Electrochemical co-deposition of sol-gel films

Abstract

A method for the co-deposition of sol-gel and one or more additives selected from a great variety of agents including monomers, oligomers, polymers, metals and others is provided. The method affords continuous films of high stability and precision. Also provided is a surface coated with a film of sol-gel and at least one additive electrodeposited according to the presently described methods.

1 - 53 . (canceled) 
   
   
       54 . A method for co-depositing on a conductive surface a film of sol-gel and at least one additive, the method comprising inducing an electrochemical reaction on the conductive surface in the presence of a composite of at least one sol-gel precursor and at least one additive, thereby obtaining a conductive surface coated with a film, the at least one additive being in the film in an amount greater than 1 ppm. 
   
   
       55 . The method according to  claim 54 , comprising:
 (i) providing a conductive surface;   (ii) providing a composite of at least one sol-gel precursor and at least one additive in a solution;   (iii) contacting the surface with the solution comprising the composite; and   (iv) applying a voltage to the surface in contact with the composite,   
     thereby inducing formation of a sol-gel film on the surface. 
   
   
       56 . The method according to  claim 54 , comprising:
 (i) providing a conductive surface;   (ii) providing a composite of at least one sol-gel precursor and at least one additive in a solution;   (iii) immersing said surface in a solution comprising said composite, alcohol, water and at least one inert salt;   (iv) applying a voltage to said surface being immersed in the solution,   
     thereby inducing formation of a sol-gel film on said surface. 
   
   
       57 . The method according to  claim 54 , wherein the at least one sol-gel precursor is at least one monomer capable of undergoing electrochemical polymerization. 
   
   
       58 . The method according to  claim 57 , wherein the monomer is selected from the group consisting of a metal alkoxide monomer, a transition metal alkoxide monomer, a silicon alkoxide monomer, a metal ester monomer, a transition metal ester monomer, a silicon ester monomer, a monomer of the formula (RO) n M(R′) 4-n , a partially hydrolyzed and/or partially condensed polymer of each of said monomers, and mixtures thereof, wherein in the formula (RO) n M(R′) 4-n :
 M is selected from a silicon atom, a metallic or semimetallic element,   R is an organic moiety selected from C 1 -C 3 -alkyl,   R′ is an organic moiety selected from C 1 -C 10 -alkyl, C 2 -C 8 -alkenyl, C 2 -C 8 -alkynyl, C 6 -C 10 -aryl and C 4 -C 10 -heteroaryl, optionally substituted by at least one group selected from C 1 -C 8 -alkyl, C 2 -C 8 -alkenyl, C 2 -C 8 -alkynyl, C 6 -C 10 -aryl, C 4 -C 10 -heteroaryl, halide, amine (primary, secondary, tertiary or quaternary), hydroxyl, thiol, and nitro, and   n is an integer from 1 to 4.   
   
   
       59 . The method according to  claim 58 , wherein the monomers are selected from the group consisting of metal alkoxide monomers and silicon alkoxide monomers. 
   
   
       60 . The method according to  claim 59 , wherein the silicon alkoxide monomer is of the formula (RO) n Si(R′) 4-n , wherein
 R is an organic moiety selected from C 1 -C 3 -alkyl,   R′ is an organic moiety selected from C 1 -C 10 -alkyl or C 6 -C 12 -aryl, optionally substituted by at least one amine or thiol group, and   n is an integer from 1 to 4,   or a partially hydrolyzed and a partially condensed polymer thereof, or a mixture thereof.   
   
   
       61 . The method according to  claim 58 , wherein M is a metal atom or a transition metal atom selected from the group consisting of silicon, zirconium, aluminum, titanium, iron, tungsten, vanadium and mixtures thereof. 
   
   
       62 . The method according to  claim 54 , wherein the at least one additive is inert to the sol-gel polymerization process. 
   
   
       63 . The method according to  claim 62 , wherein the at least one additive is capable of undergoing reduction and/or polymerization under the electrochemical conditions employed. 
   
   
       64 . The method according to  claim 62 , wherein said at least one additive is selected from the group consisting of reinforcing elements, metals, metal salts, fillers, polymers, monomers, prepolymers, nanoparticles, encapsulated materials, and composite matrix binders. 
   
   
       65 . The method according to  claim 64 , wherein said at least one additive is in the form of a plurality of micro- or nanoparticles. 
   
   
       66 . The method according to  claim 54 , comprising:
 (i) providing a conductive surface;   (ii) immersing said surface in a solution comprising sol-gel precursors, at least one alcohol, water and at least one inert salt;   (iii) inducing an electrochemical reaction on the conductive surface by applying voltage to the surface being immersed the solution; and   (iv) treating the solution with at least one metal salt;   
     thereby inducing the formation of a hybrid film of sol-gel and metal on the surface. 
   
   
       67 . The method according to  claim 66 , wherein the surface is a surface of a medical implant selected from the group consisting of a stent, an artificial heart valve, a cerebrospinal fluid shunt, a pacemaker electrode, an axius coronary shunt, an endocardial lead, an orthopedic device, and a vessel occlusion device. 
   
   
       68 . A surface coated with a film of sol-gel and at least one additive electrodeposited according to the method of  claim 54 . 
   
   
       69 . The method according to  claim 58 , wherein R is an unsubstituted organic moiety selected from C 1 -C 3 -alkyl.