Method for fabrication of metallized medical devices

• US 5,685,961 A
• Filed: 03/27/1992
• Issued: 11/11/1997
• Est. Priority Date: 03/27/1992
• Status: Expired due to Fees

• Current Assignee: P & D Medical Coatings Incorporated
• Original Assignee: P & D Medical Coatings Incorporated
• Inventors: Boxman, Raymond Leon, Shvets, Irina, DeLaurentis, Mark, Beard, Richard Burnham, Pourrezaei, Kambiz
• Primary Examiner(s): NGUYEN, NAM X
• Application Number:
  US07/859,063
• Time in Patent Office: 2,055 Days
• Field of Search: 204/192.12, 204/192.15, 204/192.14, 216/83, 252/79.1, 427/2.1, 427/2.28, 427/304
• US Class Current: 204/192.15
• CPC Class Codes: C23C 14/046 Coating cavities or hollow spaces, e.g. interior of tubes; Infiltration of porous substrates
• CPC Class Codes: C23C 14/205 by cathodic sputtering
• CPC Class Codes: C23C 14/568 Transferring the substrates through a series of coating stations C23C14/562 takes precedence
• CPC Class Codes: C23C 18/2086 with use of organic or inorganic compounds other than metals, first
• CPC Class Codes: C23C 18/285 Sensitising or activating with tin based compound or composition
• CPC Class Codes: C23C 18/30 Activating or accelerating or sensitising with palladium or other noble metal
• CPC Class Codes: C23C 18/44 using reducing agents

Abstract

Catheters and other medical devices include plural layers of metals applied to the outer surfaces, which tend to close minuscule cracks through which corrosion may attack the underlying support. In some avatars, the initial layer of material is preferably silver, applied following specific preparation steps. In other embodiments, succeeding layers of metal completely cover the initial layer, and are also of silver. The succeeding layers are deposited after deposition of the prior layer, and tend to reduce the incidence of microscopic pores or cracks and are less prone to delamination. The succeeding layers are preferably of mutually different metals between layers. In a particular avatar, in which the exposed metals are oligodynamic silver and more noble platinum, the exposed silver layer lies over a portion of the platinum layer, to thereby prevent corrosion of the silver layer from disconnecting portions of the silver layer. Fabrication methods include deposition of successive layers by means of sputtering in a longitudinal array of cylindrical magnetron sections, in which each section applies one layer of the coating over the coating applied by the preceding section. The magnetron sections may be energized and deenergized in a temporal pattern associated with the progress of the workpiece material through the array, to thereby cover or expose particular longitudinal layers. In some embodiments, a first layer of electrically conductive material is deposited by electroless methods particularly in the lumen, following which additional layers may be applied by conventional electrolytic deposition. An electroless method according to the invention includes preparation steps which may include ultrasonically cleaning the surface with a solution of isopropyl alcohol, then drying the surface with a stream of dry gas, and etching the surface with a solution of sodium naphthalene in diethylene glycol dimethyl ether.

Claims

1. A method for fabricating a catheter in which a lumen is metal-coated, comprising the steps of:

preparing an inner surface of an elongated polymer tube;

electroless depositing a layer of a metal onto said inner surface, wherein said step of preparing said inner surface comprises the steps of;

cleaning said inner surface with an ultrasonic cleaner in a solution of one of 2-Propanol and isopropyl alcohol CH₃ CHOHCH₃ ;

drying; and

etching said inner surface with a solution of sodium naphthalene in diethylene glycol dimethyl ether with a concentration of sodium naphthalene of approximately 0.7 Mol/liter.

2. A method for fabricating a catheter in which a lumen is metal-coated, comprising the steps of:

preparing an inner surface of an elongated polymer tube;

electroless depositing a layer of a metal onto said inner surface, wherein said step of preparing said inner surface comprises the steps of;

cleaning said inner surface with an ultrasonic cleaner in a solution of one of 2-Propanol and isopropyl alcohol CH₃ CHOHCH₃ ;

drying; and

etching said inner surface with a solution of sodium naphthalene in diethylene glycol dimethyl ether with a concentration of sodium naphthalene of approximately 0.7 Mol/liter;

further comprising the steps of;

washing said lumen a first time with one of N-butyl alcohol, methyl alcohol, and acetone;

rinsing with deionized water following said step of washing a first time;

following said step of rinsing, etching with sulfochromic acid solution containing about 75 g/l chromic acid, and 250 g/l sulfuric acid, at room temperature for a duration of 20 seconds;

following said step of etching with sulfochromic acid solution, washing a second time with distilled water;

following said step of etching with sulfochromic acid solution, cleaning in diluted hydrochloric acid;

following said step of cleaning in diluted hydrochloric acid, rinsing a second time with deionized water;

following said step of rinsing a second time, sensitizing with a solution containing 70 g/l stannous chloride, and 40 ml/l of hydrochloric acid, at room temperature for between 5 and 15 minutes;

following said step of sensitizing, washing a second time with deionized water;

following said sensitizing step, activating with a solution containing 1 g/l of palladium chloride, and 5 ml/l of hydrochloric acid, at room temperature for five to ten minutes;

following said step of sensitizing, rinsing a third time with deionized water;

following said step of rinsing a third time, plating by flowing a silver plating solution at room temperature through the lumen of the catheter, said silver plating solution containing 0.05 to 0.6M AgNO₃,4.3×

10^-4 M dodecylbenzenesulfonic acid acid sodium salt (C₁₂ H₂₅ C₆ H₄ SO₃ Na), 4.75M ammonium hydroxide (NH₄ OH), and a quantity of acetic acid (CH₃ CO₂ H) sufficient to bring the final pH into the range from 7.5 to 10; and

adding a reducer solution one of immediately prior to and concurrently with application of said plating solution, said reducer solution containing 0.15M of hydrazine (N₂ H₄.xH₂ O).

3. A method for coating the interior of a dielectric tube, comprising the steps of:

inserting a conductive target wire electrode into the lumen of said dielectric tube;

maintaining an atmosphere of gas around said wire electrode at a pressure sufficient to allow glow discharge; and

applying RF voltage between said wire electrode and an electrode exterior to said tube which is sufficient to cause said glow discharge, whereby said wire electrode produces coating atoms.

4. A method according to claim 3, comprising the further step of maintaining said wire electrode spaced away from the walls of said lumen.

5. A method according to claim 4, wherein said step of maintaining said wire electrode spaced includes the further step of:

tensioning said wire electrode within said dielectric tube.

6. A method according to claim 5 wherein said maintaining step includes the step of:

placing said exterior electrode about said tube with a bore of said exterior electrode concentric with said wire.

7. A method according to claim 3 wherein said step of apply RF includes the steps of:

plating said exterior electrode onto an exterior surface of said tube; and

connecting a terminal of a source of RF to said exterior electrode.

8. A method for coating the interior of a dielectric tube, comprising the steps of:

inserting an electrically conductive target wire into the lumen of said dielectric tube;

maintaining said wire spaced away from the walls of said lumen;

maintaining an atmosphere of gas around said wire sufficiently low for efficient sublimation; and

passing a current through said wire sufficient to heat said wire to sublime.

9. A method according to claim 8 wherein the material of said conductive wire is selected to be one of chromium and titanium.