US20130233717A1 - Anodized Titanium Devices and Related Methods - Google Patents

Anodized Titanium Devices and Related Methods Download PDF

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US20130233717A1
US20130233717A1 US13/777,034 US201313777034A US2013233717A1 US 20130233717 A1 US20130233717 A1 US 20130233717A1 US 201313777034 A US201313777034 A US 201313777034A US 2013233717 A1 US2013233717 A1 US 2013233717A1
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titanium
medical device
devices
titanium oxide
anatase
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John Disegi
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Synthes GmbH
DePuy Synthes Products Inc
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Synthes GmbH
DePuy Synthes Products Inc
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/26—Anodisation of refractory metals or alloys based thereon
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
    • A61L31/02—Inorganic materials
    • A61L31/022—Metals or alloys
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
    • A61L31/14—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • A61L31/16—Biologically active materials, e.g. therapeutic substances
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D7/00—Electroplating characterised by the article coated
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
    • A61L2300/10—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices containing or releasing inorganic materials
    • A61L2300/102—Metals or metal compounds, e.g. salts such as bicarbonates, carbonates, oxides, zeolites, silicates
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
    • A61L2300/40—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices characterised by a specific therapeutic activity or mode of action
    • A61L2300/404—Biocides, antimicrobial agents, antiseptic agents
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2400/00—Materials characterised by their function or physical properties
    • A61L2400/18—Modification of implant surfaces in order to improve biocompatibility, cell growth, fixation of biomolecules, e.g. plasma treatment

Definitions

  • the present disclosure relates to the field of biomechanical implants and to the field of anodized metals.
  • titanium Because of its high strength, low weight, and corrosion resistance, titanium has application to various medical implant applications. Because unwanted microbial growth is a concern in medical implant technology, some have attempted to construct titanium implants that feature titanium oxide coatings. Such coatings, however, suffer from poor adhesion to the underlying implant structure, are prone to delamination, and are also associated with a significant reduction in fatigue strength. Accordingly, there is a long-felt need in the art for titanium implant structures that have antimicrobial properties that do not suffer from the drawbacks of titanium oxide coated implant materials. There is also a related need in the field for related methods of fabricating such implants.
  • This disclosure presents, inter alia, methods to produce and activate an antimicrobial oxide surface on titanium implants.
  • electrochemical anodization parameters such as waveform and electrolyte may be controlled to produce an anatase titanium oxide surface morphology.
  • Such morphology is particularly useful in antimicrobial applications as compared to rutile, brookite, or amorphous titanium oxide surface structures.
  • the surface oxide film may be heat treated to transform the surface structure or to optimize the percentage (%) anatase in the surface film.
  • Anatase titanium oxide demonstrates antimicrobial properties when activated under specific photocatalytic conditions. Antimicrobial activation of the anatase titanium oxide can occur in the near ultraviolet wavelength of 350 to 380 nm to create reactive oxygen species and hydroxyl radicals that provide antimicrobial properties.
  • the titanium implant may be activated before the titanium implant is packaged or, alternatively, may be packaged in the operating room before implantation using a suitable light source.
  • a further advantage of the disclosed methods and implants is the ability to provide color coded titanium implants.
  • This color coding may be used to construct an implant system (e.g., color-coded by size, shape, by application, or even by patient type) that also features antimicrobial properties when activated.
  • the anodized film may be thin (in the nanometer range), and because the film is produced by electrochemical oxidation, the anatase film is extremely adherent, durable, and exhibits negligible reduction in fatigue strength for the implant.
  • FIG. 1 illustrates the x-ray crystallography spectrum for an exemplary anatase-phase material according to the present disclosure, showing the anatase phase present in the material;
  • FIG. 2 illustrates an exemplary setup for fabricating an anatase film on the surface of a titanium substrate
  • FIG. 3 illustrates several colored anatase samples according to the present disclosure
  • FIG. 4 illustrates an additional composite image of the different voltage levels we tested in a 0.5 molar sulfuric acid bath with a square wave (DC);
  • FIG. 5 illustrates x-ray diffraction data for the samples of FIG. 4 , with the anatase peak labeled;
  • FIG. 6 presents the same x-ray diffraction data with the rutile peak labeled
  • FIG. 7 illustrates a composite image of samples tested in a 0.94 molar sulfuric acid bath (square wave DC);
  • FIG. 8 presents x-ray diffraction data from the samples of FIG. 7 with the anatase peak labeled.
  • FIG. 9 presents x-ray diffraction data from sputter-coated materials as compared to a sample (top graph) according to the present disclosure, with the anatase peak in the topmost sample labeled.
  • FIG. 10 presents an SEM image showing the natural forming oxide of titanium
  • FIG. 11 presents an SEM image showing the titanium oxide after pickling in an exemplary nitric-hydrofluoric acid solution
  • FIG. 12 presents a comparatively low magnification SEM image of a gold anodized titanium sample tested in 0.5 M H2SO4;
  • FIG. 13 presents a comparatively higher magnification SEM image of a gold anodized titanium sample tested in 0.5 M H2SO4;
  • FIG. 14 presents a higher magnification SEM image of a gold anodized titanium sample tested in 0.5 M H2SO4;
  • FIG. 15 presents a low magnification SEM image of a gold anodized titanium sample tested in 2 M H2SO4;
  • FIG. 16 presents a high magnification SEM image of a gold anodized titanium sample tested in 2 M H2SO4;
  • FIG. 17 presents a high magnification SEM image of a gold anodized titanium sample tested in 2 M H2SO4;
  • FIG. 18 presents a low magnification SEM image of a green anodized titanium sample tested in 0.94 M H2SO4;
  • FIG. 19 presents a high magnification SEM image of a green anodized titanium sample tested in 0.94 M H2SO4;
  • FIG. 20 presents a high magnification SEM image of a green anodized titanium sample tested in 0.94 M H2SO4;
  • FIG. 21 presents a low reproduction SEM image obtained with the EBSD detector showing the area being scanned of the 0.94 M green anodized titanium;
  • FIG. 22 presents a grain orientation map and associated inverse pole figure map for the 0.94 M green anodized titanium
  • FIG. 23 presents an EBSD image showing the crystalline phases detected and associated area fractions for the 0.94 M green anodized titanium
  • FIG. 24 presents an x-Ray diffraction scan of a green anodized titanium sample tested in 2 M H2SO4;
  • FIG. 25 presents a low magnification SEM image of a green anodized titanium sample tested in 2 M H2SO4;
  • FIG. 26 presents a high magnification SEM image of a green anodized titanium sample tested in 2 M H2SO4;
  • FIG. 27 presents a high magnification SEM image of a green anodized titanium sample tested in 2 M H2SO4;
  • FIG. 28 presents an SEM image obtained with the EBSD detector showing the area being scanned of the 2 M green anodized titanium;
  • FIG. 29 presents an EBSD image showing the grain orientations and associated inverse pole figure map for the 2 M green anodized titanium
  • FIG. 30 presents an EBSD image showing the crystalline phases detected and associated area fractions for the 2 M green anodized titanium.
  • FIG. 31 presents an x-Ray diffraction scan of a green anodized titanium sample tested in 2 M H2SO4.
  • the present disclosure provides medical devices. These devices may be configured as, e.g., implants, supports, fasteners, and the like.
  • the medical devices suitably first include a substrate comprising titanium.
  • the substrate may be solid titanium (e.g., a solid titanium rod, sheet, plate, and the like), but may also include a titanium coating or shell associated with a core material.
  • the device may include a core that is surmounted by a titanium (pure, alloy, or even composite) coating.
  • the titanium coating may be bonded to the core or mechanically affixed or otherwise interlocked with the core.
  • a device according to the present disclosure may feature an exterior that has a region of titanium, titanium alloy, or of titanium composite, and another region that is free of titanium. Such devices are suitable for applications where the titanium-bearing portion is implanted into a subject's body, and the non-titanium bearing portion lies outside of the subject.
  • the core may be polymeric or other material (e.g., metal) that is adaptable to use in medical implants.
  • exemplary polymers include PEEK, PEKK, UHMWPE, poyphenylsulfone, HDPE, PCU, and the like. PE, PP, and PC may also be used.
  • the devices suitably include a titanium oxide film that surmounts at least a portion of the titanium of the device, with at least a portion of the titanium oxide film suitably being anatase phase.
  • the film may be anodized in form.
  • the titanium oxide film is suitably of such a thickness so as to impart a visually perceptible color to the medical device.
  • the substrate may, as described above be essentially pure titanium.
  • the substrate may be solid titanium (e.g., a solid rod, plate, or platelet).
  • the substrate may comprise a titanium alloy.
  • Virtually any implantable titanium alloys may be used in the disclosed devices. A partial, nonexhaustive listing of such alloys includes, e.g., Ti6Al7Nb, Ti6Al4V, Ti6Al4V ELI, Ti15Mo, Ti13Nb13Zr, Ti3Al2.5V, and Ti12Mo6Zr2Fe.
  • the implantable alloys may be anodized and will suitably contain a % of anatase in the mixed oxide film.
  • an anodized Ti6Al7Nb substrate is comprised of titanium oxide plus aluminum oxide plus niobium oxide and will contain less anatase than a pure titanium substrate.
  • the specific anodizing parameters required to produce an anatase titanium oxide structure will also vary for each alloy and will affect the amount of anatase that is present in the mixed oxide film.
  • the devices may feature apertures (smooth or threaded) to facilitate installation of the devices into a subject.
  • a support plate used to support a broken long bone implant may feature smooth apertures at either end, through which screws or other fasteners may be installed to fix the plate to the long bone.
  • the fasteners themselves may, as described elsewhere herein, feature anatase regions according to the present disclosure so as to render the fasteners antimicrobial.
  • the fasteners may also feature a color that matches that of the support plate so as to indicate to the user that the fasteners are adapted for use with the plate.
  • the thickness of the film may vary, depending on the needs of the user and the desired color profile.
  • the thickness is suitably in the range of from about range of 20 nm to about 500 nm, or from 100 nm to about 400 nm, or even from about 130 nm to about 275 nm.
  • These thicknesses enable the production of devices that exhibit colors of, e.g., gold, rose red, purple, aqua, and green, among others.
  • Other colors, such as bronze, brown, dark purple, blue, light blue, green-gray, and light green may also be produced by modulating the thickness of the anatase coating.
  • a device may include a first region that features a film of one thickness and another region that features a film of another thickness.
  • a device may include two or more regions that feature different colors. This may be used so as to inform the user as to the alignment of the device when in use.
  • a device may be configured to have a blue distal region and a green proximal region.
  • the disclosed devices may also be configured such that a colored region on an implant (e.g., blue) coordinate with the fasteners (blue screws, nails, etc.) that are to be used with that implant.
  • the devices may be configured to serve in a variety of applications.
  • the devices are adapted to serve as implants.
  • the implants may be suitable for long bone implant purposes or for implantation as other bones.
  • the implants may be configured as plates, strips, ribbons, or the like.
  • the implants may be configured as needles, catheters, cannulas, or even as other instruments such as scoops, rasps, and the like.
  • Implant configurations are considered especially suitable, as such configurations are capable of taking advantage of the antimicrobial characteristics of the disclosed materials.
  • the disclosed devices may also be applied as total joints (hips, wrists, shoulders, ankles, knees, spinal disc prostheses, arthoplasty devices, and the like).
  • the disclosed devices may also be applied as plates, screws, pins, intramedullary nails, neurological implants, mandibular implants, mid-face implants, spinal rods, spinal clamps, intervertebral cages, and the like.
  • the films of the disclosed devices suitably comprise a content that is suitably more than 95% anatase for commercially pure (“CP”) titanium.
  • the film may be more than about 5%, 15%, 25%, 35%, 45%, 55%, 65%, 75%, 85 A anatase phase.
  • the device film may be less than 95% anatase, depending on the composition of the mixed oxide film composition after anodizing.
  • the titanium oxide film includes greater than 95% anatase and less than about 5% rutile phase.
  • the anatase titanium oxide film can be described as a cohesive single-phase oxide that exhibits a distinct crystallographic X-Ray structure, as shown in FIG. 1 , which figure illustrates the anatase phase present in a sample according to the present disclosure.
  • the substrate may, in some embodiments, be a mixture of a polymer and titanium. Such composites may include a polymer composition combined with titanium or titanium alloy.
  • the polymer component of the substrate may be a single polymer (e.g., PEEK), or multiple polymers (e.g., PEEK and PP) or even a copolymer.
  • the substrate may comprise a mixture of titanium bodies (particles, flakes, and the like) dispersed within or on the bulk of a polymer or other matrix.
  • the film may be integral to the device.
  • the applied voltage is suitably in the range of from about 25 V to about 400 V, or from about 50 V to about 350 V, or from about 200 V to about 250 V.
  • the voltage may be applied in intervals.
  • the voltage may increase over time, or may be applied at a constant level.
  • the voltage may be increased over time.
  • the increase may be linear, exponential, or step-wise.
  • the voltage may also have a sine waveform, square waveform, triangle, or sawtooth waveform.
  • devices were fabricated using a DC rectifier. The voltage was applied with a 10 volt incremental increase every 10 seconds. A programmable square wave waveform was used, with an on-time of 1-5 micro seconds and an off time 99 microseconds.
  • the electrolyte used was a 0.94 M sulfuric acid with a bath pH of about 0.15 at room temperature.
  • Other suitable electrolytes investigated were 0.5M sulfuric acid (pH 0.30), 0.94 M sulfuric acid (pH 0.15), and 2.0 M sulfuric acid (pH ⁇ 0.30).
  • 6.0 M sulfuric acid is also a suitable electrolyte, as such an electrolyte is capable of producing a comparatively high percentage of anatase in the color anodized film.
  • Electrolytes—e.g., sulfuric acid—at from about 0.3 M to about 7.0 M or even 9.0 M (e.g., 2.8 M, 3.8 M, 5.6 M, and 6.0 M) are considered especially suitable for the disclosed techniques.
  • the electrolyte may be a salt solution, or an acid solution.
  • Various salts sodium chloride, calcium chloride, and the like
  • Various acids may be used in the electrolyte, such as acetic, citric, nitric, sulfuric, and other acids may be used.
  • An electrolyte may, for example, comprise a mixture of ACS grade nitric acid (67-70%) and distilled water.
  • the user may clean or otherwise pretreat (“pickle”) the titanium before processing, as desired.
  • pickle A variety of methods may be used to clean the titanium. For example, one may clean the titanium by scrubbing or brushing with a wire or other brush. Grinding, draw filing, and acid picking may also be used.
  • Various combinations of nitric acid plus hydorfluoric acid may be used as long as the volume % nitric acid to volume % hydrofluoric acid ratio is greater than 10:1 to minimize the occurrence of hydrogen embrittlement.
  • One may also use a water rinse to remove acid, followed by a hot water rinse to facilitate drying.
  • Another exemplary pretreatment can be a nitric acid-hydrofluoric acid solution (e.g., 20:2 ratio) Immersion in nitric-hydrofluoric acid solution is used to clean and activate the titanium surface before electrolytic anodization.
  • the ratio of nitric acid to hydrofluoric acid may be adjusted so as to avoid hydrogen pickup in the titanium material.
  • a nitric acid to hydrofluoric acid ratio of minimum ca. 10 to 1 to minimize hydrogen absorption during acid treatment is recognized in ASTM B600 Standard Guide for Descaling and Cleaning Titanium and Titanium Alloy Surfaces.
  • a user may also apply an activation process to configure the titanium film for antimicrobial activity.
  • anatase activation may be effected by the near ultraviolet wavelength of 350 to 380 nanometers so as to create reactive oxygen species and hydroxyl radical that provide antimicrobial properties.
  • titanium implants or coupons are cleaned in an alkaline bath or detergent to remove oil, cutting fluid, and other loose surface contaminants
  • the implants are then immersed in a nitric acid-hydrofluoric acid pre-treatment solution (e.g., 20:2 ratio).
  • Implants are then placed in a titanium basket or a clamping device in contact with a copper bus bar that connected to a DC rectifier power supply, as illustrated in FIG. 2 .
  • the clamped implant or basket was immersed in a 0.94 M sulfuric acid electrolyte and the voltage was increased in 10 volt incremental increase every 10 seconds.
  • a power supply may be connected through the negative lead (anode) to conductive (e.g., copper) bars running across the short lengths (side to side) of the anodizing bath to carbon counter electrodes.
  • the exemplary negative lead shown here is split into two cables for this setup with two carbon counter electrodes on each anode copper bar.
  • the power supply is also connected through the positive (cathode) lead to a copper bar that runs across the length of the anodizing bath as shown in FIG. 2 .
  • the positive lead is connected directly to the cathode copper bar and the samples are in turn connected through a metallic clamp, and the samples are then suspended in the electrolyte.
  • the carbon counter electrodes are spaced out evenly from one another in order to give the most efficient anode to cathode area in the electrolyte (the most efficient flow of electrons in solution).
  • the positive lead from the power supply could be connected to the cathode bar(s) and the negative lead connected to the anode bar(s).
  • the power (voltage and amperage) of the power supply, number and spacing of counter electrodes, and number of cathode bars would depend on the size of the anodizing bath.
  • FIG. 3 Processed titanium coupons are shown in FIG. 3 .
  • a coupon with a yellow-gold color is shown. This coupon was produced by processing at 75 V.
  • the second coupon from the upper left exhibited a pink-rose color, and was processed at 85 V.
  • the third coupon from the upper left exhibited a violet color, which coupon was processed at 95 V.
  • the coupon fourth from the upper left (processed at 105 V) exhibited an aqua blue color.
  • the foregoing samples were produced using a waveform with a time increment step size of 10 seconds and a voltage step size of 5, 10 or 20V; other voltage steps of from 0.01 V to 50 V are also suitable.
  • the voltage step size was limited to the inputs on the current power supply which had only 15 steps available; this should not be understood as limiting the present disclosure in any way.
  • the final voltages of 150V and less were increased at 10V every 10 seconds and final voltages of >150V are stepped up at 20V every 10 seconds.
  • any final voltage not an integer of 10 had a 5V end step for 10 seconds.
  • a final voltage of 70V would have a recipe of 10V 10 sec, 20V 10 sec, 30V 10 sec, 40V 10 sec, 50V 10 sec, 60V 10 sec, and 70V 10 sec.
  • a 75V final voltage would have a recipe of 10V 10 sec, 20V 10 sec, 30V 10 sec, 40V 10 sec, 50V 10 sec, 60V 10 sec, 70V 10 sec, and 75V 10 sec.
  • Another example is for a final voltage of 200V which is 20V 10 sec, 40V 10 sec, 60V 10 sec, 80V 10 sec, 100V 10 sec, 120V 10 sec, 140V 10 sec, 160V 10 sec, 180V 10 sec, and 200V 10 sec.
  • the 10 second durations of these voltages is not limiting, as voltages may be applied for from about 0.01 seconds to about 10, about 20, about 30, about 60, about 120, about 300, or even about 500 seconds.
  • the output color is related to the thickness of the surface oxide created.
  • the oxide layer created depends on the final voltage applied, the area of the sample exposed to the electrolyte (current density, A/cm 2 ), and also sample surface condition. Current for the exemplary system was set at 10 amps and the area suspended in the electrolyte was constant for all samples. Further, all samples were prepared for anodization using the same techniques previously described. Therefore, the only variable that changed color (oxide thickness) was the final applied voltage.
  • exposure time at the final voltage may noe necessarily change (purple to green for example) the final color of the surface oxide and will be in the range of the corresponding thickness values given in the following table, which table relates exemplary surface oxide thicknesses (given in nm) to surface color appearance:
  • FIG. 4 Additional, exemplary samples are shown in FIG. 4 .
  • the samples in that figure were as follows: 70V (yellow-green), 90V (pink-rose), 110V (blue), 115 (blue-violet), 120V (green), 130V (green), 140V (medium green).
  • FIG. 5 presents x-ray diffraction spectra for the samples shown in FIG. 4 .
  • each of the samples presents a characteristic anatase peak at a two-theta value of about 25.25 degrees.
  • FIG. 6 presents x-ray diffraction data for the samples shown in FIG. 4 and FIG. 5 , with the location of the characteristic rutile peak (not present in the samples) labeled.
  • FIG. 7 illustrates a composite image of samples tested in a 0.94 molar sulfuric acid bath, processed with a square wave voltage and a DC rectifier.
  • the samples 70V (green-yellow), 90V (pink-rose), and 105V (blue-rose) exhibit color that varied according to the processing conditions for the samples.
  • FIG. 8 presents x-ray diffraction data from the samples of FIG. 7 .
  • the anatase peak for the samples is labeled—as shown in the figure, each sample exhibits an anatase peak.
  • FIG. 9 presents a x-ray diffraction data for materials according to the present disclosure (uppermost chart) that exhibit a purplish color that is essentially equivalent to the color of vacuum sputter-coated materials (lower charts) which do not contain anatase in the colored oxide film.
  • the sputter-coating may not in all cases demonstrate antimicrobial properties after light activation, as sputter-coated film does not contain an anatase peak.
  • kits suitably include first and a second devices, each of the devices having at least one surface that is at least partially surmounted by a film of titanium oxide, that is at least partially anatase in phase and that confers a visually perceptible color on the devices, the first and second devices differing in visually perceptible color and in at least one other physical characteristic.
  • kits may include multiple implants featuring different colors.
  • the largest implant in the kit may feature a green color, and the smallest implant may feature a gold color.
  • the colors may also be used to distinguish between implants that differ in some other physical characteristic.
  • a kit may include a gold-colored implant adapted for use as a humerus implant, and a rose-colored implant adapted for use as a radius implant.
  • the kits may also include color-coded anchors, nails, or screws that match or approximate the color of the devices with which they are intended to cooperate.
  • fasteners may be color-coded by size, e.g., fasteners of 5 mm diameter are gold-colored, and fasteners of 10 mm diameter are rose-colored.
  • the kit may also, in some embodiments, include a source of that is operable to emit light of a wavelength and intensity sufficient to cause the titanium dioxide to exhibit a biocidal effect upon irradiation with light from the light source.
  • This light source may be a lamp, a laser, or similar.
  • One exemplary light source is the TL 20W/05 UV lamp from Phillips Co., Holland, operating at about 360 nanometers.
  • the near ultraviolet (NUV) wavelength occurs primarily between 300 nm to 400 nm and the preferred activation wavelength is from about 350 nm to about 380 nm.
  • Fluorescent black lights coated with specific phosphers on the inside of the tube may also be used, such as but not limited to, europium doped strontium flouroborate or europium doped strontium borate (368 nm-371 nm emission peak) and lead-doped barium silicate (350 nm-353 nm emission peak).
  • Other ultraviolet wavelengths outside of the preferred anatase activation range such as ultraviolet A (UVA) at 315 nm-400 nm, ultraviolet B (UVB) at 280 nm-315 nm, and middle ultraviolet (MUV) at 200 nm-300 nm may be used.
  • Antimicrobial activation may, in some embodiments, be tuned as a function of light exposure.
  • kits may include a removable package that is suitably essentially transparent to ultraviolet light.
  • the first, second, or both devices are suitably disposed within the removable package.
  • the package may be a bag, a box, and the like.
  • the kit may be disposed in a suitcase, box, or other container. As described elsewhere herein, the devices may be exposed to illumination to activate them before being sealed into a package or sealed into a kit.
  • the user suitably illuminates the implant or other device before implantation, although the devices may be illuminated after installation. Illumination and activation may also be effected after the device is fabricated, or even after the device is packaged.
  • the fabricator may package the devices in a sterile package (e.g., a bag or box) and then illuminate the device to render it antimicrobial while within the sterile package. In this way, the device may remain sterile until the user removes the package in preparation for device installation.
  • the devices may, alternatively, be illuminated first and then sterilized when in a package or sterilized and then packaged.
  • the following is illustrative examples that are exemplary only and do not serve to limit the scope of the present disclosure.
  • the X-Ray diffraction data generated from some tests show that anatase may form close to the oxide thickness associated with a gold color. In some cases, higher levels, other than green-gray and gray, of crystalline anatase and/or rutile is associated with the oxide thickness associated with a green color. For this reason, gold and green anodized samples were chosen as additional test samples.
  • FIG. 10 shows a roughened surface from the as rolled titanium sheet, while FIG. 11 shows a less roughened surface and etching of the grain boundaries.
  • FIGS. 12-14 show the surface oxide of a gold anodized titanium sample tested in 0.5 M sulfuric acid.
  • the low magnification SEM image FIG. 11
  • FIG. 12 shows a higher magnification (1000 ⁇ ) of the same area. No surface difference can be distinguished between the darker and lighter areas and is comparable to the nitric-hydrofluoric pickled surface ( FIG. 11 ).
  • FIG. 14 shows an even higher magnification (5000 ⁇ ) in which the lighter surface area has some micro porosity forming while the dark area appears to remain smooth.
  • the X-Ray diffraction data did not show any peak intensities for anatase or rutile, indicating that the surface is amorphous or the crystalline areas present have a small intensity that cannot be distinguished from the background.
  • FIGS. 15-17 show the surface oxide of a gold anodized titanium sample tested in 2 M sulfuric acid.
  • FIG. 15 is a low magnification SEM image that shows a distribution of light and dark colored areas comparable to the 0.5 M gold sample ( FIG. 12 ).
  • FIG. 16 is a higher magnification (1000 ⁇ ) image that shows a few titanium grains with little to no discernible surface morphology difference between the dark and lighter areas. However, a higher magnification (5000 ⁇ ) of the same area shown in FIG. 17 shows the lighter area to have a more mirco porous surface morphology compared to the smooth dark area. This morphology difference is similar to that shown in FIG. 14 (high magnification 0.5 M gold sample) but seems to cover more of the surface. Again, no anatase or rutile peaks were found in the x-ray diffraction data for this sample.
  • FIGS. 18-20 show the surface oxide of a green anodized titanium sample tested in 0.94 M sulfuric acid.
  • the low magnification SEM image ( FIG. 18 ) shows a distribution of light and dark colored grains without any discernible surface roughness differences.
  • FIG. 19 shows a higher magnification (1000 ⁇ ) of the same area. A surface roughness and morphology difference can be clearly seen between the darker smooth areas in the middle of the image compared to the lighter areas around the periphery.
  • FIG. 20 shows an even higher magnification (5000 ⁇ ) in which the texture differences can be distinguished as boundaries between smooth flat areas and porous rougher areas. EBSD was used to evaluate the boundary seen in FIG. 20 at an approximate magnification of 15,000 ⁇ . The high magnification was needed to distinguish the very small anatase and rutile grains.
  • FIGS. 21-23 show the SEM representation of the area being scanned.
  • FIG. 22 is a grain orientation map which shows the division of the amorphous and crystalline regions of the area scanned shown in FIG. 21 . Comparing FIGS. 21 and 22 , the boundary between the smooth area and porous area can be distinguished as the boundary between the crystalline phase and amorphous phase. Furthermore, the different grain orientations found in the anatase and rutile crystalline area shows that the crystalline oxide is formed by many small different crystals formed on a single titanium grain.
  • FIG. 23 shows the distribution of the crystalline phases. Anatase was found to be the more prominent crystalline phase, as was to be expected from the XRD data ( FIG. 24 ).
  • FIGS. 25-27 show the surface oxide of a green anodized titanium sample tested in 2.0 M sulfuric acid.
  • the low magnification SEM image ( FIG. 25 ) shows a distribution of light and dark colored grains without any discernible surface texture differences similar to the 0.94 M green sample shown in FIG. 21 .
  • FIG. 26 shows a higher magnification (1000 ⁇ ) of the same area. The texture difference seen in the 0.94 M green sample cannot be as clearly seen in FIG. 26 .
  • a higher magnification (5000 ⁇ ) image in FIG. 27 shows that the boundaries that were evident in FIG. 20 (0.94 M) are not as apparent in the 2.0 M sample. Further inspection shows that the textured areas still have micro porosity that is not found on the smooth areas.
  • EBSD was used to evaluate a representative area at an approximate magnification of 15,000 ⁇ .
  • FIGS. 28-30 show the SEM representation of the area being scanned.
  • FIG. 29 shows the amorphous and crystalline regions of the area scanned. Comparing FIGS. 28 and 29 , there is no distinguishable boundary between the amorphous and crystalline areas of the surface oxide. The different grain orientations found in the crystalline area may show that the crystalline oxide is formed by many small different textured crystals.
  • FIG. 30 shows the distribution of the crystalline phases. Anatase was found to be the more prominent crystalline phase compared to rutile.
  • the higher magnification images show a higher degree of the micro porosity surfaces for the 2 M compared to the 0.5 M sample. Without being bound to any particular theory, these areas may be the beginning of a crystalline oxide area being formed.
  • the SEM and EBSD data from the 0.94 M and 2.0 M green samples shows a preliminary trend that as the molarity increases the confluence of the crystalline phase also increases. Comparing the X-Ray diffraction scans for both samples ( FIGS. 24 and 31 ) indicates that the anatase peak heights for both samples are very similar.
  • this may be an indicator that the crystalline phases (anatase and rutile) levels are similar for each thickness (color) but the confluence of the oxide may be influenced by the molarity of the anodization bath.

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20170079752A1 (en) * 2014-03-07 2017-03-23 Nobel Biocare Services Ag Implant surface composition
WO2017061755A1 (fr) * 2015-10-05 2017-04-13 한국과학기술연구원 Composite métallique orthopédique et dentaire permettant de favoriser l'angiogenèse par la génération d'espèces réactives de l'oxygène
US20180073159A1 (en) * 2016-09-09 2018-03-15 Apple Inc. Interference colored titanium with protective oxide film
US20200383223A1 (en) * 2019-05-28 2020-12-03 Apple Inc. Titanium surfaces with improved color consistency and resistance to color change
US11357600B2 (en) 2014-12-16 2022-06-14 Nobel Biocare Services Ag Dental implant

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPWO2019026540A1 (ja) * 2017-08-01 2020-06-11 学校法人中部大学 生体活性を有する立体構造物及びその製造方法
WO2020067500A1 (fr) * 2018-09-28 2020-04-02 株式会社三菱ケミカルホールディングス Matériau antimicrobien, corps stratifié, corps stratifié antimicrobien, élément médical, procédé de production de matériau antimicrobien, procédé de production de corps stratifié antimicrobien, et procédé antimicrobien
CN109297998A (zh) * 2018-11-29 2019-02-01 上海航天精密机械研究所 一种室温下快速制备钛及钛合金ebsd试样的方法
JP7479665B2 (ja) 2020-01-10 2024-05-09 国立大学法人北海道国立大学機構 二酸化チタン皮膜を有するＮｉＴｉ合金の製造方法
JP7502601B2 (ja) 2020-03-06 2024-06-19 日本製鉄株式会社 チタン材およびその製造方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030074062A1 (en) * 2001-08-01 2003-04-17 Monzyk Bruce F. Photolytic artificial lung
US20060190058A1 (en) * 2004-12-03 2006-08-24 Greenberg Robert J Visual prosthesis for improved circadian rhythms and method of improving the circadian rhythms
US20110112649A1 (en) * 2009-11-09 2011-05-12 Biomet Manufacturing Corp. Radial and ulnar replacement
EP2546372A2 (fr) * 2008-10-21 2013-01-16 Keystone Dental, Inc. Composant métallique pour des applications médicales, chirurgicales et implantologicales

Family Cites Families (28)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS60253439A (ja) * 1984-05-29 1985-12-14 京セラ株式会社 チタン系義歯床用金属部材
JPS63158050A (ja) * 1986-12-19 1988-07-01 川原　春幸 着色金属製人工歯根
JPS6483692A (en) * 1987-09-22 1989-03-29 Kobe Steel Ltd Colored titanium material
JPH0282966A (ja) * 1988-09-20 1990-03-23 Oonitsuku Kk 歯科材処理方法
JP2661451B2 (ja) * 1992-02-14 1997-10-08 株式会社ニコン インプラントとその製造方法
JPH06154255A (ja) * 1992-11-18 1994-06-03 Nikon Corp インプラントの製造方法
JPH078511A (ja) * 1993-06-24 1995-01-13 Nikon Corp インプラント及びその製造方法
JP3129041B2 (ja) * 1993-08-05 2001-01-29 株式会社ニコン インプラント及びその製造方法
JPH0747115A (ja) * 1993-08-05 1995-02-21 Nikon Corp インプラント及びその製造方法
JPH0747116A (ja) * 1993-08-05 1995-02-21 Nikon Corp インプラントの製造方法
JPH08173523A (ja) * 1994-12-20 1996-07-09 Nikon Corp 骨内インプラント及びその製造方法
SE513481C2 (sv) * 1997-05-16 2000-09-18 Nobel Biocare Ab Implantatelement utfört av titan med en titanoxidyta modifierad med eloxidering
JPH119679A (ja) * 1997-06-20 1999-01-19 Nikon Corp インプラントの製造方法
JPH1143799A (ja) * 1997-07-24 1999-02-16 Nikon Corp 生体親和性酸化チタン皮膜の製造方法
GB0208642D0 (en) * 2002-04-16 2002-05-22 Accentus Plc Metal implants
US20060229715A1 (en) * 2005-03-29 2006-10-12 Sdgi Holdings, Inc. Implants incorporating nanotubes and methods for producing the same
JP4883603B2 (ja) * 2005-09-08 2012-02-22 学校法人近畿大学 骨代替材料の製造方法
US20110125263A1 (en) * 2007-08-24 2011-05-26 Brown University Method for producing nanostructures on a surface of a medical implant
AU2008306596B2 (en) * 2007-10-03 2013-04-04 Accentus Plc Method of manufacturing metal with biocidal properties
US8545559B2 (en) * 2007-10-05 2013-10-01 Washington State University Modified metal materials, surface modifications to improve cell interactions and antimicrobial properties, and methods for modifying metal surface properties
GB0720982D0 (en) * 2007-10-25 2007-12-05 Plasma Coatings Ltd Method of forming a bioactive coating
JP5463502B2 (ja) * 2008-06-27 2014-04-09 国立大学法人東北大学 超音波照射陽極酸化法による二酸化チタン製造法
JP5646809B2 (ja) * 2008-10-29 2014-12-24 国立大学法人佐賀大学 抗菌製品及びその製造方法
JP2010215438A (ja) * 2009-03-15 2010-09-30 Tokyo Institute Of Technology 酸化チタン膜および酸化チタン膜形成方法
GB0905354D0 (en) * 2009-03-30 2009-05-13 Accentus Plc Metal treatment
JP2011019786A (ja) * 2009-07-17 2011-02-03 Nagoya Univ 酸化チタン被膜材料及びその製造方法
WO2011024216A1 (fr) * 2009-08-25 2011-03-03 株式会社プロステック Pièce médicale et son procédé de fabrication
JPWO2011093414A1 (ja) * 2010-01-27 2013-06-06 国立大学法人 東京医科歯科大学 金属酸化物、金属材料、生体親和材料、および金属酸化物の製造方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030074062A1 (en) * 2001-08-01 2003-04-17 Monzyk Bruce F. Photolytic artificial lung
US20060190058A1 (en) * 2004-12-03 2006-08-24 Greenberg Robert J Visual prosthesis for improved circadian rhythms and method of improving the circadian rhythms
EP2546372A2 (fr) * 2008-10-21 2013-01-16 Keystone Dental, Inc. Composant métallique pour des applications médicales, chirurgicales et implantologicales
US20110112649A1 (en) * 2009-11-09 2011-05-12 Biomet Manufacturing Corp. Radial and ulnar replacement

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
Kern et al. Thin Solid Films, 494, 2006, 279-286. *
Mantzila et al. Electrochimica Acta 51, 2006, 3537-3542. *

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20170079752A1 (en) * 2014-03-07 2017-03-23 Nobel Biocare Services Ag Implant surface composition
US11357600B2 (en) 2014-12-16 2022-06-14 Nobel Biocare Services Ag Dental implant
US11918434B2 (en) 2014-12-16 2024-03-05 Nobel Biocare Services Ag Dental implant
WO2017061755A1 (fr) * 2015-10-05 2017-04-13 한국과학기술연구원 Composite métallique orthopédique et dentaire permettant de favoriser l'angiogenèse par la génération d'espèces réactives de l'oxygène
US20180073159A1 (en) * 2016-09-09 2018-03-15 Apple Inc. Interference colored titanium with protective oxide film
US20200383223A1 (en) * 2019-05-28 2020-12-03 Apple Inc. Titanium surfaces with improved color consistency and resistance to color change
US11032930B2 (en) * 2019-05-28 2021-06-08 Apple Inc. Titanium surfaces with improved color consistency and resistance to color change

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