc.

However, the procedure herein invention is especially suitable for the modification of metal, semiconductor and carbon surfaces with amines easily affordable and inexpensive commercials, unless look for a very specific application for which an amine is required of very special characteristics (like some of those will indicate later). Thus, for example, they can be cited as commercial amines especially useful for carrying out the Procedure of the present invention, the following: propylamine, butylamine, pentylamine and hexylamine in their different linear or branched chain forms, cyclohexylamine, benzylamine, 4-nitrobenzylamine and 3-nitrobenzylamine.

As for the reaction conditions, in the In case of protic solvents, it is necessary that the molar ratio of the solution of the amine is greater than 1: 1 of the amine with respect to to the acid, so that there is deprotonated amine in said solution. Thus, it is preferred to use an amine solution in a aprotic solvent in which the surface to be treated is submerged. It is also preferred that said reaction is carried out in inert atmosphere On the other hand, the concentration conditions and temperature are not especially relevant for the reaction, being determined normally in each case, although it is true that there is a maximum time beyond which the surface is saturated and It no longer admits more coating amine. However, in General terms could be verified, that the following conditions are especially suitable for carrying out the Procedure of the invention in most cases:

- concentration of amine in the solvent aprotic: 5-20 mM,

- treatment time: 30-180 minutes

- treatment temperature: 5-40 ° C approximately, used as solvent preferred aprotic acetonitrile (ACN) and as an inert atmosphere preferred an atmosphere based on N2 or Ar.

The nature of the coating layers of surfaces with the amine produced by the procedure of the present invention have been studied and characterized mainly by two techniques, namely:

-

cyclic voltammetry: applicable in the case of amines with electroactive groups, by example nitrobenzylamines;

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IRRAS ("Infrared Reflexion Absortion Spectroscopy "): applicable in the case of amines without electroactive groups.

Through these techniques it has been proven in general that the coating is constituted by a monolayer of the amine used in the process, which is deposited on the surface forming a covalent bond capable of resisting a wash after 8-12 minutes (preferably 10 minutes) in an ultrasonic bath to remove from the surface molecules adsorbed by weaker interactions with the atoms of the metal surface. That monolayer as well treated has a final thickness between 10-200 Angstroms.

The second object of the present invention corresponds to superficially modified products obtained by this procedure.

In accordance with the provisions in the paragraphs precedents the product resulting from the process of the present invention is a metal, semiconductor or carbon surface superficially modified with an amine coating RNH_ {2} where R has the meaning given above for the Formula 1).

Said coating of said modified product superficially it is constituted by a monolayer of said amine covalently bonded to said metal surface, of semiconductor or carbon with a thickness between 10-200 Angstroms.

Said metal of said modified product superficially it is selected from the group formed by gold, Platinum, copper, iron, zinc, nickel, cobalt, aluminum and titanium mainly, as well as steel and certain alloys of titanium and chrome-cobalt. Said material semiconductor of said surface modified product is selected from the group consisting of Si (100), Si (111) and silicon hydrogenated The modification of carbon surfaces, of semiconductors and, above all, metal surfaces have multiple industrial applications as discussed in preceding paragraphs.

Hence the industrial interest that follows from the present invention and that will be obvious to any expert in the technique in view of the following applications indicated at merely illustrative title (from the teachings of the present invention, experts may come up with other many applications within the scope of protection of the same):

one.

Protection of metal surfaces against corrosion either by the layers obtained directly or by polymer layers obtained at from substituents capable of giving reactions of polymerization, for example:

4

2.

Lubrication metal surfaces putting on the surface molecules that improve their friction properties (example: molecules perfluorinated) or molecules that have a great affinity for lubricants (for example long alkyl chains, which have large affinity for oils and mineral fats).

3.

Two adhesion metal surfaces, previously modified by the process described, each other. This requires that the modification be carried out with amines that carry reactive groups that can react subsequently between them to join the two surfaces modified. Thus, for example, an outline is shown below. in which the R and R 'groups are seen that are susceptible to react with each other to achieve the union of the two surfaces previously modified metal:

5

Four.

Improvement metal surfaces (titanium, titanium alloys, steel stainless, chrome-cobalt alloys) intended for join biomaterials for applications in the medical field and related, for example:

to. Use of polyethylene glycol chains replacing the aromatic core, which worsens the adhesion of proteins

b. Use of proteins such as Protein Morphogenic bone susceptible to stimulate bone growth.

C. Antibiotic use replacing the group aromatic to form bactericidal surfaces.

On the occasion of these last examples of applications, remember the case of amine substituents of formula (I), when it was commented that in special cases they could substituents of a very specific nature are required if any desired final application so demanded.

Brief description of the figures

- Figure 1: Cyclic Voltammetry Records on carbon electrodes corresponding to the conditions described in the Example, below

- Figure 2: Cyclic Voltammetry Records on gold electrodes corresponding to the conditions described in the Example, below.

- Figure 3: Cyclic Voltammetry Records on platinum electrodes corresponding to the conditions described in the Example, below.

- Figure 4: Cyclic Voltammetry Records on copper electrodes corresponding to the conditions described in the Example, below.

- Figure 5: Cyclic Voltammetry Records on iron electrodes corresponding to the conditions described in the Example, below.

- Figures 6A-6C: IRRAS spectra of hexylamine (Fig. 6A), gold modified with hexylamine (Fig 6B), Hexyl amine modified platinum (6C), according to the conditions described in the Example, below.

- Figure 7A-7E: IRRAS spectra cyclohexylamine (Fig. 7A), gold modified with cyclohexylamine (Fig 7B), cyclohexylamine modified platinum (7C), aluminum modified with cyclohexylamine (7D), copper modified with cyclohexylamine (7E) according to the conditions described in the Example, later.

- Figure 8A-8E: IRRAS spectra of benzylhexylamine (Fig. 8A), gold modified with benzylhexylamine (Fig 8B), benzylhexylamine modified platinum (8C), aluminum modified with benzylhexylamine (8D), copper modified with benzylhexylamine (8E) according to the conditions described in the Example, later.

Embodiments of the invention

The present invention is further explained. by the following Example, which has merely character illustrative and non-limiting of the present invention, whose scope should be considered delimited exclusively by the Note Claims attached.

Example Modification of metal surfaces with primary amines and study of the coatings obtained Modification of metal surfaces

The modification method was carried out spontaneously, according to the present invention, on different types of metals with different amines and in different terms.

The modification of each metal surface is performed by immersing said surface in a solution 15-20 mM of the corresponding amine in acetonitrile (ACN), under an inert atmosphere (N2 or Ar), during variable time periods dependent on said concentration. Prior to said modification treatment, the surface metallic must have been polished and cleaned with ethanol and acetone, successively, in an ultrasonic bath.

The results obtained in the different Modification processes carried out are summarized in Tables 1 to 6 which are included later, whose headings are set the specific conditions in which each process has been carried out.

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TABLE 1 Surface concentration of nitrobenzyl groups in immersion time function in a 9.11 mM solution of 4-nitrobenzylamine in ACN

24

TABLE 2 Surface concentration of nitrobenzyl groups in immersion time function in an 18.22 mM solution of 4-nitrobenzylamine in ACN

25

TABLE 3 Surface concentration of nitrobenzyl groups as a function of immersion time in a 8.75 mM solution of 3-nitrobenzylamine in ACN

26

TABLE 4 Surface concentration of nitrobenzyl groups as a function of immersion time in a 16.31 mM solution of 3-nitrobenzylamine in ACN

27

TABLE 5 Surface concentration of nitrobenzyl groups as a function of immersion time in a 10.21 mM solution of 4-nitrophenylethylamine in ACN

28

TABLE 6 Surface concentration of nitrobenzyl groups as a function of immersion time in a 10.21 mM solution of 4-nitrophenylethylamine in ACN

29

In general terms, it can be seen that the modification process is faster at higher concentrations of amine, obtaining results of the same order in the middle of time if the concentration is doubled.

Quantification of coatings

In the event that the modification of the surface has been made with 4-nitrobenzylamine (amine with an electroactive group), the quantification of coatings obtained is carried out by voltammetry Cyclic This quantification is carried out from the integration of the area of the voltagram corresponding to the group reduction nitro The records corresponding to the Figures are thus obtained 1 to 5, which have been carried out under the following conditions Experimental:

- Cyclic Voltammetry on C electrode (d = 3 mm) at 0.1 V s -1 in a) a 9.11 mM solution of 4-nitrobenzylamine in ACN + 0.1 M NBu 4 BF 4,  b) in a solution of ACN + NBu 4 BF 4 0.1 M with the unmodified electrode and c) in an ACN + solution NBu 4 BF 4 0.1 M after modifying the electrode by immersion for 120 min in the 9.11 mM solution of 4-nitrobenzylamine. The corresponding records are shown in Figure 1 (voltagrams a, b and c, respectively).

- Cyclic Voltammetry on Au electrode (d = 1 mm) at 0.1 V s -1 in a) an 18.2 mM solution of 4-nitrobenzylamine in ACN + NBu 4 BF 4 0.1 M, b) in a solution of ACN + NBu 4 BF 4 0.1 M after modify the electrode by immersion for 1 hour in the 18.2 mM solution of 4-nitrobenzylamine. The corresponding records are shown in Figure 2 (voltagrams upper and lower respectively).

- Cyclic Voltammetry on Pt electrode (d = 1 mm) at 0.1 V s -1 in a) a 9.11 mM solution of 4-nitrobenzylamine in ACN + NBu 4 BF 4 0.1 M, b) in a solution of ACN + NBu 4 BF 4 0.1 M after modify the electrode by immersion for 2 hours in the 9.11 mM solution of 4-nitrobenzylamine. The corresponding records are shown in Figure 3 (voltagrams upper and lower respectively).

- Cyclic Voltammetry on Cu electrode (d = 1 mm) in a solution of ACN + NBu 4 BF 4 0.1 M with the electrode modified by immersion for 2 hours in a 9.11 mM solution of 4-nitrobenzylamine in ACN. He corresponding record is shown in Figure 4.

- Cyclic Voltammetry on Fe electrode (d = 1 mm) in a solution of ACN + NBu 4 BF 4 0.1 M with the electrode modified by immersion for 2 hours in a 9.11 mM solution of 4-nitrobenzylamine in ACN. He corresponding record is shown in Figure 5.

In the event that the modification of the surface has been made with amines without electroactive groups (hexylamine, cyclohexylamine, benzylamine), quantification of The coatings obtained are carried out by IRRAS. Be thus obtain the spectra corresponding to surfaces modified with said amines and subsequently cleaned in a bath ultrasound for 5 minutes in ethanol and 5 minutes acetone. Such spectra are illustrated in Figures 6 to 8.

As can be seen in Figure 6A, it is shown the hexylamine spectrum with the typical vibration bands in the IR of the NH2 group in the region of 3000-3100 cm -1. For their part, Figures 6B and 6C show the Gold and platinum surface spectra modified with hexylamine respectively, in which it can already be seen clearly a single vibration band around 3200 cm -1 corresponding to the group -NH-.

\hbox{N-H}

entre 3000 y 3500 cm^{-1}.Similarly, Figure 7A shows the spectrum of cyclohexylamine and Figures 7B, 7C, 7D, 7E show the spectra of gold, platinum, aluminum and copper surfaces modified with cyclohexylamine respectively, clearly showing the variation of the bands in the zone of vibration of the links

 \ hbox {NH} 

between 3000 and 3500 cm -1.

For its part, Figure 8A shows the spectrum of benzylamine and in Figures 8B, 8C, 8D and 8E are show the surface spectra of gold, platinum, aluminum and copper modified with benzylamine. As in the cases above, the variation offered by the appearance of the vibration bands corresponding to the links N-H of the amino groups.

Claims (50)

1. Method for the modification of metal, semiconductor and carbon surfaces, characterized in that it comprises contacting said metal, semiconductor or carbon surface with a solution of a primary amine of formula (I): (1) RNH2 where R is selected from an alkyl group C3-C6 straight or branched chain, a group C3-C6 cycloalkyl, and an aryl group, may be said groups unsubstituted or substituted with one or more substituents that do not adversely affect the reaction between the amine and the surface to Modify. 2. Method according to claim 1, characterized in that said metal surface is selected from the group consisting of a surface of gold, platinum, copper, iron, zinc, nickel, cobalt, aluminum and titanium, steel, titanium and chromium-cobalt alloys . 3. Method according to claim 1, characterized in that it is carried out on a carbon surface. 4. Method according to claim 2, characterized in that it is carried out on a gold surface. 5. Method according to claim 2, characterized in that it is carried out on a platinum surface. 6. Method according to claim 2, characterized in that it is carried out on a copper surface. 7. Method according to claim 2, characterized in that it is carried out on an iron surface. 8. Method according to claim 2, characterized in that it is carried out on a zinc surface. 9. Method according to claim 2, characterized in that it is carried out on an aluminum surface. 10. Method according to claim 2, characterized in that it is carried out on a titanium surface. 11. Method according to claim 2, characterized in that it is carried out on a steel surface. 12. Method according to claim 2, characterized in that it is carried out on a surface of titanium alloys. 13. Method according to claim 2, characterized in that it is carried out on a surface of chromium-cobalt alloys. 14. Method according to claim 2, characterized in that it is carried out on a nickel surface. 15. Method according to claim 2, characterized in that it is carried out on a cobalt surface. 16. Method according to claim 1, characterized in that it is carried out on a surface of semiconductor material. 17. Method according to claim 16, characterized in that it is carried out on a surface of Si (100). 18. Method according to claim 16, characterized in that it is carried out on a surface of Si (111). 19. Method according to claim 16, characterized in that it is carried out on a surface of hydrogenated silicon. 20. Method according to any of the preceding claims characterized in that it is carried out with an amine of formula (I) in which said radical R has no substituents. 21. Method according to claims 1 to 19, characterized in that it is carried out with an amine of formula (I) in which said radical R has one or more substituents that do not adversely affect the reaction between said metal surface and said amine. 22. Method according to claim 21, characterized in that it is carried out with an amine of formula (I) in which said radical R has one or more substituents selected from the group consisting of methyl, ethyl, nitro, halogen, vinyl, hydroxyl, carboxyl 23. Method according to claims 20 to 22 above, characterized in that said radical R is a straight or branched C3-C6 alkyl group. 24. Method according to any of claims 20 to 22, characterized in that said radical R is a C3-C6 cycloalkyl group. 25. Method according to any of claims 20 to 22, characterized in that said radical R is an aryl group. 26. Method according to claim 25, characterized in that said aryl group is benzyl. 27. Method according to claim 26, characterized in that it is carried out with an amine of formula (I) selected from the group consisting of benzylamine, 4-nitrobenzylamine and 3-nitrobenzylamine. 28. Method according to claim 23, characterized in that it is carried out with an amine of formula (I) selected from the group consisting of propylamine, butylamine, pentylamine and hexylamine in its different linear or branched chain forms. 29. Method according to claim 24, characterized in that it is carried out with an amine of formula (I) which is cyclohexylamine. 30. Method according to any of the preceding claims, characterized in that it is carried out in a protic solvent in a molar ratio greater than 1: 1 of the amine with respect to said solvent. 31. Method according to any of claims 1 to 30, characterized in that it is carried out in an aprotic solvent. 32. Method according to claim 31, characterized in that said aprotic solvent is acetonitrile. 33. Method according to any one of the preceding claims, characterized in that it is carried out in an inert atmosphere. 34. Method according to any of the preceding claims, characterized in that it is carried out using a concentration of 5-20 mM of said amine in the solution. 35. Method according to any of the preceding claims, characterized in that it is carried out by keeping said solution of said amine in contact with said surface for a period of 30-180 minutes. 36. Method according to any of the preceding claims, characterized in that it is carried out at a contact temperature between said solution of said amine and said surface of 5-40 ° C. 37. Method according to any of the preceding claims, characterized in that after the step of contacting said carbon, semiconductor or metal surface with said solution of said amine, the surface thus treated is subjected to a washing operation in a bath Ultrasound 38. Method according to any one of the preceding claims, characterized in that the modified surface obtained is provided with a coating consisting of a monolayer of said amine having a thickness between 10 Angstroms and 1 mm. 39. Product obtained by the process according to any of the preceding claims, characterized in that it is a surface metal, semiconductor or carbon surface modified with a coating of an amine of formula RNH2, where R has the meaning given above. for the formula (I). 40. Product according to claim 39, characterized in that said metal is selected from the group consisting of gold, platinum, copper, iron, zinc, nickel, cobalt, aluminum, titanium, steel and alloys of titanium and chromocobalt. 41. Product according to claim 39, characterized in that said semiconductor is selected from the group consisting of Si (100), Si (111) and hydrogenated silicons. 42. Product according to any of claims 39 to 41, characterized in that said amine is selected from the group consisting of propylamine, butylamine, pentylamine and hexylamine, in its different linear or branched chain forms, cyclohexylamine, benzylamine, 4-nitrobenzylamine and 3- nitrobenzylamine 43. Product according to any of claims 39 to 42, characterized in that said coating is constituted by a monolayer of said amine covalently bonded to said metal, semiconductor or carbon surface with a thickness between 10-200 Angstroms. 44. Use of the product according to the claims 39 to 43, for the protection of metal surfaces against corrosion. 45. Use of the product according to the claims 39 to 43, for the lubrication of metal surfaces. 46. Use of the product according to the claims 39 to 43, for the adhesion of two metal surfaces, previously modified, each other. 47. Use of the product according to the claims 39 to 43, as a previously modified metal surface, for binding to biomaterials in medical and related applications. 48. Use according to claim 47, characterized in that said biomaterial is polyethylene glycol. 49. Use according to claim 47, characterized in that said biomaterial is bone morphogenic protein. 50. Use according to claim 47, characterized in that said biomaterial is an antibiotic.