Combined plasma and gamma radiation polymerization method for modifying surfaces

• US 5,376,400 A
• Filed: 01/13/1993
• Issued: 12/27/1994
• Est. Priority Date: 10/24/1990
• Status: Expired due to Fees

• Current Assignee: University of Florida Research Foundation, Incorporated (State University System of Florida)
• Original Assignee: University of Florida Research Foundation, Incorporated (State University System of Florida)
• Inventors: Yahiaoui, Ali, Burns, James, Goldberg, Eugene P.
• Primary Examiner(s): Beck, Shrive
• Assistant Examiner(s): DUDASH, DIANA L
• Application Number:
  US08/003,682
• Time in Patent Office: 713 Days
• Field of Search: 427/2, 427/536, 427/535, 427/538, 427/539, 427/495, 427/496, 427/498, 427/501, 427/507, 427/322, 427/327, 427/299, 427/488
• US Class Current: 427/2.24
• CPC Class Codes: A61L 2400/18 Modification of implant surfaces in order to improve biocompatibility, cell growth, fixation of biomolecules, e.g. plasma treatment
• CPC Class Codes: A61L 27/34 Macromolecular materials
• CPC Class Codes: A61L 29/085 Macromolecular materials
• CPC Class Codes: B05D 1/60 Deposition of organic layers from vapour phase vapour phase deposition in general C23C14/00, C23C16/00
• CPC Class Codes: B05D 3/068 using ionising radiations (gamma, X, electrons)
• CPC Class Codes: B05D 3/142 Pretreatment
• CPC Class Codes: B05D 3/144 of polymeric substrates
• CPC Class Codes: C03C 17/32 with synthetic or natural resins C03C17/30 takes precedence
• CPC Class Codes: C03C 2218/31 Pre-treatment
• CPC Class Codes: C03C 23/0035 by gamma-rays
• CPC Class Codes: C03C 23/004 by electrons, protons or alpha-particles
• CPC Class Codes: C03C 23/006 by plasma or corona discharge
• CPC Class Codes: C04B 2111/00836 for medical or dental applications
• CPC Class Codes: C04B 35/00 Shaped ceramic products characterised by their composition porous ceramic products C04B38/00; ceramic articles characterised by particular shape, see the relevant classes, e.g. linings for casting ladles, tundishes, cups or the like B22D41/02; ceramic substrates for microelectronic semi-conductors H01L23/15; Ceramics compositions containing free metal bonded to carbides, diamond, oxides, borides, nitrides, silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides or sulfides other than as macroscopic reinforcing agents C22C; shaping of ceramics B28B; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products chemical preparation of powders of inorganic compounds C01; infiltration of sintered ceramic preforms with molten metal C04B41/51
• CPC Class Codes: C04B 41/0027 Ion-implantation, ion-irradiation or ion-injection
• CPC Class Codes: C04B 41/009 characterised by the material treated
• CPC Class Codes: C04B 41/455 the coating or impregnating process including a chemical conversion or reaction
• CPC Class Codes: C04B 41/48 Macromolecular compounds
• CPC Class Codes: C04B 41/83 Macromolecular compounds
• CPC Class Codes: C08J 7/123 Treatment by wave energy or particle radiation C08J7/18 takes precedence
• CPC Class Codes: C23C 26/00 : Coating not provided for in groups C23C2/00 - C23C24/00
• CPC Class Codes: C23C 8/36 : using ionised gases, e.g. ionitriding

Abstract

A method for modifying the surface of a material by:

a. exposing the surface to a glow discharge plasma to activate the surface;

b. exposing the surface to an ethylenically unsaturated monomer or mixture of monomers; and

c. irradiating the activated surface with gamma radiation or electron beam radiation in the presence of the ethylenically unsaturated monomer to form a graft polymerized coating thereon.

Claims

1. A method for modifying a surface of a hydrophobic material by a gamma-irradiation or electron beam irradiation induced polymerization thereon of one or a mixture of ethylenically unsaturated monomers so as to form a hydrophilic polymeric coating on said surface, the improvement comprising the steps of:

a) exposing said surface to a glow discharge plasma (GDP) having a power from about 1 to about 500 W and for a time sufficient to induce grafting sites on said surface for the surface graft polymerization of steps b and c;

b) exposing said surface to a solution of an ethylenically unsaturated monomer or mixture thereof capable, via said ethylenic unsaturation, of gamma-irradiation or electron beam induced polymerization; and

c) irradiating said activated surface with gamma or electron beam radiation in the presence of said ethylenic unsaturated monomer or mixture thereof to thereby form a hydrophilic polymeric surface coating on said surface, said polymerization being initiated by said gamma or electron beam radiation wherein said polymerization is conducted under the following conditions;

i) monomer concentration in said solution in the range of from about 0.1% to about 50%, by weight;

ii) total gamma or electron beam dose in the range of from about 0.001 to less than about 0.50 Mrad; and

iii) gamma dose rate in the range of from about 10 to about 2500 rads/min, or electron beam dose rate in the range of from about 10 to about 10⁸ rads/min.

2. The method of claim 1, wherein said material is metallic, polymeric, ceramic, glass or quartz.

3. The method of claim 2, wherein said material is polymethylmethacrylate, polypropylene, polyvinylidene fluoride, polydimethylsiloxane, a polycarbonate, a polycarbonate/polydimethylsiloxane copolymer, polyethylene, polyvinylchloride, polytetrafluoroethylene, polyperfluoroethylenepropylene copolymers, polyurethanes, or polyurethane/polydimethylsiloxane copolymers.

4. The method of claim 2, wherein said material is iron, stainless steel, tantalum, titanium, aluminum, copper or chromium, or alloys thereof.

5. The method of claim 1, wherein said material is a biomedical article.

6. The method of claim 5, wherein said bio-medical article is a prosthetic implant or surgical instrument.

7. The method of claim 1, wherein said GDP is RF-, microwave- or DC discharge-generated.

8. The method of claim 1, wherein said surface is exposed to RF-GDP for a time in the range of from about 0.1 sec. to about 120 min.

9. The method of claim 1, wherein said GDP treated surface is exposed to air, water vapor or oxygen before said gamma-irradiation induced polymerization.

10. The method of claim 1, wherein said GDP treated surface is pre-soaked in one or more of said ethylenically unsaturated monomers or in a first aqueous solution of one or more monomers, having a concentration of monomer therein of from 5 to about 95% by weight, and conducting said gamma-irradiation or electron beam induced polymerization in a second aqueous solution of one or more of said monomers.

11. The method of claim 1, wherein said monomer is N-vinylpyrrolidone, hydroxyethylmethacrylate, acrylamide, dimethylacrylamide, diemthylaminoethylmethacrylate, acrylic acid, methacrylic acid, a vinyl substituted polyethylene or polypropylene glycol, a vinylpyridine, or a vinylsulfonic acid.

12. The method of claim 1, wherein said monomer or mixture of monomers is gamma-irradiation induced copolymerized with an ionic monomer or mixture thereof, the total monomer concentration in said solution being in the range of from about 0.1% to about 50%, by weight.

13. The method of claim 12, wherein said ionic monomer is a vinylsulfonic acid or a vinylcarboxylic acid.

14. The method of claim 13, wherein said vinylsulfonic acid is styrene sulfonic acid, vinylsulfonic acid, or a sulfoalkylacrylate.

15. The method of claim 13, wherein said vinyl-carboxylic acid is acrylic, methacrylic or crotonic acid.

16. The method of claim 12, wherein said ionic monomer is an amino-functional monomer.

17. The method of claim 16, wherein said amino-functional monomer is a vinylpyridine, an aminostyrene, an aminoacrylate or an aminomethacrylate.

18. The method of claim 1, wherein said monomer or mixture of monomers is gamma-irradiation induced polymerized in the substantial absence of oxygen.