WO1996016196A2 - Deposition au laser de revetements - Google Patents

Deposition au laser de revetements Download PDF

Info

Publication number
WO1996016196A2
WO1996016196A2 PCT/GB1995/002703 GB9502703W WO9616196A2 WO 1996016196 A2 WO1996016196 A2 WO 1996016196A2 GB 9502703 W GB9502703 W GB 9502703W WO 9616196 A2 WO9616196 A2 WO 9616196A2
Authority
WO
WIPO (PCT)
Prior art keywords
laser
coating
substrate
deposition
fluence
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/GB1995/002703
Other languages
English (en)
Other versions
WO1996016196A3 (fr
Inventor
Steven Melvyn Howdle
Eugene Nikolaevich Antonov
Viktor Nikolaivich Bagratashvili
Vladimir Karpovich Popov
Emil Naumovich Sobol
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.)
University of Nottingham
Original Assignee
University of Nottingham
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by University of Nottingham filed Critical University of Nottingham
Priority to AU38764/95A priority Critical patent/AU3876495A/en
Publication of WO1996016196A2 publication Critical patent/WO1996016196A2/fr
Publication of WO1996016196A3 publication Critical patent/WO1996016196A3/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/24—Vacuum evaporation
    • C23C14/28—Vacuum evaporation by wave energy or particle radiation
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
    • A61F2/00—Filters implantable into blood vessels; Prostheses, i.e. artificial substitutes or replacements for parts of the body; Appliances for connecting them with the body; Devices providing patency to, or preventing collapsing of, tubular structures of the body, e.g. stents
    • A61F2/02—Prostheses implantable into the body
    • A61F2/30—Joints
    • A61F2/30767—Special external or bone-contacting surface, e.g. coating for improving bone ingrowth
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K6/00—Preparations for dentistry
    • A61K6/80—Preparations for artificial teeth, for filling teeth or for capping teeth
    • A61K6/831—Preparations for artificial teeth, for filling teeth or for capping teeth comprising non-metallic elements or compounds thereof, e.g. carbon
    • A61K6/838—Phosphorus compounds, e.g. apatite
    • 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
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/28—Materials for coating prostheses
    • A61L27/30—Inorganic materials
    • A61L27/32—Phosphorus-containing materials, e.g. apatite
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/02—Pretreatment of the material to be coated
    • C23C14/021—Cleaning or etching treatments
    • C23C14/022—Cleaning or etching treatments by means of bombardment with energetic particles or radiation
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/12—Organic material
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/58—After-treatment
    • C23C14/5806—Thermal treatment
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/58—After-treatment
    • C23C14/584—Non-reactive treatment
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
    • A61F2/00—Filters implantable into blood vessels; Prostheses, i.e. artificial substitutes or replacements for parts of the body; Appliances for connecting them with the body; Devices providing patency to, or preventing collapsing of, tubular structures of the body, e.g. stents
    • A61F2/02—Prostheses implantable into the body
    • A61F2/30—Joints
    • A61F2/3094—Designing or manufacturing processes
    • A61F2002/3097—Designing or manufacturing processes using laser
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
    • A61F2310/00—Prostheses classified in A61F2/28 or A61F2/30 - A61F2/44 being constructed from or coated with a particular material
    • A61F2310/00005—The prosthesis being constructed from a particular material
    • A61F2310/00011—Metals or alloys
    • A61F2310/00023—Titanium or titanium-based alloys, e.g. Ti-Ni alloys
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
    • A61F2310/00—Prostheses classified in A61F2/28 or A61F2/30 - A61F2/44 being constructed from or coated with a particular material
    • A61F2310/00389—The prosthesis being coated or covered with a particular material
    • A61F2310/00592—Coating or prosthesis-covering structure made of ceramics or of ceramic-like compounds
    • A61F2310/00796—Coating or prosthesis-covering structure made of a phosphorus-containing compound, e.g. hydroxy(l)apatite

Definitions

  • the present invention concerns the coating of sub ⁇ strates using laser deposition (laser sputtering) techniques, and relates in particular, although not exclusively, to deposition of bioco patible coatings, particularly of apatite-based (calcium phosphates) based materials.
  • Medical and dental implants and prostheses are normally formed from metals or alloys which can provide sufficient mechanical strength for the intended purpose.
  • corrosion products from degradation of these materials may give rise to tissue irritation and inflammation.
  • This problem is frequently overcome by giving the implant a biocompatible coating.
  • the mineral basis of bone is calcium hydroxyapatite [Ca 1Q (P0. ) 6 (0H)_] , and this and other calcium phospates are thus commonly used for this purpose.
  • Techniques employed for the coating process include RF plasma spraying, electrophoretic deposition, sol-gel chemical methods and laser sputtering.
  • the coating process normally requires the substrate to be maintained at a temperature of approximately 400 to 500°C in order to achieve adequate coating, but this precludes the use as the substrate of materials having relatively low melting points such as polymers and plastics.
  • the present invention seeks to mitigate or obviate these or other difficulties and to provide improved coating methods and coated substrates.
  • a method of coating a substrate by laser deposition which method comprises a pre-deposition laser treatment of a surface of the substrate prior to coating .
  • the laser is a pulsed laser.
  • the pre-deposition laser treatment may be carried out using the same laser as the deposition process.
  • the treatment may be effected by scanning the substrate surface with the laser.
  • the pre-deposition laser treatment is carried out immediately prior to the coating process.
  • the substrate may be retained between treatment and coating in an appropriate controlled atmosphere .
  • the coating applied comprises an apatite or hydroxyapatite.
  • the laser deposition coating process may be carr ⁇ ied out at a temperature less than 500°C, and in parti ⁇ cular at ambient temperature.
  • the method may further comprise a step of heating the coated substrate to a temperature higher than that at which the coating process was carried out to change or modify the morphology of the coating.
  • the invention further provides a method of coating a metallic substrate according to any of the preceding paragraphs.
  • a second aspect of the invention provides a method of coating a substrate of a polymer or a plastics material by laser deposition, wherein the coating process is carried out at a temperature below the melting or softening temperature of the substrate.
  • the laser is a pulsed laser.
  • the method may include a pre-deposition laser treatment of a surface of the substrate prior to coating .
  • the laser treatment may be carried out using the same laser as the deposition process.
  • the treatment may be achieved by scanning the substrate surface with the laser .
  • the laser treatment step is carried out immediately prior to the coating process.
  • the substrate may be retained between treatment and coating in an appropriate controlled atmosphere .
  • the coating applied comprises an apatite or hydroxyapatite.
  • a method of coating a substrate comprising applying a first stage coating by a method according to the first or second aspect of the invention, and subsequently applying a second stage coating to increase the thickness of the coating layer.
  • the second stage coating may be applied by a second laser deposition step.
  • the second laser deposition step may employ one or more deposition parameters or characteristics different from the first.
  • the second stage coating may be applied by plasma spraying or any other suitable technique .
  • a method of coating a substrate by laser deposition comprising controlling at least one laser deposition characteristic selected from the group comprising laser fluence, vacuum chamber atmosphere and vacuum gas pressure, whereby to control the composition and/or microparticle distribution of the laser deposited coating.
  • the laser fluence and/or chamber gas pressure may be selected to control the macroparticle size distribution.
  • the chamber gas pressure, chamber atmosphere, and/or the laser fluence may be selected to control the composition of the coating.
  • the laser fluence may be controlled within the
  • the laser fluence may be controlled within the
  • the laser fluence is controlled
  • the laser fluence may be controlled
  • the vacuum gas pressure may be controlled within the range of 0.001 to 100Pa, preferably within the range of 2 to 100Pa, more preferably it is controlled at substantially 4Pa.
  • the vacuum chamber atmosphere may comprise air. Carbon dioxide and/or water may be bled into the atmosphere. This would have the effect of altering the composition of the coating.
  • a method of coating a substrate by laser deposition comprising controlling at least one laser deposition characteristic selected from the group comprising laser fluence, vacuum chamber atmosphere and vacuum gas pressure, whereby to control the stability to dissolution in fluids of the laser deposited coating.
  • the vacuum chamber gas pressure may be controlled within the range of 0.001 to 100Pa, preferably 2 to
  • 100Pa more preferably it is controlled at substantially 4Pa.
  • the stability to dissolution of a laser deposited apatite or hydroxyapatite coating in a body fluid or a simulated body fluid may be controlled by the method.
  • the laser fluence may be controlled within the
  • the laser fluence may be controlled within the range 2 to 15 J/cm 2 , preferably 9 J/cm2.
  • the laser fluence may be controlled within the range of 0.7 to 11 J/cm preferably within
  • the laser fluence may be controlled
  • the vacuum chamber atmosphere may comprise air.
  • Carbon dioxide and/or water may be bled into the atmosphere. This would have the effect of altering the composition of the coating.
  • a substrate having a coating applied by a method as hereinbefore described.
  • the coating may comprise an apatite or hydroxyapatite.
  • the substrate may comprise a metal, an alloy, a polymer or a plastics material .
  • the coating (target) has an absorptivity sufficient to allow evaporation at accessible values of laser fluence.
  • a medical or dental implant having a coating applied by a method according to the first, second or third aspect of the invention.
  • the coating may comprise hydroxyapatite or an apatite.
  • Fig. 1 is a graph of film adhesion as a function of fluence for various targets
  • Fig. 2 represents FT-IR spectra of various films
  • Fig. 3 shows size distribution of macroparticles relative to volume for hydroxyapatite coatings
  • Fig. 4 shows average nearest neighbour distance between macroparticles in two different size ranges
  • Fig. 5 shows average calcium/phosphorus ratio relative to pressure in deposition chamber
  • Fig. 6 shows average calcium/phosphorus ratio for hydroxyapatite coatings against distance from centre of ablation plume.
  • HA hydroxyapatite
  • NA natural apatite
  • the focussed UV laser beam was scanned periodically across the target in order to avoid the formation of deep craters in the target.
  • the laser pulse repetition rate was 5 Hz pulse energy up to 300 J (controlled by attenuator) and laser
  • the target to substrate distance was 3.5 cm and a Ti foil target (0.05 mm thickness) was used as substrate for deposition (titanium is an important implant material).
  • the film thickness was varied fro ⁇ rf-O.1 to ⁇ *-+ 2 L/m and o the deposition rate was in the range 0.02 to 5 A/pulse.
  • the deposited apatite films were examined by scanning electron microscopy (SEM), Fourier Transform infra-red spectroscopy (FT-IR) and Raman spectroscopy.
  • SEM scanning electron microscopy
  • FT-IR Fourier Transform infra-red spectroscopy
  • Raman spectroscopy The film adhesion was determined by a scratch test. The scratching was made by a corundum point with I Lfm radius. The adhesive force was determined by the maxium vertical load which could be applied to the point, without stripping the film from the substrate.
  • the films deposited from HA (Comparative Example) and NA samples were mirror-like and scanning electron micrographs showed smooth surfaces with round shaped particles of 1-10 lm in size. Both the quantity and the size of particles was controlled by increasing the laser fluence. The films deposited from bone tissue were much more spongy and round shaped particles appeared only at
  • the films were investigated by FT-IR spectroscopy.
  • the vibration bands of the phosphate ions (PO 4.) of HA appear in the range 550-610 cm -1 and 1000-1100 cm-1
  • Example 1 The experiments of Example 1 were repeated with the additon of a laser precleaning step in which the deposition laser was first used to scan the surface of the substrate to be coated immediately prior to the deposition process.
  • Results of initial scratch tests indicate significantly greater adhesion of coatings with inclusion of the precleaning step compared with the adhesion of coatings applied under identical conditions but excluding laser precleaning.
  • Spectroscopic and microscopic investigation indicates that, other than the adhesion differences, the coatings are identical.
  • the improved adhesion may be due to changes to interface properties induced by the laser precleaning.
  • the apatite coating process is preceded by a laser precleaning step and is carried out at relatively low temperatures
  • the apatite coating achieved is amorp ⁇ hous rather than crystalline. Its mechanical adhesion propert.es appear, however, better than those of crystalline coatings formed using conventional techniques. If a crystalline coating is particularly required, a metal substrate initially coated at relatively low temperature may be subsequently heat-treated in order to cause the amorphous coating to be converted to crystalline.
  • the substrate may be retained between cleaning and coating in a suitably controlled atmosphere, if coating is not to be carried out immediately.
  • the surface properties of the coating may be predetermined by selection of appropriate laser deposition characteristics such as laser fluence, vacuum chamber atmosphere and residual gas pressure in the chamber.
  • the distribution of macroparticles, their sizes, and the overall chemical composition of the coating can be determined by these parameters.
  • the biocompatibility of the coatings i.e. the way in which cells interact with the surface, is very closely dependent upon the macroparticle distribution and chemical composition. Fine control over the biocompatability of the coatings produced is therefore possible.
  • the properties may be tuned for the particular application of an implant to be coated, for example cell interaction with an artificial heart valve should be discouraged to prevent blockage and failure, whereas strong cell interaction and growth is encouraged with a hip replacement.
  • the stability to dissolution in fluids of the coatings may also be controlled by selection of deposition characteristics such as laser fluence and vacuum chamber residual gas pressure.
  • deposition characteristics such as laser fluence and vacuum chamber residual gas pressure.
  • the erosion resistance is increased.
  • Apatite films were deposited on substrates at ambient temperature in an evacuable chamber with residual pressure (Pr )controlled from 2 to 100 Pa.
  • Laser deposition was achieved with a KrF laser operated at a pulse duration of 20 ns and pulse repetition rate of 10 Hz.
  • the laser fluence (F) was varied from 0.5 to
  • Substrate materials were commercial Ti foil (300,(m thickness) and Ti-Al-V alloy. Hydroxyapatite (HA) and dense crystalline natural apatite (NA) were used as targets.
  • the laser deposited films typically 0.2 to 1.2t/m in thickness, were examined by SEM and EDAX analysis. From the SEM micrographs, all macroparticles measuring more than 0.2// in diameter were counted in order to calculate average distances between the macroparticles (MP) and to obtain the distribution of the MP by volume. EDAX analysis allows measurement of the local stoichiometry and thus the Ca/P ratio of the smooth surface, the MP , and an average across an area of the film.
  • the method of the invention may be used to apply a first-stage coating to a substrate, the thickness of the coating subsequently being increased in a second-stage process, which may use plasma spraying or another suitable technique.
  • the second stage may be a further pulsed laser deposition, which may use different deposition and laser parameters from the first .
  • the invention is described herein with particular reference to the application of biocompatible coatings to medical and dental implants, its scope is not limited in this respect.
  • the invention may be applied to organic and metallic as well as to inorganic coatings.
  • the ability to deposit such coatings on polymers or plastics at ambient temperatures may find use in the production of filters (for example for blood products) or of polymeric materials with novel electrical or optical properties.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Oral & Maxillofacial Surgery (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • Epidemiology (AREA)
  • Transplantation (AREA)
  • Cardiology (AREA)
  • Heart & Thoracic Surgery (AREA)
  • Dermatology (AREA)
  • Inorganic Chemistry (AREA)
  • Orthopedic Medicine & Surgery (AREA)
  • Toxicology (AREA)
  • Biomedical Technology (AREA)
  • Medicinal Chemistry (AREA)
  • Vascular Medicine (AREA)
  • Plastic & Reconstructive Surgery (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Materials For Medical Uses (AREA)
  • Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)

Abstract

La présente invention concerne un procédé de revêtement d'un substrat par déposition au laser, ledit procédé comportant un traitement de prédéposition au laser d'une surface du substrat avant l'opération de revêtement. On peut déposer ledit revêtement sur des matières plastiques ou polymères, en dessous de la température de ramolissement. Le substrat peut être un implant médical ou dentaire, et le revêtement une apatite ou une hydroxyapatite. On peut intervenir sur la composition, la compatibilité biologique et la stabilité relative à la dissolution dans certains fluides du revêtement grâce à la sélection d'au moins une des caractéristiques de déposition du laser.
PCT/GB1995/002703 1994-11-18 1995-11-20 Deposition au laser de revetements Ceased WO1996016196A2 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU38764/95A AU3876495A (en) 1994-11-18 1995-11-20 Laser deposition of coatings

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB9423277A GB9423277D0 (en) 1994-11-18 1994-11-18 Pulsed laser deposition of coatings
GB9423277.4 1994-11-18

Publications (2)

Publication Number Publication Date
WO1996016196A2 true WO1996016196A2 (fr) 1996-05-30
WO1996016196A3 WO1996016196A3 (fr) 1996-07-18

Family

ID=10764591

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/GB1995/002703 Ceased WO1996016196A2 (fr) 1994-11-18 1995-11-20 Deposition au laser de revetements

Country Status (3)

Country Link
AU (1) AU3876495A (fr)
GB (1) GB9423277D0 (fr)
WO (1) WO1996016196A2 (fr)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998021380A1 (fr) * 1996-11-12 1998-05-22 Universidad De Vigo Procede d'amelioration de l'osteointegration d'implants de fixation osseuse
WO1999042631A1 (fr) * 1998-02-19 1999-08-26 Universidad De Vigo Revetements biocompatibles produits par laser
FR2785834A1 (fr) * 1998-11-17 2000-05-19 Armines Ass Pour La Rech Et Le Procede de traitement de surface d'un materiau destine a recevoir un revetement
DE10137763A1 (de) * 2001-08-02 2003-04-30 Siemens Ag Verfahren zur Oberflächenvorbehandlung einer zu beschichtenden Oberfläche eines Substrates mit einem Beschichtungsmaterial
US10370426B2 (en) 2015-12-31 2019-08-06 Hanmi Pharm. Co., Ltd Triple glucagon/GLP-1/GIP receptor agonist
US10696725B2 (en) 2015-06-30 2020-06-30 Hanmi Pharm. Co., Ltd. Glucagon derivative and a composition comprising a long acting conjugate of the same
US11135271B2 (en) 2014-12-30 2021-10-05 Hanmi Pharm. Co., Ltd. Glucagon derivatives with improved stability
US11142559B2 (en) 2016-06-29 2021-10-12 Hanmi Pharm. Co., Ltd. Glucagon derivative, conjugate thereof, composition comprising same, and therapeutic use thereof

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115429940B (zh) * 2022-08-30 2024-01-26 电子科技大学 一种增强生物活性涂层稳定性的方法

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5242706A (en) * 1991-07-31 1993-09-07 The United States Of America As Represented By The Secretary Of The Navy Laser-deposited biocompatible films and methods and apparatuses for producing same
IT1250211B (it) * 1991-11-22 1995-04-03 Fiat Auto Spa Procedimento per il trattamento superficiale a mezzo laser di metalli da rivestire.
JP3255469B2 (ja) * 1992-11-30 2002-02-12 三菱電機株式会社 レーザ薄膜形成装置

Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998021380A1 (fr) * 1996-11-12 1998-05-22 Universidad De Vigo Procede d'amelioration de l'osteointegration d'implants de fixation osseuse
ES2113834A1 (es) * 1996-11-12 1998-06-01 Univ Vigo Metodo de mejora de la osteointegracion de implantes de fijacion osea.
US6339913B1 (en) 1996-11-12 2002-01-22 Universidad De Vigo Method for improving the osteointegration of osseus fixing implants
WO1999042631A1 (fr) * 1998-02-19 1999-08-26 Universidad De Vigo Revetements biocompatibles produits par laser
ES2143938A1 (es) * 1998-02-19 2000-05-16 Univ Vigo Recubrimientos biocompatibles producidos mediante laser.
FR2785834A1 (fr) * 1998-11-17 2000-05-19 Armines Ass Pour La Rech Et Le Procede de traitement de surface d'un materiau destine a recevoir un revetement
WO2000029129A1 (fr) * 1998-11-17 2000-05-25 Armines Procede de traitement de surface d'un materiau destine a recevoir un revetement
DE10137763C2 (de) * 2001-08-02 2003-08-14 Siemens Ag Verfahren zur Oberflächenvorbehandlung einer zu beschichtenden Oberfläche eines Substrates mit einem Beschichtungsmaterial
DE10137763A1 (de) * 2001-08-02 2003-04-30 Siemens Ag Verfahren zur Oberflächenvorbehandlung einer zu beschichtenden Oberfläche eines Substrates mit einem Beschichtungsmaterial
US11135271B2 (en) 2014-12-30 2021-10-05 Hanmi Pharm. Co., Ltd. Glucagon derivatives with improved stability
US10696725B2 (en) 2015-06-30 2020-06-30 Hanmi Pharm. Co., Ltd. Glucagon derivative and a composition comprising a long acting conjugate of the same
US11261227B2 (en) 2015-06-30 2022-03-01 Hanmi Pharm. Co., Ltd. Glucagon derivative and a composition comprising a long acting conjugate of the same
US11667688B2 (en) 2015-06-30 2023-06-06 Hanmi Pharm. Co., Ltd. Glucagon derivative and a composition comprising a long acting conjugate of the same
US10370426B2 (en) 2015-12-31 2019-08-06 Hanmi Pharm. Co., Ltd Triple glucagon/GLP-1/GIP receptor agonist
US10400020B2 (en) 2015-12-31 2019-09-03 Hanmi Pharm. Co., Ltd. Long-acting conjugate of triple glucagon/GLP-1/GIP receptor agonist
US10981967B2 (en) 2015-12-31 2021-04-20 Hanmi Pharm. Co., Ltd. Long-acting conjugate of triple glucagon/GLP-1/GIP receptor agonist
US11332508B2 (en) 2015-12-31 2022-05-17 Hanmi Pharm. Co., Ltd. Triple glucagon/GLP-1/GIP receptor agonist
US11142559B2 (en) 2016-06-29 2021-10-12 Hanmi Pharm. Co., Ltd. Glucagon derivative, conjugate thereof, composition comprising same, and therapeutic use thereof

Also Published As

Publication number Publication date
WO1996016196A3 (fr) 1996-07-18
GB9423277D0 (en) 1995-01-11
AU3876495A (en) 1996-06-17

Similar Documents

Publication Publication Date Title
Blind et al. Characterization of hydroxyapatite films obtained by pulsed-laser deposition on Ti and Ti-6AL-4v substrates
Sato et al. Enhanced osteoblast adhesion on hydrothermally treated hydroxyapatite/titania/poly (lactide-co-glycolide) sol–gel titanium coatings
Hahn et al. Aerosol deposition of hydroxyapatite–chitosan composite coatings on biodegradable magnesium alloy
Pichugin et al. The preparation of calcium phosphate coatings on titanium and nickel–titanium by rf-magnetron-sputtered deposition: Composition, structure and micromechanical properties
Nelea et al. Hydroxyapatite thin films grown by pulsed laser deposition and radio-frequency magnetron sputtering: comparative study
Koch et al. Pulsed laser deposition of hydroxyapatite thin films
US6136369A (en) Device for incorporation and release of biologically active agents
US6069295A (en) Implant material
AU736802B2 (en) Calcium-phosphate coated implant element
Torkaman et al. Electrochemical and in vitro bioactivity of nanocomposite gelatin-forsterite coatings on AISI 316 L stainless steel
Lo et al. Physical, chemical, and biological characterization of pulsed laser deposited and plasma sputtered hydroxyapatite thin films on titanium alloy
US20080275546A1 (en) Inhibitory cell adhesion surfaces
Shtansky et al. A new combined approach to metal-ceramic implants with controllable surface topography, chemistry, blind porosity, and wettability
Vladescu et al. Enhancement of the mechanical properties of hydroxyapatite by SiC addition
Jamesh et al. Evaluation of corrosion resistance and cytocompatibility of graded metal carbon film on Ti and NiTi prepared by hybrid cathodic arc/glow discharge plasma-assisted chemical vapor deposition
WO1996016196A2 (fr) Deposition au laser de revetements
Gnanavel et al. Biocompatible response of hydroxyapatite coated on near-β titanium alloys by E-beam evaporation method
Thampi et al. Enhancement of bioactivity of pulsed magnetron sputtered TiCxNy with bioactive glass (BAG) incorporated polycaprolactone (PCL) composite scaffold
Grubova et al. Sand-blasting treatment as a way to improve the adhesion strength of hydroxyapatite coating on titanium implant
Lo et al. Hydroxyapatite thin films deposited onto uncoated and (Ti, Al, V) N‐coated Ti alloys
Man et al. Surface characteristics and corrosion behavior of laser surface nitrided NiTi shape memory alloy for biomedical applications
EP3195825B1 (fr) Implant dentaire
Azis et al. Effect of annealing on microstructure of hydroxyapatite coatings and their behaviours in simulated body fluid
Greish et al. Structural evaluation, preliminary in vitro stability and electrochemical behavior of apatite coatings on Ti6Al4V substrates
Wang et al. Biocompatibility study of plasma-coated nitinol (NiTi alloy) stents

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A2

Designated state(s): AL AM AT AU BB BG BR BY CA CH CN CZ DE DK EE ES FI GB GE HU IS JP KE KG KP KR KZ LK LR LS LT LU LV MD MG MK MN MW MX NO NZ PL PT RO RU SD SE SG SI SK TJ TM TT UA UG US UZ VN

AL Designated countries for regional patents

Kind code of ref document: A2

Designated state(s): KE LS MW SD SZ UG AT BE CH DE DK ES FR GB GR IE IT LU MC NL PT SE BF BJ CF CG CI CM GA GN ML MR NE SN TD TG

121 Ep: the epo has been informed by wipo that ep was designated in this application
122 Ep: pct application non-entry in european phase
REG Reference to national code

Ref country code: DE

Ref legal event code: 8642

NENP Non-entry into the national phase

Ref country code: CA