WO1996022864A1 - Articles usinables au laser - Google Patents

Articles usinables au laser Download PDF

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Publication number
WO1996022864A1
WO1996022864A1 PCT/US1996/001455 US9601455W WO9622864A1 WO 1996022864 A1 WO1996022864 A1 WO 1996022864A1 US 9601455 W US9601455 W US 9601455W WO 9622864 A1 WO9622864 A1 WO 9622864A1
Authority
WO
WIPO (PCT)
Prior art keywords
electrode
substrate
siloxane
ablating
laser
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/US1996/001455
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English (en)
Inventor
John Swanson
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
PI Medical Corp
Original Assignee
PI Medical Corp
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Filing date
Publication date
Application filed by PI Medical Corp filed Critical PI Medical Corp
Publication of WO1996022864A1 publication Critical patent/WO1996022864A1/fr
Anticipated expiration legal-status Critical
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Classifications

    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C59/00Surface shaping of articles, e.g. embossing; Apparatus therefor
    • B29C59/16Surface shaping of articles, e.g. embossing; Apparatus therefor by wave energy or particle radiation, e.g. infrared heating
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B23MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23KSOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K26/00Working by laser beam, e.g. welding, cutting or boring
    • B23K26/36Removing material
    • B23K26/40Removing material taking account of the properties of the material involved
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B23MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23KSOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K2101/00Articles made by soldering, welding or cutting
    • B23K2101/34Coated articles ; Surface treated articles
    • B23K2101/35Surface treated articles
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B23MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23KSOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K2103/00Materials to be soldered, welded or cut
    • B23K2103/30Organic materials
    • B23K2103/42Plastics other than composite materials
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B23MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23KSOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K2103/00Materials to be soldered, welded or cut
    • B23K2103/50Inorganic materials other than metals or composite materials
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B23MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23KSOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K2103/00Materials to be soldered, welded or cut
    • B23K2103/50Inorganic materials other than metals or composite materials
    • B23K2103/52Ceramics
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C35/00Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
    • B29C35/02Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould
    • B29C35/08Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation
    • B29C35/0805Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation using electromagnetic radiation
    • B29C2035/0827Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation using electromagnetic radiation using UV radiation
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C35/00Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
    • B29C35/02Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould
    • B29C35/08Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation
    • B29C35/0805Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation using electromagnetic radiation
    • B29C2035/0838Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation using electromagnetic radiation using laser
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29KINDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2083/00Use of polymers having silicon, with or without sulfur, nitrogen, oxygen, or carbon only, in the main chain, as moulding material
    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05KPRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00Apparatus or processes for manufacturing printed circuits
    • H05K3/0011Working of insulating substrates or insulating layers
    • H05K3/0017Etching of the substrate by chemical or physical means

Definitions

  • the present invention has broad application in the field of the micromachining of articles of manufac ⁇ ture such as in the fabrication of circuit boards, optical wave guides, diffraction grating, industrial sensors, and microporous membranes, and has particular application in the field of fabrication of biomedical devices, and more specifically of prostheses, implants and drug delivery systems. It further has application in the fabrication of prostheses and implants that include electrically conductive material, such as electrodes for placement within living beings to stimulate tissue elec- trically and to detect electrical activity in living tissue.
  • Such devices include cochlear implants, nerve cuff electrodes, subdural strip electrodes such as epileptogenic mapping sensors, cortical electrical sensors, catheters, catheter sensors, cardiac leads for pacemakers and for defibrillation, and electrode arrays of various configurations.
  • polymeric silicone materials for medical prostheses and implants
  • microporous polymeric reservoirs for the delivery of drugs is also known.
  • osmotically driven capsules formed of polymeric materials and having ports through the capsule wall for the delivery of drugs is known.
  • U.S. Patent No. 4,602,624 discloses the fabrication of a neural cuff by clamping the ends of a substrate sheet of elastomeric material across a first steel plate, stretching it, cutting out windows of a predetermined size, placing conductive foil over the windows, coating exposed metal with polymeric material to insulate the same, overcoating the entire substrate sheet and metal with uncured silicone elastomer and placing thereover another silicone elastomeric sheet, clamping the entire assembly between the first steel plate and a second steel plate, curing the uncured silicone elastomer and then trimming the so-laminated assembly to the desired dimensions.
  • U.S. Patent No. 4,903,702 discloses the fabrication of an epileptogenic mapping sensor by cutting two strips of flexible silicone dielectric, one with windows cut therein, placing insulated leads and associ- ated contacts between the strips and in alignment with the windows, placing a radioopaque dielectric ring between one contact and the bottom strip, and then laminating the assembly by heat.
  • U.S. Patent No. 5,037,497 discloses the fabrication of an array of recessed radially oriented bipolar electrodes suitable for use as an auditory prosthesis by a complex seven-step injection molding process that requires the formation of a multiplicity of dielectric annuli and the application of a vacuum to hold the annuli and electrodes in place during molding.
  • the essence of the present invention lies in the discovery that a certain class of dielectric material is ablatable by laser UN irradiation, and so is cleanly removable and formable into predetermined shapes, textures and patterns thereby.
  • an appropriately focused laser beam of UV light is directed onto a substrate of dimethylphenyl-substituted siloxane ("DMPS") to ablate the siloxane material to selectively remove portions thereof or to form the substrate into a prede ⁇ termined shape or to render it microporous or to define an active electrode site on a portion of an electrode conductor body.
  • DMPS dimethylphenyl-substituted siloxane
  • FIGS. 1-3 are schematics of various substrates comprising DMPS being laser-ablated to form the same into predetermined shapes and textures.
  • FIGS. 4-5 are schematics of an exemplary biologically implantable, multiple-conductor microelectrode.
  • FIGS. 6a and 6b are schematics of an exemplary biologically implantable epileptogenic mapping sensor.
  • the dielectric material comprising dimethylphenyl-substituted polysiloxanes may be cleanly ablated by UN laser beams, making such material ideally suited for "machining" on a microscopic scale, which in turn allows for the simple fabrication of biomedical and drug delivery devices, including, but not limited to, protheses, cochlear implants, intraocular implants, electrically conductive muscle stimulators and sensors, osmotic drug delivery capsules and microporous membranes.
  • functional group-terminated homopolymers, copolymers and terpolymers of DMPS having a wide degree of phenyl substitution comprise a suitable laser-ablatable material that may readily be removed so as to form a substrate of the material into a predetermined morphology or shape.
  • the siloxane material is represented by the structure
  • Me is methyl; Ph is phenyl;
  • R., and R 2 are selected from hydrogen, halogen, methyl, phenyl, vinyl, acrylyl, methacrylyl, alkynyl and epoxyl;
  • R' is alkyl, alkenyl, alkoxy or aryl containing from 1 to 18 carbon atoms
  • R" is alkylene, alkenylene, alkoxylene or arylene containing from 1 to 18 carbon atoms; and n is an integer from 400 to 1300.
  • Such dimethylphenyl-substituted siloxanes are photopolymerizable, with polymerization being initiated by free radical initiators.
  • free radical initiators include azos, peroxides, epoxides, certain ketones, aryliodonium salts and aryliosulfonium salts.
  • Specific examples of such initiators include azo- is-isobutyronitrile, dibenzoylperoxide, epichlorohydrin, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, benzophenone and ,2-diethoxyacetophenone.
  • the degree of phenyl substitution of such DMPS material is from 5 to 50 mol%, preferably from 10 to 30 mol%, and most preferably about 15 mol%.
  • the DMPS may be modified with silica or other compatible filler, vary ⁇ ing in amounts from 0 to 35 wt%.
  • the molecular weight may vary from 15,000 ⁇ 5000 to 50,000 ⁇ 20,000.
  • the ratio of terminal functional groups to SiO units may vary from 1:20 to 1:650, and is preferably in the range of 1:200 to 1:550.
  • FIG. la a cross-sectional view of a DMPS substrate 10 situated under a focusing lens 12 for a UN laser beam.
  • FIG. lb shows the substrate 10 with a channel 15 formed therein by ablation from UV laser beam 13.
  • FIG. lc shows the substrate 10 having a series of microvoids 25 formed therein by UV laser ablation, so as to effectively form a textured surface.
  • FIG. Id shows the substrate 10 having microholes 35 formed therethrough by UV laser ablation, so as to render the substrate microporous.
  • FIG. le is substantially the same as FIG. lc except that the substrate 10 has been coated with a non-UV-absorbing material 11, such as Teflon*, which is transparent to the wavelength of the laser beam.
  • a non-UV-absorbing material 11 such as Teflon*
  • FIG. 2 is a cross-sectional schematic of a conductive wire 40 coated with a different laser- ablatable coating 30 of parylene, which in turn is surrounded by a cylindrical DMPS substrate 20, the wire being exposed by laser ablation that forms an opening 45 through both coating 30 and substrate 20.
  • FIG. 3 is a cross-sectional view of a microelectrode comprising a DMPS substrate 22 surrounding an electrically conductive body 42 that is exposed by laser ablation.
  • the DMPS material absorbs laser radiation generally in the UV range. More specifically, and for example, a frequency-quadrupled YAG (FQY) laser operated in the fundamental transverse electromagnetic (TEM ⁇ ,) mode is suitable to ablate portions of the coating.
  • FQY frequency-quadrupled YAG
  • TEM ⁇ , fundamental transverse electromagnetic
  • this laser is Q-switched at around 1-20 KHz, producing a 40-50 ns full-width half maximum (F HM) pulse which is focused by a focusing lens to a spot about ⁇ 25 ⁇ m, producing a fluence of approximately 1-50 joules/cm 2 , at an average power of 5-500 milliwatts.
  • F HM full-width half maximum
  • Such a laser has a 266 nanometer wavelength which is in the UN range.
  • Such a highly focused laser beam in the ultraviolet frequency band is readily absorbed by the DMPS dielectric coating material described herein, and is also absorbed by the surfaces of metals such as platinum or iridium, typically used as the electrically conductive metals in biomedical prostheses, with the result that the DMPS dielectric material is both vaporized and photo- ablated, removing it cleanly from the surfaces of the conductive metal.
  • the FQY laser beam spot can be moved by computer software control to scan the DMPS dielectric material to selectively and cleanly remove it, thereby shaping the DMPS material into virtually any prede- termined shape, texture or even porosity in the event microscopic holes are produced.
  • Scanning control may be provided, for example, by equipment designed to control lasers for use in manufacture of integrated circuit products, such as is available from Electro Scientific Industries, Inc. , of Beaverton, Oregon.
  • the UN laser is utilized together with exhaust and positive gas pressure systems to keep debris away from the focus ⁇ ing lens and the area where dielectric material is being ablated. Operation of the laser at powers of 5-500 milliwatts provides an effective range of etch depths of approximately 5-150 microns in DMDPS.
  • FIGS. 4-5 show various aspects of an exemplary biologically implantable multiconductor microelectrode 70 capable of being fabricated according to the present invention.
  • the microelectrode 70 includes an electric ⁇ ally conductive core 72 and fine wires 74 extending from a helically stranded multiconductor cable, each wire being insulated by coatings 76 of flexible dielectric material.
  • the fine wires 74 are wrapped around the conductive core 72 in a helical serving in which the individual fine wires 74 lie alongside one another without overlapping.
  • Each of the fine wires 74 has an individual thin coating 76 of dielectric material, and a further coating 78 of DMPS dielectric material adhesively attaches the fine wires 74 to one another and to the core 72, forming a monolithic, elongate multiconductor microelectrode body.
  • an active electrode site 86 is provided on each of the fine wires 74 by ablating the DMPS dielectric material of the coatings 76 and 78 from the wire over a micro-area, forming a circular opening 88 through the DMPS material 78 and other dielectric material 76 insulating each of the fine wires 74.
  • the openings 88 of the electrode sites 86 may be left as depressions relative to the outer surface of the outer coating 78 of DMPS dielectric material, or deposits of metal 90 having desired conductivity and resistance to electrochemical corrosion may be provided by electrophoretic deposition, the deposits 90 being attached to and electrically interconnected to the surface of fine wires 74, either partly filling the openings 88, as shown in FIG. 5b, filling the openings flush with the outer surface of the DMPS dielectric material, as shown with deposit 92 in FIG. 5c, or forming small bumps standing proud above the outer surface of the DMPS dielectric material, as shown with deposit 94 shown in FIG. 5d.
  • a generally planar array of active electrode sites 100 of a biologically implantable multiconductor microelectrode 120 may be fabricated according to the present invention and used in connection with a biologically implantable cable 130 similar to that disclosed in commonly owned U.S. Patent No. 5,201,903, the disclosure of which is hereby incorpo ⁇ rated herein by reference.
  • a series of fine wires 103 extends to each electrode site 100 of the microelectrode 120, which has a generally planar body comprising a lamination of two strips of DMPS material 110a and 110b and electrically conductive foil 105, best seen in FIG. 6b.
  • Active electrode sites 100 are provided by ablating openings through the DMPS dielectric material of the body 110 with the use of a UV laser as previously described, to provide a clean electrically conductive contact.
  • Example 1 To demonstrate the peculiarly attractive laser-ablatability of the DMDPS material, 100 m ⁇ -thick coatings of vinyl-terminated poly(dimethylphenylsiloxane) commercial available from McGhan Nusil Corporation of Carpenteria, California as Nusil R-2655 having a degree of phenyl substitution of 5 mol% were made on a 304 stainless steel substrate. Coatings of the same thick ⁇ ness of vinyl-terminated dimethylsiloxane having no phenyl substitution were made on the same substrate immediately adjacent the phenyl-substituted siloxane coatings.

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  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Plasma & Fusion (AREA)
  • Mechanical Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • Electrotherapy Devices (AREA)

Abstract

Procédé de formation d'un article (10) constitué de siloxane à substitution diméthylphényle, l'étape clé de ce procédé consistant en l'ablation de l'article (10) à l'aide d'un rayon laser UV (13) fourni par une lentille de focalisation (12) afin de former des microvides (25) dans la surface de l'article (10).
PCT/US1996/001455 1995-01-25 1996-01-24 Articles usinables au laser Ceased WO1996022864A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US37763395A 1995-01-25 1995-01-25
US08/377,633 1995-01-25

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WO1996022864A1 true WO1996022864A1 (fr) 1996-08-01

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998030317A1 (fr) * 1997-01-10 1998-07-16 Morphometrix Technologies Inc. Procede de fabrication de membranes microfiltrantes
WO2001094098A1 (fr) * 2000-06-09 2001-12-13 University Of Warwick Science Park Limited Emballage
WO2019099156A1 (fr) * 2017-11-15 2019-05-23 Laitram, L.L.C. Composants de transporteur en plastique superhydrophobes et procédés de moulage de ces composants
US10842653B2 (en) 2007-09-19 2020-11-24 Ability Dynamics, Llc Vacuum system for a prosthetic foot

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4460371A (en) * 1981-11-24 1984-07-17 Dennison Manufacturing Company Silicone pressure sensitive adhesive and uses
GB2233334A (en) * 1989-06-29 1991-01-09 Exitech Ltd Surface treatment of polymer materials by the action of pulses of UV radiation
US5401376A (en) * 1993-04-09 1995-03-28 Ciba Corning Diagnostics Corp. Electrochemical sensors

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4460371A (en) * 1981-11-24 1984-07-17 Dennison Manufacturing Company Silicone pressure sensitive adhesive and uses
GB2233334A (en) * 1989-06-29 1991-01-09 Exitech Ltd Surface treatment of polymer materials by the action of pulses of UV radiation
US5401376A (en) * 1993-04-09 1995-03-28 Ciba Corning Diagnostics Corp. Electrochemical sensors

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998030317A1 (fr) * 1997-01-10 1998-07-16 Morphometrix Technologies Inc. Procede de fabrication de membranes microfiltrantes
WO2001094098A1 (fr) * 2000-06-09 2001-12-13 University Of Warwick Science Park Limited Emballage
US10842653B2 (en) 2007-09-19 2020-11-24 Ability Dynamics, Llc Vacuum system for a prosthetic foot
WO2019099156A1 (fr) * 2017-11-15 2019-05-23 Laitram, L.L.C. Composants de transporteur en plastique superhydrophobes et procédés de moulage de ces composants
CN111263728A (zh) * 2017-11-15 2020-06-09 莱特拉姆有限责任公司 超疏水塑料输送机部件和其成型方法

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