PROCESS FOR INCORPORATING METAL NANOPARTICLES IN A POLYMERIC ARTICLE AND ARTICLES MADE THEREWITH
A process of incorporating metal in the form of nanoparticles into the surface layer of a polymeric article and the resultant articles are disclosed. The process includes bringing at least a part of the surface of said article in contact with a solvent mixture that contains (a) water, (b) a carrier conforming to R 1 —[—O—(CH 2 ) n ] m OR 2 where R 1 and R 2 independently one from the other denote a radical selected from the group consisting of linear and branched C 1-8 alkyl, benzyl, benzoyl, phenyl and H, n is 2 or 3, and m is 1-35, (c) a metal precursor, and optionally (d) a leveling agent, for a time sufficient to enable infusion of at least some of said metal precursor into said article to obtain an article having a treated surface layer; and treating the surface layer with a reducing agent to produce metal in the form of nanoparticles. The inventive articles prepared by the inventive process exhibit advantageous electrical and/or optical properties.
1 . A process of incorporating metal in the form of nanoparticles in a polymeric article comprising:
(a) applying to at least a portion of the surface of said article a solvent mixture containing
(i) a metal precursor,
(ii) water,
(iii) at least one carrier conforming structurally to
R 1 —[—O—(CH 2 ) n ] m OR 2
where R 1 and R 2 independently one from the other denote a radical selected from the group consisting of linear and branched C 1-18 alkyl, benzyl, benzoyl, phenyl and H, n is 2 or 3, and m is 1-35,
and optionally
(iv) a diol selected from the group consisting of linear and branched C 2-20 -aliphatic diols, poly(C 2-4 -alkylene glycol), C 5-8 -cycloaliphatic diols, monocyclic aromatic diols and aromatic dihydroxy compounds to obtain a treated article, the applying being for a time and at temperature sufficient to infuse of at least some of said metal precursor into said article to obtain an article having a treated surface layer; and
(b) treating at least a portion of said treated surface layer with a reducing agent solution under conditions calculated to reduce the metal precursor to yield metal in the form of nanoparticles.
2 . The process of claim 1 , wherein said polymeric article contains at least one member selected from the group consisting of polyurethane, polymethylmethacrylate, polyester, polyamide, polystyrene, polyetherimide, and acrylonitrile-butadiene-styrene (“ABS”).
3 . The process of claim 1 , where the reducing agent is a substance capable of donating electrons to said precursor, and reduce it to the corresponding metal.
4 . The process of claim 3 wherein said substance is at least one member selected from the group consisting of citrate, ammonium compound, hydrazine, amine, hypophosphite, borohydride, hydrogen, carbon monoxide, formaldehyde, formate, acetate, oxalate, sulfanilate and alcohol.
5 . The process of claim 3 wherein said substance is at least one member selected from the group consisting of triethylamine (“TEA”), ammonium citrate, potassium citrate and sodium citrate.
6 . The process of claim 1 wherein the reducing agent conforms to
N R 1 , R 2 , and R 3 , (i)
where R 1 , R 2 and R 3 are independently one of the others selected from alkyl, benzyl, benzoyl, phenyl and H; or to
N + R 1 , R 2 , R 3 , R 4 X − (ii)
where R 1 , R 2 , R 3 and R 4 are independently selected from alkyl, benzyl, benzoyl, phenyl and H and X − is a nitrate, sulfate, hydroxyl, halide or other suitable anions.
7 . The process of claim 1 wherein said precursor is at least one moderately water soluble metal compound selected from the group consisting of oxides, hydroxyls, nitrides, nitrates, carbides, carbonates, bicarbonates, sulfides, sulfites, sulfates, iodates, chromates, dichromates, chlorites, chlorates, bromates, perchlorates, perbormates, periodates, phosphites, phosphates, arsenites, arsenates, acetates, halides, and complex anions.
8 . The process of claim 7 wherein the precursor is at least one metal salt.
9 . The process of claim 1 wherein said metal is at least one member selected from the group consisting of silver and gold.
10 . The process of claim 1 wherein said metal precursor is a member selected from the group consisting of AuX, AuX 3 where X denotes bromine, chlorine or iodine, and AuX 4 − Y + , where X denotes bromine, chlorine or iodine, and Y denotes Na + , K + or H + .
11 . The process of claim 5 wherein said precursor is a member selected from the group consisting of AuBr 3 , AuBr 4 − K + , AuBr 4 − Na + , AuBr 4 − H + , AuCl, AuCl 3 , AuCl 4 − K + , AuCl 4 − Na + , AuCl 4 − H + , AuI and AuI 3 .
12 . The process of claim 1 wherein said metal precursor is a member selected from the group consisting of
AgX
where X denotes fluorine, chlorine, bromine, iodine, BF 4 − , BrO 3 − , ClO 3 − , ClO 4 − , PF 6 , SBF 6 − , IO 3 − , MnO 4 − , VO 3 − , or ReO 4 − ,
AgX 2
where X denotes fluorine,
Ag 2 X
where X denotes O − 2 , CrO 4 − 2 , SO 3 − 2 , or SO 4 − 2 ,
Ag 3 X
where X denotes AsO 4 − 3 or PO 4 − 3 and
Ag 8 X
where X denotes W 4 O 16 − 8 .
13 . The process of claim 1 wherein said precursor is a member selected from the group consisting of AgBF 4 , AgBr, AgBrO 3 , AgCl, AgClO 3 , AgClO 4 , AgF, AgF 2 , AgPF 6 , AgSbF 6 , AgIO 3 , AgMnO 4 , AgNO 2 , AgNO 3 , Ag 2 O, AgVO 3 , AgReO 4 , Ag 2 CrO 4 , Ag 2 SO 3 , Ag 2 SO 4 , Ag 3 AsO 4 , Ag 3 PO 4 , and Ag 8 W 4 O 16 .
14 . The process of claim 1 wherein said applying is by immersion, spraying or flow coating.
15 . The process of claim 1 wherein said reducing agent solution comprise triethylamine (“TEA”).
16 . The article prepared by the process of claim 1 characterized in that it exhibits at least one property selected from electrical and optical that differs from the corresponding property of the pre-process article.
17 . A polymeric article comprising a polymeric material, said polymeric article having a surface layer comprising infused metal nanoparticles, wherein said nanoparticles comprise the reduction product of infused metal precursors with a reducing agent solution.
18 . The polymeric article of claim 17 , wherein said polymeric material is selected from the group consisting of polyurethane, polymethylmethacrylate, polyester, polyamide, polystyrene, polyetherimide, and acrylonitrile-butadiene-styrene (“ABS”).
19 . The polymeric article of claim 17 wherein the reducing agent is a substance capable of donating electrons to said precursor, and reduce it to the corresponding metal.
20 . The polymeric article of claim 19 wherein said substance is at least one member selected from the group consisting of citrate, ammonium compound, hydrazine, amine, hypophosphite, borohydride, hydrogen, carbon monoxide, formaldehyde, formate, acetate, oxalate, sulfanilate and alcohol.
21 . The polymeric article of claim 19 wherein said substance is at least one member selected from the group consisting of triethylamine (“TEA”), ammonium citrate, potassium citrate and sodium citrate.
22 . The polymeric article of claim 17 wherein the reducing agent conforms to
N + R 1 , R 2 , and R 3 , (i)
where R 1 , R 2 and R 3 are independently one of the others selected from alkyl, benzyl, benzoyl, phenyl and H; or to
N + R 1 , R 2 , R 3 , R 4 X − (ii)
where R 1 , R 2 , R 3 and R 4 are independently selected from alkyl, benzyl, benzoyl, phenyl and H and X − is a nitrate, sulfate, hydroxyl, halide or other suitable anions.
23 . The polymeric article of claim 17 wherein said precursor is at least one moderately water soluble metal compound selected from the group consisting of oxides, hydroxyls, nitrides, nitrates, carbides, carbonates, bicarbonates, sulfides, sulfites, sulfates, iodates, chromates, dichromates, chlorites, chlorates, bromates, perchlorates, perbormates, periodates, phosphites, phosphates, arsenites, arsenates, acetates, halides, and complex anions.
24 . The polymeric article of claim 17 , wherein the precursor is at least one metal salt.
25 . The polymeric article of claim 17 , wherein said metal is at least one member selected from the group consisting of silver and gold.
26 . The polymeric article of claim 17 , wherein said metal precursor is a member selected from the group consisting of AuX, AuX 3 where X denotes bromine, chlorine or iodine, and AuX 4 − Y + , where X denotes bromine, chlorine or iodine, and Y denotes Na + , K + or H + .
27 . The polymeric article of claim 17 wherein said precursor is a member selected from the group consisting of AuBr 3 , AuBr 4 − K + , AuBr 4 − Na + , AuBr 4 − H + , AuCl, AuCl 3 , AuCl 4 − K + , AuCl 4 − Na + , AuCl 4 − H + , AuI and AuI 3 .
28 . The polymeric article of claim 17 wherein said metal precursor is a member selected from the group consisting of
AgX
where X denotes fluorine, chlorine, bromine, iodine, BF 4 − , BrO 3 − , ClO 3 − , ClO 4 − , PF 6 , SBF 6 − , IO 3 − , MnO 4 − , VO 3 − , ReO 4 − ,
AgX 2
where X denotes fluorine,
Ag 2 X
where X denotes O − 2 , CrO 4 − 2 , SO 3 − 2 , or SO 4 − 2 ,
Ag 3 X
where X denotes AsO 4 − 3 or PO 4 − 3 and
Ag 8 X
where X denotes W 4 O 16 − 8 .
29 . The polymeric article of claim 17 wherein said precursor is a member selected from the group consisting of AgBF 4 , AgBr, AgBrO 3 , AgCl, AgClO 3 , AgClO 4 , AgF, AgF 2 , AgPF 6 , AgSbF 6 , AgIO 3 , AgMnO 4 , AgNO 2 , AgNO 3 , Ag 2 O, AgVO 3 , AgReO 4 , Ag 2 CrO 4 , Ag 2 SO 3 , Ag 2 SO 4 , Ag 3 AsO 4 , Ag 3 PO 4 , and Ag 8 W 4 O 16 .
30 . The polymeric article of claim 17 , wherein said reducing agent solution comprises triethylamine (“TEA”).
31 . The composition of claim 17 , wherein said nanoparticles have at least one dimension of up to about 100 nanometers.
32 . The polymeric article of claim 17 , wherein said nanoparticles have at least one dimension of Up to about 50 nanometers.
33 . The polymeric article of claim 17 , wherein said nanoparticles have at least one dimension of up to about 10 nanometers.
34 . The polymeric article of claim 17 , wherein said surface layer has a depth of no more than about 50 microns.
35 . The polymeric article of claim 17 , wherein said surface layer has a depth of about 25 to about 30 microns.