CA2205107A1 - Implant material and process for producing it - Google Patents
Implant material and process for producing itInfo
- Publication number
- CA2205107A1 CA2205107A1 CA002205107A CA2205107A CA2205107A1 CA 2205107 A1 CA2205107 A1 CA 2205107A1 CA 002205107 A CA002205107 A CA 002205107A CA 2205107 A CA2205107 A CA 2205107A CA 2205107 A1 CA2205107 A1 CA 2205107A1
- Authority
- CA
- Canada
- Prior art keywords
- thc
- implantable device
- calcium
- surface roughness
- implant
- 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.)
- Abandoned
Links
- 239000007943 implant Substances 0.000 title claims abstract description 14
- 238000000034 method Methods 0.000 title claims abstract description 9
- 239000000463 material Substances 0.000 title claims description 5
- 239000011575 calcium Substances 0.000 claims abstract description 45
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 29
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000001506 calcium phosphate Substances 0.000 claims abstract description 4
- 229910000389 calcium phosphate Inorganic materials 0.000 claims abstract description 4
- 235000011010 calcium phosphates Nutrition 0.000 claims abstract description 4
- 239000011148 porous material Substances 0.000 claims abstract description 4
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 claims abstract description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 3
- 230000003746 surface roughness Effects 0.000 claims abstract 5
- 238000004381 surface treatment Methods 0.000 claims abstract 5
- 238000001556 precipitation Methods 0.000 claims abstract 2
- 239000000126 substance Substances 0.000 claims abstract 2
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 238000001356 surgical procedure Methods 0.000 claims description 2
- 230000002378 acidificating effect Effects 0.000 claims 1
- 239000000316 bone substitute Substances 0.000 claims 1
- 229910010293 ceramic material Inorganic materials 0.000 claims 1
- 239000002131 composite material Substances 0.000 claims 1
- 239000004053 dental implant Substances 0.000 claims 1
- 229910003460 diamond Inorganic materials 0.000 claims 1
- 239000010432 diamond Substances 0.000 claims 1
- 229910001092 metal group alloy Inorganic materials 0.000 claims 1
- 229920005615 natural polymer Polymers 0.000 claims 1
- 238000009991 scouring Methods 0.000 claims 1
- 229920001059 synthetic polymer Polymers 0.000 claims 1
- 238000000576 coating method Methods 0.000 description 27
- 239000011248 coating agent Substances 0.000 description 23
- 239000010936 titanium Substances 0.000 description 16
- 229910045601 alloy Inorganic materials 0.000 description 11
- 239000000956 alloy Substances 0.000 description 11
- 239000012981 Hank's balanced salt solution Substances 0.000 description 9
- 229910052586 apatite Inorganic materials 0.000 description 6
- 210000000988 bone and bone Anatomy 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 5
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 5
- VSIIXMUUUJUKCM-UHFFFAOYSA-D pentacalcium;fluoride;triphosphate Chemical compound [F-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O VSIIXMUUUJUKCM-UHFFFAOYSA-D 0.000 description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 229910052719 titanium Inorganic materials 0.000 description 4
- 241000282337 Nasua nasua Species 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 241000256844 Apis mellifera Species 0.000 description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910001651 emery Inorganic materials 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 238000000338 in vitro Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- GXMBHQRROXQUJS-UHFFFAOYSA-N (2-hept-2-ynylsulfanylphenyl) acetate Chemical compound CCCCC#CCSC1=CC=CC=C1OC(C)=O GXMBHQRROXQUJS-UHFFFAOYSA-N 0.000 description 1
- 241000180579 Arca Species 0.000 description 1
- 101100283604 Caenorhabditis elegans pigk-1 gene Proteins 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 101100114828 Drosophila melanogaster Orai gene Proteins 0.000 description 1
- 101100536931 Escherichia coli (strain K12) thiD gene Proteins 0.000 description 1
- 101100159279 Escherichia coli (strain K12) yajL gene Proteins 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 241000283986 Lepus Species 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 235000014676 Phragmites communis Nutrition 0.000 description 1
- 101150107341 RERE gene Proteins 0.000 description 1
- 101100007331 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) COS3 gene Proteins 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 229910001069 Ti alloy Inorganic materials 0.000 description 1
- 229910000883 Ti6Al4V Inorganic materials 0.000 description 1
- 230000001464 adherent effect Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- XKRFYHLGVUSROY-UHFFFAOYSA-N argon Substances [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- -1 argon ion Chemical class 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000003185 calcium uptake Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- UZUODNWWWUQRIR-UHFFFAOYSA-L disodium;3-aminonaphthalene-1,5-disulfonate Chemical compound [Na+].[Na+].C1=CC=C(S([O-])(=O)=O)C2=CC(N)=CC(S([O-])(=O)=O)=C21 UZUODNWWWUQRIR-UHFFFAOYSA-L 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- ZZUFCTLCJUWOSV-UHFFFAOYSA-N furosemide Chemical compound C1=C(Cl)C(S(=O)(=O)N)=CC(C(O)=O)=C1NCC1=CC=CO1 ZZUFCTLCJUWOSV-UHFFFAOYSA-N 0.000 description 1
- 238000001727 in vivo Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000010884 ion-beam technique Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229920000747 poly(lactic acid) Polymers 0.000 description 1
- 239000004626 polylactic acid Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- GGWBHVILAJZWKJ-KJEVSKRMSA-N ranitidine hydrochloride Chemical compound [H+].[Cl-].[O-][N+](=O)\C=C(/NC)NCCSCC1=CC=C(CN(C)C)O1 GGWBHVILAJZWKJ-KJEVSKRMSA-N 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 101150115956 slc25a26 gene Proteins 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 101150072109 trr1 gene Proteins 0.000 description 1
Classifications
-
- 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
-
- 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
- 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
- A61L27/02—Inorganic materials
- A61L27/04—Metals or alloys
- A61L27/06—Titanium or titanium 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
- 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
- A61F2002/30001—Additional features of subject-matter classified in A61F2/28, A61F2/30 and subgroups thereof
- A61F2002/30667—Features concerning an interaction with the environment or a particular use of the prosthesis
- A61F2002/30677—Means for introducing or releasing pharmaceutical products, e.g. antibiotics, into the body
-
- 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
- A61F2002/30906—Special external or bone-contacting surface, e.g. coating for improving bone ingrowth shot- sand- or grit-blasted
-
- 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
-
- 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
- A61F2310/00005—The prosthesis being constructed from a particular material
- A61F2310/00179—Ceramics or ceramic-like structures
-
- 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
-
- 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
- A61F2310/0097—Coating or prosthesis-covering structure made of pharmaceutical products, e.g. antibiotics
-
- 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
- A61F2310/00976—Coating or prosthesis-covering structure made of proteins or of polypeptides, e.g. of bone morphogenic proteins BMP or of transforming growth factors TGF
-
- 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
Abstract
The invention provides a nanotechnology process for implant surface treatment for producing an implant article. The nanotechnology process comprises subjecting a non-porous material to a mechanical or chemical surface treatment until a surface roughness with an average peak distance (Ra value) between 10 and 1,000 nm is obtained. The roughened surface can subsequently be subjected to precipitation of calcium phosphate from a solution containing calcium and phosphate ions.
Description
BO ~91 CA 02205107 1997-05-12 Impl~nt matenial ~od proce~s fo~ producing it The present i~ .Aio~ relates to an implantable dcvice, to a pIocess of ~-~)duci~ a device and to the l, ~ Ji~l usc of such ~ device.
US Patent 5,456,7~ 5 an implant havi~g a pOrOUS mrplli~ surfac~
5 which has been t eated by sandbla ~ d rcductive acid etching IeSlllti~ in a surface mi~o-roug}rPCc havi~g a m~simllm pcak-to-va~ley height of about 20 to 30 ~Im anda ~u~slmes.. spa~ing of abollt 1-5 ~. Thc G~t~Cly sharp, oomb-like ~ uClul~ iS
n~ in order to a~hieve ylffinPnt ad~si~I~ bet~een the implant aDd tilc coating mate~ ua~dydtite) foImed on it by ~ e the h~l~u,~atilc in the implallt.
loA !~ .bad~ 0~ mo6t L~Lo.~yo~dtitc-cootGd impl~ntS is that the ,~l~r.l,n.j"~ of~l~OAyap~ t; onto the ~mplant lequires high ~ ~r~ S, ~hich lim~t the choice of sub~ Pn~lc and rcsult in hi~her ~oe~ costs. ~e ~Gviullsly ;r~J~ for coating implant m~trr1~lc ~v~th ~ uAyd~dlite is plasma ~posilioll (for a review, see P. Scrckian, ;D I~ylapatite Coahngs zn Or~or~
15Sur,~e y, Ed. Geesink and ~mlcy, ~ave~ Press NY, 1993, p. 81--87). A~other dis--advantage of the pl~ a depositic.n ~ cl -;qlJ~, ~n addieion tû the high h~
involved, rcsidcs in the ~elatively ~ge particle 6ize, in the order Of 30-70 ,um.
'rbe aim Of thc plescnt in~ention is to p~ovidc an i--pl~nt~le device that can bc used in a wide vanety of biomedical ~p~ innc (surgery, bo~e-rel~1~e.n~, 20 prosth-~lontirc etc.), and rcsults in an ~f~ i bonc r.,.~ iOll and can be pluccs~d at ambient ~ erdt~
The aim is ac~ieved by a s~aped article sultable ~ an implant of a 601id, i.e.
non-fluid, po~ous or non-porous ~nOterial havirlg a wrface na~o~ou~nfisc with anaYelage pcak dist~cc (~a value) bct~Yecn 10 l~m and 1,000 mn, giving risc to the;2s f~ nP.tinn of a c~ coaffllg when placcd in s~ t1nnc of boIle-foIming Ihe suIface ro~nP~ is a ~ntical factor of t~c artide ~.g to the inve~ltion. The surface r~ehJl~c is defined bercin by the a~er~gc peak dir~nr~, i e the avaage spacing bctwcen prOtrUSiOns ûn the urface (Ra vable). I~his average peak 30 distance can be d~t~ Pd e.g. by means of Sc~nni~~ l~lcctron Mic~ (SEM:). I~
general, the avcrage peak distance sllould bc 1,000 nm ol less. Ihe most suitable ~o~ghnP~c depends on ~e ~e of ~e ~naterial of the ~rticle. ~or article~ msde of !;t.~ ., the avcrage peak dist~nce can bc C.K. fraln 10 to 200 nm, for polymer~cn~ thc p.~ .d peak distance is ~om ~0 to 500 , l,vh~l~ for s~inless steel ~e pealc ~li~aDr~ i~ adva~tageously between 50 alld 1,000 nm. Ill genaal, the yl~r,.~d 5 averagc pe~lc distance Ia~ge is bet~eeII 2 and ~0~ nm.
Ihe depth of 1:he surface ro~ ;s of t1~e ar~clc i6 le66 cr~tieal th~ t~e peak n~ However, a ~ depdl ~ des~rable, in pa~ticular a peak height - w~th respccs to tllc de~epest sitcs on the 6u~facc - of at least 20 , ~Ip to about 2,000 ~m.
The psefared average depth is of the same o~dcr of lf~;h.~l~ as the aveaagc peakdi~nr~ and is i~ particular fro~ S0 nm to 1,000 nm. The averagc dcpth can also be d~ tf, ~ cd b5~ mcans of Sca~llin~ ElectIoD l!~ic~
I~e s~bstr~ts of the implant article can bc of various nlaterials. These includcmetals, in particula~ pa~iblr metals s~ch a~ -...., t ~lt~llml~ r~iQbi~lm ~ i~ and alloys thereof, as wcll as ~ stcel. Anotller uscful class of bio-15 "~ b~e m~trn~lC co-np.~cs a~ganic nah~ and~synt~ l;c poly~ .s such as poly-cthylene, ~l~lu~,lene, yolyl~luo~ ylcnc CIeflon~), which may also be bio-lc polymc~s such as POIYZ~ O1;C acid, polylactic acid or c~tain poly-s,lc~l ~idcs C~nir matcrials such as calcium ~h~CI~ , alumiDa or hir~ c, as wdl as .:o...~ite materials, can also be used as an implant s ~h~tr The mate~ial may be 20 porous or non-pornus. Whe~e it is porous, the po~s are ~ I;n~ c~ om the valleys of the su~f~ce ron~n~.eC by thcir depth: i.e. tbc pores have depths ~ i .11y ~eatcr than 2 ~un, and the s~rface roug~n~-cc may be ~ os~d on thc pore walls.
The sub~atc having the sllrfacc ~ou~nr-ss a6 d~fined above can vcry ,~1;. ;. ..,lly be coated with a layer of ~ calc~um ~h~ h~ cithcr in vitro, or in vivo. If the calcium 25 ph~ e coat~ng is applied ~ vitro, the c~lcilun rb~crh~te layer caII bc rclatively thirl, the order of ~m a e.~ 50 ~m to 200 ,~un, Pc~i~l1y ~om 1 to 50 llm. Ihe calcium c~p~~ preferably ~orms small crystals, ~ e an ~l~o.tphuub-like Shu~lu~. Thc calcium rhns~.h -~ can be any u~nhin~hr " of calcium and p} .~ ions, ~ptjnn~lly together witb e.g. L~ AidC, chlonde, ~lrb~tr nitrate etc. anions or h~hoO_~, sodium, 30 ~l~ssi-~ , m~Psium etc, eations. F~c~al)ly~ e calaum p~o's~ b iS not a hydlOAy-apatite, sirlce thc latter tends to havc too large particles.
The ~alci~un coating can be ~pplicd from a solution co~t~ in~ calcium and ~0~0391 CA 0220~l07 l997-0~-l2 ~.h~,h~t~ iOnS. The solution may be ~ tt ~1 nr even supcr-~dtuldtc~, but it may also bc relatively diluted. This is an '~ advanta~e of ebe prcsen~ i.. ~e. ltio~ since it allows the ~-~Atlnl- of a calci~ ph~ coaein~ ~om ppr~ir~lly any solutiou c~uPl and ~h~h t~ ions. Ihe p~ e of the calcium l~h~l~h~te con-s eaining snlytion may be behveen 4 and 10, ~fefer~ lly ~h._ ~ and 8.
~io.. also providcs B process of producing a shaped article as descr~be~l abovc, c~r~ .e ~u~);ectil~g a solid m~ter~l tO a ".~ i~l or rh~.mir~l suIface t e~ until a s~ce rou~nPcc with ~c ~qui~ed averagc pealc ~ nc~ (~a value) is o~tained.
0 ~e nlc~l~a~ surfac~ 1seatl~clt may e.g. be a ~anding or sco~ng treatment USiDg coll~,. ,lti~al 5~0~ emery paper OI ~lass papeI having an approyriate fiIIe-~c~, e.g. glade 4000, ~~pti~lly in the p~ , of water or other fluids. Dialnond paste c~n aJso bc used in t~e "~r~ ;c~l surface ~lf ~,r~t The s~ ace ron~ninE~ can further bc obt~ by powder bl, ~inE using suitab~c f~nc pO..~lS. Ihe cJ~r.";~,~l surface ~ Cllt may e.g. be a tIcatment with a s~ g, prefcrably mine~al, acid sQ~ n, suchas h,~ 3~ hydro~h1~ llrhllnc~ nitIic, perchloric acid or ~ ln,~ nc thereof, optio~ally followed by o~ ci~ agents such as nitric acid, pc..,.- :.lc, L~o~ ides or I~L~ ." ~lU"i~C, opt~ n:ll1y followed by neutra~isiIIg steps. It is iu,~o~"Jt that ~e surface rough~rlin~ is perf~ r~ under wntrolle~ c4~;1ir.n~c to ensl re a unifûrm r,esult.
~o The ~ulr~cl, lo~ fd imrl~nt~ deviccs accu~ g to the inv ~tion are inte~ed for l~ m~'~ ~l use, i.e. ~ a bonc ~ ;, a joint p~C-th~ ~ic, a dental impl,ant ~rqsth~ s)~a~n~si1lof~r;q~implant,avcltebralsur3~eryaid,atl~s~ nF.~ device (stoma and the lilcc) and other medical or COS3~ devices. Such imr1sntC can serve as a bone ~ Or bone l~ei~.n~,ll.,.ll, but also as a means of fi~cirlg a device to a~srti~.1~ bone.
Ihe imr~ h1~ devtces can be plovided as such, i.e. withûllt calciuln rh~l.h ~le coating. Bone f~ st;orl can then be induccd in ~vo due to the presence of thc specific sn~face lu~d. .;.,~,, whicb can ~esult in the form~tior~ of a calcium ph~s~..k~; coatirlg in situ. The articles caIl also bc pre coated ~ntb calci~ )hosp1~t~, 30 thc p~ecoat servi~ then to acccleldtc and enha~nee bonc fnrm ~inn a~d fix~tion of the implaïlt ~ the target olg~isnl.
B0~0391 CA 02205107 1997-05-12 EXAMPLE 1.
~cri~ls and Mdhods Ti 6AI-4V a~d l~-AI-25Fe s~ 6, 9.15 mm and 5 mm ~n ~ t~ ~L~ely and 15 n~m t~ck, werc uscd. They werc ~und flat in SiC paper6, 1~00, 4000 grit aud s J'~ ~ r~ down to 1 ,u~. 316L 5~;nlP~ tccl samples, ca. 80 mm2, were aEso ground in SiC papcss, 1200 and 4000 grit. ALI samplcs ~ere UlllA~ y de~e,d in 90% cthaIlol ~or 20 minutes followed by a 20-minute double ~i~l6C with distilled water and dried under ~ flow of hot air. Ibe 611rface rou~)~AF-,-~C wcre ~l~e~vl~d with a laser profilomcter (Perki~ Flmer). Table 1 shows the results of the followi~lg roug~
0 pa~-~--P~u~ Ra ~ .elic mean of the roughness hcight, Rz - mean pcalc-t~vallcy heig~t aIld Rma,~ n ~ul-gh~ . depth.
After surface p- lichil~ aDd clr~n;T~ all sample6 wcre ~,s~d in Ha~ks' P~ cd Salt Soh~ n (HI~SS) ~t 3~~C for 14 days in sepa~atc pol~,lhylcLI~ eo..~ . To allo~
a U~ AI~ supply of sol~tion this was changed cve~y 48 ho~ls. ~npty pol~Ah~lenc 5 ro~ were used as reference. A sample of each ~etli~ t solution was stored iD 2 pPnti~ rfTM at 4~C Ca and P ~ t~tjonc in these sol-,tlon~ ~cre later n~ 1 by atomic d~ul~liull s~l.o...l,~y ~anan SpectAA 300) and s~c~hol,holo-metry (Vitalab 21, Vitalab ~iPntifie), lc~ ly. All the results are the averagc of at least tbree mc~u.c...e..ls.
20 All surfaoes were o~ by sc~A~nni~e elect~on ~ u ~o~r (Philip~ SEM 525M) before aDd after ~mmersioD a~ alyscd by ~MA (Voyager ~MA, ~ORAI~ I~hu~e.~
X~ (Philips Ihin-f~lm XRD) was used to c~ .",i"r the shucture of ~c ~lC lJII-Ic la~er, alld AFM was used to obsc~vc its molphology oP polished tit~uulll alloys. ~esults and d;~
2s Flg. 1 shc~ws ~e Ca CO~ t;ul.~ as a fU~n of time. A l~ OtO ;C d.,G~L5C of theCa c~n~.,h~ was clP,~e~Pd in thc sol1lti~n~ that were in contact w~th the alloys. The ~ne ~h~ ~----r~ -- waS obse.~,~ for the l~.rc,cuce HBSS. Until day 5 all curves we~e s~milar but aftcr day 5 the Ti-6AI-4V 1 ,unl samples e~ibited a highcr ~c~s~, which rcaches 123+1.5 ppm. For both Ti-6AI-4V 4000 and 1~ .5~e 1 ~ samples the 30 C~a ~4~e ~"t~ation dc~l~ more rapidly afte~ day 7 ~ similar fi~al Ca uptake c .~ .ations, ~1+2.3 and 63~1.5 ppm, l.s~ ,ly. All ot~er s~u~r~c - h;bi~
uptake valucs between S and 20 ppm.
Fig. 2 shows thc P ~ ~ ~ io~ as a fanction of timc. The P uptake cunes, likc the Ca .t. ".;,r 1;ol.~, also sbowcd a d~ as a f~ction of time. Thc Ti-6AI-4V 400~ d 1 ~ and the ~ 25~e 1 ~m sho~ved tbc highest P uptake; 29~.1, 34~1.5 and 58 ~ I ? ~ ppDI, ,~cLi~ . Ihcse filldings suggest that a Ca and P rich prectpitatc is formcd on all tltc surfaces ~om HBSS. ~n fact, a ~vhite fil~ d~;t~,d on tbe poly-~jl~c that ~o,.~ r~A with HBSS could bc see~. Ti-Al-25Fe 40(10 and 1200 sho~ved 5 thc hwest C~ and P upt~kc. Ihc decrease m both Ca and P was attributed to the growth of ~ nudei OII the surfaces ~Om tl~ S 501~ nn Simil_r b~vio~ was found by Li et a~ [~1 ~ter ;II~UJ~ of silica-gcl alld gel-dcrived titania in ~;im-~lAt~d ~ody Fl~ud; Radin et ul. [2] also ~po~ted a ~ in Ca and P
c~ n~ o~l in .Cim~ te~ y.cihln~ Soll~inn after the h ~ ;o~ of ceramic 0 pa~ticles.
~lg. 3 shows SEM ~h ~ o~ ~aphs of the md~l sur~aocs aftcT imm~rsioJl iI] HBSS.
t'l .. ~p - ~ . ¢ the p~ ~t- V AI~h~ aIl Fig. 3 it can bc secn that thc ylc~ layeI has a platc k~lQgr on which "globules" and/or ~y~tals graw. ~A revealed 8 high~
q~antity of Ca aDd P on these E~cutidcs than in the pl~te p~c~ . It was possiblc to ls obsene that the plates Ji~lu~cd on some of the ~f ~s, na~cly l~ 6AI-4V 1200 a~d 1 ~un, rl-AI-25Fe 1 ,uln and st~inless steel 1200. Ihe o~ ~t~tio~ of the L~ es does not seem to dcpend on the ori~nt~t;tm of thc eJin~j~ fiaws as it is p~ssible to observe a random ~ackil~g of thc plates. The ~ r;p;l;~lr fo~med on ~l-~Al~V 4000 s~ows aconti~~ te~ture at the samc ma~ifirat ~. as thc other ol)s~;.v~tions. It was only 20 possiblc to detect ha~ cs on these s~ Ps, on the Ca and P rich layer, at mq~ific~tjcmc l~ hcr tban 2400 x.
Ii et ~ [6] p~lîol,l,ed a series of e pl .;~,....~t~ vhich silica-~el was iJ ~-J- ~
SBP. T~cy SUggESt that thc regulation of apatitc g~wth is ~latcd to the (~atP mol~r rstio of the fluids. Fu~ishiro ~ a~ [11 obt~ncd .li~ s by ;~ c;~.e Fe 25 and l~ Ca(edta)2--~aH2PO~ s~ ti~n ~arious ~n~.nlr~ of C:a(edta)~~ had a direct effect Oll the - ,~ of the llyd~ atite film.
Ihe SE~ Obsei~vdtiOllS wggcst that the mo~phology of the p.~ic;~ t~ layer sccms to be . ~It both o~ nlat~:rial and surfaoe finichir~ as the i...,..~ C:O.. flllid was the same ;.. .cllt~.
30 Fig. 4 shows an AFM Fh~olnif~ognd~h from a 'ri-AI-25Fc 1 ~m samplc. rt is alJl a~ t that the calcium ~ho~ t~ rich coating is cv~ A by thc a~ln...~ of s~ he.i~l particlcs. Similar Iesults were ol~k~h-cd foI the Ti-~Al-4V 1 ,4n 6urf~ It fiecms that thc ~olmatioII of the coat~ng staIts with h~,t~,~0~ 1S preriri~tinn of nuclci whiCh gather wit4 timc until all the surface is covercd.
It was _~;c:.~lr that the r~ 2.5Fe alloy s~faccs 4000 and 1200 did not e~ibit plate ~ t s. It was only possible to obseIvc small scatt~rcd depos~ts whicb had a similar "los~-logy to c~ ;l;o~ on the flat ~ou.ld ~ ,owed thc presesne of no C~ or P. T~c same aC~icitinn on tbe c ystals showcd the ~.~s~ -~e 5 of the alloy clr .r ~1C~ Ca and P, ~60ri~'l,d wit-h Si. Si seems to act as a nucleus fo~ the p~ 1;n-- and grawth of thc c~stals. This il-lyu~ily is l,loL.dl)l~ due to t~c SiC~ emery paper used dunng Ulc surface pl~ Eithcr the dcg ~g and ~ ";.~e of thc surface was not suff;t ie~t~ on these .n~ s, to ~ o~c the SiC or somc SiC particles might bc ~Lud~olcl in thc alloy's su~facc as n~ 2.5Fe is a 60~tcr m~tPri~l tha~ ~e 10 oth~ alloy6.
Fig. S e~hibits ~IA spcctra acquL~e~ in a T~-6AI-4Y 4000 sarnple bcfoIc and after n , ~ in HBSS. Onc can observe thc pl~ce of thc alloy ele~ t~ as wdl as ve~y well defined Ca and P pcaks on the after-i-~ ;n,~ spectra. The C~ t~d CalP ratiois 1 ~0 0~ whicl~ ;c~ s t~at the ~-~ci~ probably co~sists ~nly of ~ir~1r;l-m 15 phos~hatc ~ig. 6 shows XR~ spectra ~quir~d On non-i~JJ~ d (A) and i~ d (B) Ti~
4V 1 ~ rf~<fC On the i.~ cd samples one can obser~e t~c app~ce of a well defincd ~002] pc~k and a broade~ vhich seems to be ~ d by the junction Of p~s [211~ a~d [ll:Z] in(~ ti~ thc amorphous ~h~- t~ irs of t~c calcium 2u Fho~h~ts. These results suggest that the l,~r ~r ;~ layel ~as an - . .ol ykO~ apatite-l~ce ~ rc. S~lar res~lts were oln~ed for the Ti-Al-25Fc 1 ~rn r ' S
The l~ of this laye~ was plc~;ously t~ .";. ~d by S~iM obscrvations and is ca S ~. Ii et a~ [6] mo~ d the d~ ,lo~ ,t ~!t of ~ o"ydpdite dcposits on gel-derived titania, as a ~ . of time, after iU~ cl~;on in ~5iFn~ t~d Body Pluid. I~ tbc initial 2~ ~itages they dete~d ~It~rc~ Ciyildt~,s all ovcr the surface which ~ - e d in ~un:lbcr and size until, cvcntually, all thc sur~cc was covered by a 10 ~ m coating. Duchc~ne et a~ [5~ ~po~hd the fn~n~tinn of small dcposits on titas~iunl discs after 1~ay CAY~JSU~j to a Simulated Physiological Solutiou. ~ro weeks of ~ clclnial ;.. ,n~ ~ ? jnr~ we~c needcd to produce a~ apatite layer w-ith a ~h~ cc of 1~0 Han~wa et a~ [3] also ~polhd that apatite is naturally formed on Ll~iu~l~ wbe iul~l is h~el~d in a solution whose pH is similar to tbat of thc bioliquid. Theyt~,d a tl .~C~; of 7 mn of the apatite film grown on Ti~ 4V which malce6 it imros6itll~ for this layer to cxhibit ~ny l,.o~.tics of calcium l,h..~ te in this e.l~ilu~c.,l The prcscnt re6ults indicate t~at a calcium r~ with aII apatite-like structure is Daturally fonned on thc surfaces of polLchcd titaT.uuln ~lloys. I~e ll.:~L .~r sc of this layer malces it a sL~itablc surface for bonc ;---h-- l;~ ,r~5 of at least 1 llm are needed for thc calawn l-hr~ h- ~ to sho~ up~ll;cs and cause bone ;...1~..i;~..
~, The nto~rhn'~y of calcium phosphate yle~p;~ depeIlds o~ thc mcta1 s~t~tr- and its surface c~ s It is possible to p~oduce a ~aturally formcd calciuun ~kos~h-~
coa~g by ;."...r,,~ , mctals such ~s titan~um alloys and s~ir-lecc stcel in HBSS.
Ti~ 4V 4000 sce~ls to be the surface that is most favouIable to produce a 0 cnntinl-ous a~d more adhe.~ t ~ te-like coating ~;apable of bone in~luchon LE 2. Dete~nina~on orcalcium p' -sp' ~te depth di~ tio~ on a tita~i~m alloy bul~l~ate using ~-my photoel~hon ~pect~
d~tcs the .~ ~~ r - - of the depth Cli~t~ t~ of sct~d cl~ s in a ~11m, p~;os~ho,u~ d oxygen - ~-4--1~ g coating on a tit~nillm alloy Sa~SlplC
g dcpth ~.~,r,L,.g X-ray Pbot~-1~rt~on Sp.,cl~oscop~, (XPS or ESCA).
'~J~
The samples we~ titanium aUoy plates that h~d bee~ surfacc trcated acco~d~ to the c~eA~ of E~cample 1 to prodl~cc a calcium ~h~s~ coat~ ~hcn ;.. ~ ,~cd m ~jfir~ ulio..S Or s;~ trd body nuids. The salnples were mn-l~tcd dire~y tO
20 a Sl~l~ XPS ~iamplc holder using a sp~g clip ~..;.. ~,. - ....~, with no pre-treahnent.
Thc outer coat~Dg sur~acc was ~ ~~r;. ;r"~ lly ~hJ~ e that no clccllosla~ic ~dl~ problems v.rere ~ tl cd during ~-ray ~rladiation or ion beam etching. All a~alysis v"ere carried out usmg a Su~faoe Scicnce L~lu~ s (SSI) M-probc opc,rating at a base p~e~ul~ of 3~10-9 tO~r.
25 A~
sulvey ~;tlUIU was ~ ûm the "as rc~;~,~3~ surface, to d(t ~ r t~e sulrface co.llposition of thc coating and therefore d~ the Pl~n~nt~ to be .llollilol~d for thc dcpth profile. The XPS de~th profile was o~ h~r~ by ~ t;~ argon ion ~t~e ;nt (ovcr ~n area of approx. 2 x 2 mm) and data ~ icit;~n (from a~l area of30 approx. 300 llm di~eter centre~ in the etched crater). F,~Pntc analysed were carbo~, oxygen, ~~ m~ rh~horusl magnesium and tiPnil~n- Etc~ timc per stcp wa~ variable ~o~ 15 to 120 seconds per cycle and the etc~ ~ate was 3 nm/min using a total sputter time of 4470 s~o~lc ~SJ~
~hc surf~oe rh-~mi~l C~ (il2 atomic percent) of the 'tas ~ dn ooatm~
carbon 44.9%, o~cygen 33.8%, cal~iu~ 10.5%, ~ k~,o~s 8.8%, ~ t~ ll 2.0%
aI~d tit~nil~m 09~o (figur~ 7). Ihe depdl profile o~ the coating rcvcaled a gradual 5 t~n~hnn of c:~c~um and yl.n5r~ om thc coati~g to the su~~ tr;~ ; the ~ nld1 j~l.. of these ~Tem~ntc in thc ~ur~ce toxide la~er), and thus a chpmi~l bonding between coa~ng a~d subs~r~t~ (fi~ure 8). The calcium - o~ygen ~ o~l~h~ uu:~ laye~
(ca~ ml llh~ k ~) i6 tdlm ted aS belllg l~r C ~ -Iy 90 nm, ~lminC a sputter ~ateof 3 nm per mimlte ~ TiT~d on ~ t nt~ F- ~On ;fT~ film On ~ ' and that ~L
10 ~t;u1. . ~ is dcfmed .~ the poi~ wh~c the titauium rcaches approx. ~0% of its inal valuc. A thiJ~ layer of lit~ ,", oxide 5~"~rAt-.~ the calcium 1-~-05~T~t~ layer from the alloy snhStrtqtr- The i~ betwee~ the calciu~ phrS~ TI; aDd t.l i.....
shows ~ges in the oxygcn, ~h~h~oùs~ calcium .~d tit~ tJ~ 5 Thc XPS
pe~ birK~ing ~n~I~ of calcium and ~ )hn~u~ d~e;~ at the I f~~: with the 15 ti~ whcre a ~jt~njlnn û~ide layer is foumd. A~ tL~ egion is lLkely to occur at the bo~ and oxygen has been ~ep' t ~ f~n the calcium E,hosph-~r- to form tih~ u dio~cide at the int~ ~. Metallic titanium is pre6cnt below tbe L~tc~hase Fegion. Mv~ ~ ci ~ ~ is dctect~d a~ 2 - 4 atomic percent thrû~ghout the cal~ .h ~
l~ycr and i..c~eases slightly in co~r ~ation ~ith dcpth towardc the interface with thc iu~ll (oxide). Grbon is found in the b~ of the ti~n;u~n Thc cal~ tc layer t~at ~s fonncd ûn thc titanium alloy c~ ;~t~o iS chf~ y bound to the su~ ta its surface o~ude layer.
EXAMP~E 3. P~epara~on of b~omhnetIc caIci~m phosphate c(iali~gs OD ~etallic 2s Implant~
Ihis e~mrlc illustr~tes a DCW t~o-step rb~i~t l.Gd~lt for prcpar~Dg aII implant w~th a ~fic surfacG ro~ghn~cc., rr.s..l~ [ in a me~allic su~facc that allows f~ct p~ ;n~ of bin~ lci~ phn~rh~te (Ca-P) coatings ~om in vi~o super--saturated r '~fir -i~!n sol~ (SCS). The specific surfa~e lo~ esults in the 30 following advantages: (i) the l,;u..~ coatings directly induccd f~om SCS are ~b~ IIy bouDd t~ mctallic subs~ and show higher bone-bondin~ sbility, (ii) the ro~tin~ can be produced onto c~npleY-sh~pcd and/or maclo-porolls i~nrlq~tc, and (iii) it is ~ controllable and cost-effective way to aC4ulr~ Ca-P ~o~tin~
BO ~91 CA 02205107 1997-05-12 Mmniab a~d A~ethods A nc~ly dcveloped two step rbpmir~l h~ .lcltwaS ~"F,, r~ -~ on thc m~tallic i~plant ~"~t~ lc, i.e. c~c.wally pu~e tita~ium (rp.Ti), ~ 116A14V aDd po~ous t~nt~ n CIa), to produce a ~fic surface 5~ zh-n~ss~ ~ur~g this treannent, two selies s of ~h~mi.~ol r~ae. ~ W~ ~d for titanium (cp.r~ d Ti6~1~V) ~d p-lt~l~m implant m~t~l5~ ~ ,cli~ , that resulted ~n the p~ i of t~c speciS~
~c ~ for the pl~dtil)ll of the coating. For the fo~met, tbc samples were treatbdwi~ a ~e of HCI and H2SO4, followed by j"""r,~ n in a NaOH s~iutinn The pOlOUs t~nt~ samples were t~bated with a mixture of HCI, H~S04 and HF, followed 10 by i,~~ - s,oJ~ m ~2~2 Two ki~ds of SCSs with di~ t ~a and P c4~r~ alions, f~st r~ fioatinn solution (FCS) and coln~erc;al Ha~}~s' b~ salt solution,ffIBSS), were used for ~~
p c~ti~ rO prolhote thc C~--P t~ m OD the metallic s~ ~s, a pqr~l~ ;f;r".l;"" (~re-Ca) ~lu~dulb ~a6 p~ r~ o~ half the t~eated samples before 15 ;---- .." Fi~ ~ ~ the SCS. The Pre-Ca was carried out by ;. ~f ~-h~ ~;~ the samples in 05N
Na~HPO4 ovc~night and then t.~ r~ e them into saturated Ca(OH)~ fo~ S h The ~CS
solution volume used for imm~on was 15 ml per cm2 of sample 6urface arca. I~e samples vvele ,a~u~l ed in sealed poly~ly~buc v~als at 37CC in a calibrated water-bath.
~nniT~e elcctroD mic~03copy (S~M) togcther ~vith cnc~gy dispe~se X-ray ~
20 analyses, ~-ray di~ ion (XR~ ared (D?.) s~ Lo~o~lletry werc used to t~ the ob~ P c~
~esults T~e l~ cli~ Ca-P coatings were fast l)r~ d on the treated ~p.ri and Ti6A14 samples by ~ ~sio.~ iQ both FCS and HBSS no matter whcthcr the Pre-Ca p~ucc~h 25 wa~ ~.fo~ cd or llot. But the P~c-Ca ~ o.~t~ 0uld /lr~m~t~ y ~peed-up tbe t~t~ ate of the Ca-P coatings as listed in table 2.
Figure 9 show6 that a h:~mim~ Ca-P coating, ~,~ "ntely 16~ thick, was formed o~ treated ~:p.Ti after 16 hours of ~ iO~ vi~ Prc~a. ~e coating got thicker with ~ n~ time asiT~irato~d by ~D~ (~Igure 10) and XRI) (figurc 11) 30 ~sults. Tbc p.~, -;yitatiOn ~ate of thc Ca-P coating irl ~IBSS is slower than tbat in FCS.
But thc coati~g ~om HBSS (figure 12) ~vas mu~ denser than that ~m F~:S. The coating from HBSS ma~nly ~ ;ct~l of apatite (~Igure 13). Riomi~Pt;r Ca-P c~
~40391 CA 02205107 1997-05-12 could ~o be precipitated on pO~ S Ta samples (f;gure 14) after the Lc~t.. ~ nt. Ihe sur~ce ~o~tent ~hangc of t~e sample was Art~rteA by E~X as show~ L~ fi~ure 15. lt is ~ h, that no ~ pi~ftiO~ was o~ ,d on aIIy untIeated s~nples after 2 wceks of ;~ r..~ CS or TIBSS, eve~ with Pre-Ca. The for~nation of a spe~fic ht~jllm s alld t~nt~l~lm o~de laye~ their llc7tm~nt~ is pr~bably the ma~n r~son for the i~lu~ p~cipitation of Ca-P c~ ~i~ by means of in vitro ;---- ~ s in~l in SCS. Tbe p~u~i of thc h~ ~ for titanium impl~ and tf~ h~ could not be c - ~.1. ~er.~, o~ no Ca-P ooating was acquihcd.
Co. ~
10 This bi'~ tt;r calcium I~hosF~h~te coating study has show~ tha~:-. Ihe neuvly du~,lopcd tw~step trcatment is an cffective mcthod to prepare ~ ;oc,~
- mctallic implaIIt s~lrfaccs allo~ing f~st yle~ip~ of adherent b;QY~ PI;r Ca-P
C4 ~ y in v~o in.~ .. iu SCS. The rh~nie~l Ieagents nccded for thc treatme~t of tit~n~ n ~pl~nt . ~ and t~nt~h~n a~e di~ t from eac~ oth~.
15 . The p~ of Ca-P coat~gs could be r1-~ n~tiC~IIy accele~ated by means of pre-calcify~ the treated samples befo~c thc ;~ n--~.
. Ihe ~ ;nn ~ate and ~ -l-4Sjtinn of tbe Ca-P coati~gs can be ~ t~d by controlli~g ~c c~ -Q-~J~I~ of the SCSs (EiCS o~ ~BSS) for ;~ r~;on Table 1- Surface rou~Dess me~ure~ents results zo Surface fiuisb R8 (~Im) Rz ~1~) ~ (l~m) ~-6AI-4V 1200 grit 0,47 0.01 3.74~0.04 5.13~0.08 rl-~Al~V4000grit 0.~~0.03 1.91~0.31 2.46~0~4 ~ 4V 1 llm 0.03+0.00 o ~s~o.ns 0.48~0.03 n-Al-2~Fe 1200 g~it 0.4~0.03 2.g7_0~5 3.47_0.48 2s 15~ 25~e 4000 gr~t 0.23-0.01 1.97~0.18 2.46~034 Ti-AI-2.5Fc ~ ~un 0.04~0.01 0.28+0.11 0.36+019 316 L 1200 gnt 0.3+0.06 2.32-0.47 2.96+0.03 316 L 4000 grlt 0.04+û.01 0.35+0.1 0.46 ~ 0.1 ~040391 CA 02205107 1997-05-12 11 , Table 2 - Iist Of Ca2~ d HPo42- c~ t;~,c, precipihtion rate aod ~f Ca-P coa~neS OII cp.n ~d T~ 4V.
C~t~io.~ ~mM) Ca2~ 3.0 1 26 Hpo42 1.87 0.78 ~" rate of ~o Pre-C~ 0.5 ~ mlwk S cûa~ Prc~ ~r 3 ~wk ('~ s;tic~ of coating apatitc, OCPapa~dtc ~ ptions Figur~ 1 - Ca ~- ~.~.dLiul~ as a functiQn of time Figure 2 - P CO~ LiOI- as a fi~nction of time 0 F~gure 3 - SEM ph~l -;~ ~ographs of the metal s~facc~ after imme~sio~ IBSS. A: -6AI-4V 1200; B: Ti 6Al-4V 4000, C: Ti~ 4V 1 ~m; D~ 1-25Fe 1 llm, E: Ti-AI-25Fe 4000; F - st~jnl~cc cteel 1200 Fgure 4 - AFl~ ~l-ot~ og~aph of a r~ 5Fe 1 ,~n sample aftcr I ~,.sio~ in ~BSS. In~,l~g J~ .;ri~o~j9~ ~om field n to 3. S~ nin~ le~gth ~m field 3:
15 ~Im.
F~gun; S - ~MA spec~a ~c4uhc~ on a Ti-6Al-4V 41)00 sample bcfore (A) and after Figure ~ - XRD ~ acquired on a non-h .,.scd (A) ~nd ;~ 3) li-6~1-4V 1 ~m ~e ~o Fgure 7. Sur~ace chP~nieAl cr. ~ (in atomic perccnt) of the "as ~ ,1 coating. Tc 8. Dept~ profile of the coating, ~om coating to ~ t~.
Figure ~ nni~ electrorl rnicrograph of the Ca-P coatinK (CP) pr~ ~ o~ cp.Ti ~i) afte~ lfi hou~s ûf i~ r ~ -~.. in E~CS with Pre-Ca ~ure 10. ED~ spectra of the cp.Ti 6~1rfaces Don-trea~ed, treated and ;",. -r"~'~1 ill FCS
with Pre-Ca for ~lifrG~c~ hou~s. Thc ~h~ APr of O kQ pea~ is cle~rll~ seen afterthe l.e~t~ c .-. ~e Ca and P co~tPDts i. ~ d with the i~lGIc--- of ;~
time.
re 11. XRD pattP~s of the cp.Ti suIfaces after dlrrc~ t hûuss of i~T~m~hr~ iD. FCS
with Pre-Ca. The counts of apatitc peaks get higher with incl~ascd ;...~ ,.6io t~mes. Octa calcium ph~;rh~t~ (OCP) starts to be formcd at around 8 hours.
CA 02205l07 l997-05-l2 Figurc 1~ nr:~ dectro~ h of a de~sc Ca-P ~oatmg (CP~ on c~.Ti from ~SS a~ 1 weck Of inlmr ~ with Pre-Ca The laycr betwec:u coating aDd ~.uL~ r~ the til~;ul~l ~dc layer (OL), ~smed as a Iesult of the s ~lgure 13 Ihi~-film XRD patte~ of a densc Ca-P coating ~ il. d by j~mPrcinn in~iS with Pre-(::a fa~ 1 week.
~gu~ 14. S~-~s-nni~ elect~ ph of porous i ~ Tn CTa) after 2 day6 ;...~ ~ ~ cioJ~
S with Pre-Ca. I~e coating is fosmed ~ol.gLwl t~e porous Tng~P~gl Figu~ 15. EDX spec~a of (a) noII-trcated, (b) tIeated, and (c) Pre-Ca treated, 2 day 0 FCS ;.. ~c.~ed po~ous ~ n~ ~ra) sa~plc.
Litera~u~e rc~e. ~
1. Y. Fujishiro, T. Sato and A. Oku~i, rco~tjng of h~d~u~y~alitL on metal platcs using thc~ iccor~7~ioD of calaum -EDTA c}lelste in l,~h~c ~ ~ sol-~jnn~ under hydrothennal c~ t1OD~", J. Ma~er. ~ ter in Med, 6, pp. 172-176, 1995 2. S.R. Radin and P. DUC~ C~ 1. BianL Ua~er. Res." 27, pp. 35, 1993 3. T Hanaw~, "T~tanium ~d its o~de film: a ~~!bch~qt~- for fo~g apatite", in Proc.
of the ~one Riow~t~ql T~lt~.lf~ W(!rlrshnp Toronto, Dec. 19~Q, J.E. Davie6 ed.J
Uni~r. Toronto Press, pp. 49-61, 1991 4. ~. Leit~o, M.A. Barbosa and K. dc Groot, "In vitr~ rRI~;ri~ali~f~ of 0~ ~3~1ic z0 i~plant m~t~ql~n~ J. M~ter. Sc: ~ate~ in Med, 6, pp. 84~852, 1995 5. P D~ c, S. Radin and K. lshilcawa, "~e ~te of dciuIn rh~
- ;~ ioL. o~ metal and Q~nR~~ and the ~ t~r~n~hip to l);o~ivily", in Bo~c ~on~ g Rjomqt~iRI~, P. Pucheyne, r. Kokubo ~ CA. Ya~ Blitters~ill~ (eds), Reed ~tb~re C~ vu~ic~tio~Ns~ pp. 213-218, 1~g2 zS 6. Ii, P, P~D Thesis, Leiden I~ ity (1993)
US Patent 5,456,7~ 5 an implant havi~g a pOrOUS mrplli~ surfac~
5 which has been t eated by sandbla ~ d rcductive acid etching IeSlllti~ in a surface mi~o-roug}rPCc havi~g a m~simllm pcak-to-va~ley height of about 20 to 30 ~Im anda ~u~slmes.. spa~ing of abollt 1-5 ~. Thc G~t~Cly sharp, oomb-like ~ uClul~ iS
n~ in order to a~hieve ylffinPnt ad~si~I~ bet~een the implant aDd tilc coating mate~ ua~dydtite) foImed on it by ~ e the h~l~u,~atilc in the implallt.
loA !~ .bad~ 0~ mo6t L~Lo.~yo~dtitc-cootGd impl~ntS is that the ,~l~r.l,n.j"~ of~l~OAyap~ t; onto the ~mplant lequires high ~ ~r~ S, ~hich lim~t the choice of sub~ Pn~lc and rcsult in hi~her ~oe~ costs. ~e ~Gviullsly ;r~J~ for coating implant m~trr1~lc ~v~th ~ uAyd~dlite is plasma ~posilioll (for a review, see P. Scrckian, ;D I~ylapatite Coahngs zn Or~or~
15Sur,~e y, Ed. Geesink and ~mlcy, ~ave~ Press NY, 1993, p. 81--87). A~other dis--advantage of the pl~ a depositic.n ~ cl -;qlJ~, ~n addieion tû the high h~
involved, rcsidcs in the ~elatively ~ge particle 6ize, in the order Of 30-70 ,um.
'rbe aim Of thc plescnt in~ention is to p~ovidc an i--pl~nt~le device that can bc used in a wide vanety of biomedical ~p~ innc (surgery, bo~e-rel~1~e.n~, 20 prosth-~lontirc etc.), and rcsults in an ~f~ i bonc r.,.~ iOll and can be pluccs~d at ambient ~ erdt~
The aim is ac~ieved by a s~aped article sultable ~ an implant of a 601id, i.e.
non-fluid, po~ous or non-porous ~nOterial havirlg a wrface na~o~ou~nfisc with anaYelage pcak dist~cc (~a value) bct~Yecn 10 l~m and 1,000 mn, giving risc to the;2s f~ nP.tinn of a c~ coaffllg when placcd in s~ t1nnc of boIle-foIming Ihe suIface ro~nP~ is a ~ntical factor of t~c artide ~.g to the inve~ltion. The surface r~ehJl~c is defined bercin by the a~er~gc peak dir~nr~, i e the avaage spacing bctwcen prOtrUSiOns ûn the urface (Ra vable). I~his average peak 30 distance can be d~t~ Pd e.g. by means of Sc~nni~~ l~lcctron Mic~ (SEM:). I~
general, the avcrage peak distance sllould bc 1,000 nm ol less. Ihe most suitable ~o~ghnP~c depends on ~e ~e of ~e ~naterial of the ~rticle. ~or article~ msde of !;t.~ ., the avcrage peak dist~nce can bc C.K. fraln 10 to 200 nm, for polymer~cn~ thc p.~ .d peak distance is ~om ~0 to 500 , l,vh~l~ for s~inless steel ~e pealc ~li~aDr~ i~ adva~tageously between 50 alld 1,000 nm. Ill genaal, the yl~r,.~d 5 averagc pe~lc distance Ia~ge is bet~eeII 2 and ~0~ nm.
Ihe depth of 1:he surface ro~ ;s of t1~e ar~clc i6 le66 cr~tieal th~ t~e peak n~ However, a ~ depdl ~ des~rable, in pa~ticular a peak height - w~th respccs to tllc de~epest sitcs on the 6u~facc - of at least 20 , ~Ip to about 2,000 ~m.
The psefared average depth is of the same o~dcr of lf~;h.~l~ as the aveaagc peakdi~nr~ and is i~ particular fro~ S0 nm to 1,000 nm. The averagc dcpth can also be d~ tf, ~ cd b5~ mcans of Sca~llin~ ElectIoD l!~ic~
I~e s~bstr~ts of the implant article can bc of various nlaterials. These includcmetals, in particula~ pa~iblr metals s~ch a~ -...., t ~lt~llml~ r~iQbi~lm ~ i~ and alloys thereof, as wcll as ~ stcel. Anotller uscful class of bio-15 "~ b~e m~trn~lC co-np.~cs a~ganic nah~ and~synt~ l;c poly~ .s such as poly-cthylene, ~l~lu~,lene, yolyl~luo~ ylcnc CIeflon~), which may also be bio-lc polymc~s such as POIYZ~ O1;C acid, polylactic acid or c~tain poly-s,lc~l ~idcs C~nir matcrials such as calcium ~h~CI~ , alumiDa or hir~ c, as wdl as .:o...~ite materials, can also be used as an implant s ~h~tr The mate~ial may be 20 porous or non-pornus. Whe~e it is porous, the po~s are ~ I;n~ c~ om the valleys of the su~f~ce ron~n~.eC by thcir depth: i.e. tbc pores have depths ~ i .11y ~eatcr than 2 ~un, and the s~rface roug~n~-cc may be ~ os~d on thc pore walls.
The sub~atc having the sllrfacc ~ou~nr-ss a6 d~fined above can vcry ,~1;. ;. ..,lly be coated with a layer of ~ calc~um ~h~ h~ cithcr in vitro, or in vivo. If the calcium 25 ph~ e coat~ng is applied ~ vitro, the c~lcilun rb~crh~te layer caII bc rclatively thirl, the order of ~m a e.~ 50 ~m to 200 ,~un, Pc~i~l1y ~om 1 to 50 llm. Ihe calcium c~p~~ preferably ~orms small crystals, ~ e an ~l~o.tphuub-like Shu~lu~. Thc calcium rhns~.h -~ can be any u~nhin~hr " of calcium and p} .~ ions, ~ptjnn~lly together witb e.g. L~ AidC, chlonde, ~lrb~tr nitrate etc. anions or h~hoO_~, sodium, 30 ~l~ssi-~ , m~Psium etc, eations. F~c~al)ly~ e calaum p~o's~ b iS not a hydlOAy-apatite, sirlce thc latter tends to havc too large particles.
The ~alci~un coating can be ~pplicd from a solution co~t~ in~ calcium and ~0~0391 CA 0220~l07 l997-0~-l2 ~.h~,h~t~ iOnS. The solution may be ~ tt ~1 nr even supcr-~dtuldtc~, but it may also bc relatively diluted. This is an '~ advanta~e of ebe prcsen~ i.. ~e. ltio~ since it allows the ~-~Atlnl- of a calci~ ph~ coaein~ ~om ppr~ir~lly any solutiou c~uPl and ~h~h t~ ions. Ihe p~ e of the calcium l~h~l~h~te con-s eaining snlytion may be behveen 4 and 10, ~fefer~ lly ~h._ ~ and 8.
~io.. also providcs B process of producing a shaped article as descr~be~l abovc, c~r~ .e ~u~);ectil~g a solid m~ter~l tO a ".~ i~l or rh~.mir~l suIface t e~ until a s~ce rou~nPcc with ~c ~qui~ed averagc pealc ~ nc~ (~a value) is o~tained.
0 ~e nlc~l~a~ surfac~ 1seatl~clt may e.g. be a ~anding or sco~ng treatment USiDg coll~,. ,lti~al 5~0~ emery paper OI ~lass papeI having an approyriate fiIIe-~c~, e.g. glade 4000, ~~pti~lly in the p~ , of water or other fluids. Dialnond paste c~n aJso bc used in t~e "~r~ ;c~l surface ~lf ~,r~t The s~ ace ron~ninE~ can further bc obt~ by powder bl, ~inE using suitab~c f~nc pO..~lS. Ihe cJ~r.";~,~l surface ~ Cllt may e.g. be a tIcatment with a s~ g, prefcrably mine~al, acid sQ~ n, suchas h,~ 3~ hydro~h1~ llrhllnc~ nitIic, perchloric acid or ~ ln,~ nc thereof, optio~ally followed by o~ ci~ agents such as nitric acid, pc..,.- :.lc, L~o~ ides or I~L~ ." ~lU"i~C, opt~ n:ll1y followed by neutra~isiIIg steps. It is iu,~o~"Jt that ~e surface rough~rlin~ is perf~ r~ under wntrolle~ c4~;1ir.n~c to ensl re a unifûrm r,esult.
~o The ~ulr~cl, lo~ fd imrl~nt~ deviccs accu~ g to the inv ~tion are inte~ed for l~ m~'~ ~l use, i.e. ~ a bonc ~ ;, a joint p~C-th~ ~ic, a dental impl,ant ~rqsth~ s)~a~n~si1lof~r;q~implant,avcltebralsur3~eryaid,atl~s~ nF.~ device (stoma and the lilcc) and other medical or COS3~ devices. Such imr1sntC can serve as a bone ~ Or bone l~ei~.n~,ll.,.ll, but also as a means of fi~cirlg a device to a~srti~.1~ bone.
Ihe imr~ h1~ devtces can be plovided as such, i.e. withûllt calciuln rh~l.h ~le coating. Bone f~ st;orl can then be induccd in ~vo due to the presence of thc specific sn~face lu~d. .;.,~,, whicb can ~esult in the form~tior~ of a calcium ph~s~..k~; coatirlg in situ. The articles caIl also bc pre coated ~ntb calci~ )hosp1~t~, 30 thc p~ecoat servi~ then to acccleldtc and enha~nee bonc fnrm ~inn a~d fix~tion of the implaïlt ~ the target olg~isnl.
B0~0391 CA 02205107 1997-05-12 EXAMPLE 1.
~cri~ls and Mdhods Ti 6AI-4V a~d l~-AI-25Fe s~ 6, 9.15 mm and 5 mm ~n ~ t~ ~L~ely and 15 n~m t~ck, werc uscd. They werc ~und flat in SiC paper6, 1~00, 4000 grit aud s J'~ ~ r~ down to 1 ,u~. 316L 5~;nlP~ tccl samples, ca. 80 mm2, were aEso ground in SiC papcss, 1200 and 4000 grit. ALI samplcs ~ere UlllA~ y de~e,d in 90% cthaIlol ~or 20 minutes followed by a 20-minute double ~i~l6C with distilled water and dried under ~ flow of hot air. Ibe 611rface rou~)~AF-,-~C wcre ~l~e~vl~d with a laser profilomcter (Perki~ Flmer). Table 1 shows the results of the followi~lg roug~
0 pa~-~--P~u~ Ra ~ .elic mean of the roughness hcight, Rz - mean pcalc-t~vallcy heig~t aIld Rma,~ n ~ul-gh~ . depth.
After surface p- lichil~ aDd clr~n;T~ all sample6 wcre ~,s~d in Ha~ks' P~ cd Salt Soh~ n (HI~SS) ~t 3~~C for 14 days in sepa~atc pol~,lhylcLI~ eo..~ . To allo~
a U~ AI~ supply of sol~tion this was changed cve~y 48 ho~ls. ~npty pol~Ah~lenc 5 ro~ were used as reference. A sample of each ~etli~ t solution was stored iD 2 pPnti~ rfTM at 4~C Ca and P ~ t~tjonc in these sol-,tlon~ ~cre later n~ 1 by atomic d~ul~liull s~l.o...l,~y ~anan SpectAA 300) and s~c~hol,holo-metry (Vitalab 21, Vitalab ~iPntifie), lc~ ly. All the results are the averagc of at least tbree mc~u.c...e..ls.
20 All surfaoes were o~ by sc~A~nni~e elect~on ~ u ~o~r (Philip~ SEM 525M) before aDd after ~mmersioD a~ alyscd by ~MA (Voyager ~MA, ~ORAI~ I~hu~e.~
X~ (Philips Ihin-f~lm XRD) was used to c~ .",i"r the shucture of ~c ~lC lJII-Ic la~er, alld AFM was used to obsc~vc its molphology oP polished tit~uulll alloys. ~esults and d;~
2s Flg. 1 shc~ws ~e Ca CO~ t;ul.~ as a fU~n of time. A l~ OtO ;C d.,G~L5C of theCa c~n~.,h~ was clP,~e~Pd in thc sol1lti~n~ that were in contact w~th the alloys. The ~ne ~h~ ~----r~ -- waS obse.~,~ for the l~.rc,cuce HBSS. Until day 5 all curves we~e s~milar but aftcr day 5 the Ti-6AI-4V 1 ,unl samples e~ibited a highcr ~c~s~, which rcaches 123+1.5 ppm. For both Ti-6AI-4V 4000 and 1~ .5~e 1 ~ samples the 30 C~a ~4~e ~"t~ation dc~l~ more rapidly afte~ day 7 ~ similar fi~al Ca uptake c .~ .ations, ~1+2.3 and 63~1.5 ppm, l.s~ ,ly. All ot~er s~u~r~c - h;bi~
uptake valucs between S and 20 ppm.
Fig. 2 shows thc P ~ ~ ~ io~ as a fanction of timc. The P uptake cunes, likc the Ca .t. ".;,r 1;ol.~, also sbowcd a d~ as a f~ction of time. Thc Ti-6AI-4V 400~ d 1 ~ and the ~ 25~e 1 ~m sho~ved tbc highest P uptake; 29~.1, 34~1.5 and 58 ~ I ? ~ ppDI, ,~cLi~ . Ihcse filldings suggest that a Ca and P rich prectpitatc is formcd on all tltc surfaces ~om HBSS. ~n fact, a ~vhite fil~ d~;t~,d on tbe poly-~jl~c that ~o,.~ r~A with HBSS could bc see~. Ti-Al-25Fe 40(10 and 1200 sho~ved 5 thc hwest C~ and P upt~kc. Ihc decrease m both Ca and P was attributed to the growth of ~ nudei OII the surfaces ~Om tl~ S 501~ nn Simil_r b~vio~ was found by Li et a~ [~1 ~ter ;II~UJ~ of silica-gcl alld gel-dcrived titania in ~;im-~lAt~d ~ody Fl~ud; Radin et ul. [2] also ~po~ted a ~ in Ca and P
c~ n~ o~l in .Cim~ te~ y.cihln~ Soll~inn after the h ~ ;o~ of ceramic 0 pa~ticles.
~lg. 3 shows SEM ~h ~ o~ ~aphs of the md~l sur~aocs aftcT imm~rsioJl iI] HBSS.
t'l .. ~p - ~ . ¢ the p~ ~t- V AI~h~ aIl Fig. 3 it can bc secn that thc ylc~ layeI has a platc k~lQgr on which "globules" and/or ~y~tals graw. ~A revealed 8 high~
q~antity of Ca aDd P on these E~cutidcs than in the pl~te p~c~ . It was possiblc to ls obsene that the plates Ji~lu~cd on some of the ~f ~s, na~cly l~ 6AI-4V 1200 a~d 1 ~un, rl-AI-25Fe 1 ,uln and st~inless steel 1200. Ihe o~ ~t~tio~ of the L~ es does not seem to dcpend on the ori~nt~t;tm of thc eJin~j~ fiaws as it is p~ssible to observe a random ~ackil~g of thc plates. The ~ r;p;l;~lr fo~med on ~l-~Al~V 4000 s~ows aconti~~ te~ture at the samc ma~ifirat ~. as thc other ol)s~;.v~tions. It was only 20 possiblc to detect ha~ cs on these s~ Ps, on the Ca and P rich layer, at mq~ific~tjcmc l~ hcr tban 2400 x.
Ii et ~ [6] p~lîol,l,ed a series of e pl .;~,....~t~ vhich silica-~el was iJ ~-J- ~
SBP. T~cy SUggESt that thc regulation of apatitc g~wth is ~latcd to the (~atP mol~r rstio of the fluids. Fu~ishiro ~ a~ [11 obt~ncd .li~ s by ;~ c;~.e Fe 25 and l~ Ca(edta)2--~aH2PO~ s~ ti~n ~arious ~n~.nlr~ of C:a(edta)~~ had a direct effect Oll the - ,~ of the llyd~ atite film.
Ihe SE~ Obsei~vdtiOllS wggcst that the mo~phology of the p.~ic;~ t~ layer sccms to be . ~It both o~ nlat~:rial and surfaoe finichir~ as the i...,..~ C:O.. flllid was the same ;.. .cllt~.
30 Fig. 4 shows an AFM Fh~olnif~ognd~h from a 'ri-AI-25Fc 1 ~m samplc. rt is alJl a~ t that the calcium ~ho~ t~ rich coating is cv~ A by thc a~ln...~ of s~ he.i~l particlcs. Similar Iesults were ol~k~h-cd foI the Ti-~Al-4V 1 ,4n 6urf~ It fiecms that thc ~olmatioII of the coat~ng staIts with h~,t~,~0~ 1S preriri~tinn of nuclci whiCh gather wit4 timc until all the surface is covercd.
It was _~;c:.~lr that the r~ 2.5Fe alloy s~faccs 4000 and 1200 did not e~ibit plate ~ t s. It was only possible to obseIvc small scatt~rcd depos~ts whicb had a similar "los~-logy to c~ ;l;o~ on the flat ~ou.ld ~ ,owed thc presesne of no C~ or P. T~c same aC~icitinn on tbe c ystals showcd the ~.~s~ -~e 5 of the alloy clr .r ~1C~ Ca and P, ~60ri~'l,d wit-h Si. Si seems to act as a nucleus fo~ the p~ 1;n-- and grawth of thc c~stals. This il-lyu~ily is l,loL.dl)l~ due to t~c SiC~ emery paper used dunng Ulc surface pl~ Eithcr the dcg ~g and ~ ";.~e of thc surface was not suff;t ie~t~ on these .n~ s, to ~ o~c the SiC or somc SiC particles might bc ~Lud~olcl in thc alloy's su~facc as n~ 2.5Fe is a 60~tcr m~tPri~l tha~ ~e 10 oth~ alloy6.
Fig. S e~hibits ~IA spcctra acquL~e~ in a T~-6AI-4Y 4000 sarnple bcfoIc and after n , ~ in HBSS. Onc can observe thc pl~ce of thc alloy ele~ t~ as wdl as ve~y well defined Ca and P pcaks on the after-i-~ ;n,~ spectra. The C~ t~d CalP ratiois 1 ~0 0~ whicl~ ;c~ s t~at the ~-~ci~ probably co~sists ~nly of ~ir~1r;l-m 15 phos~hatc ~ig. 6 shows XR~ spectra ~quir~d On non-i~JJ~ d (A) and i~ d (B) Ti~
4V 1 ~ rf~<fC On the i.~ cd samples one can obser~e t~c app~ce of a well defincd ~002] pc~k and a broade~ vhich seems to be ~ d by the junction Of p~s [211~ a~d [ll:Z] in(~ ti~ thc amorphous ~h~- t~ irs of t~c calcium 2u Fho~h~ts. These results suggest that the l,~r ~r ;~ layel ~as an - . .ol ykO~ apatite-l~ce ~ rc. S~lar res~lts were oln~ed for the Ti-Al-25Fc 1 ~rn r ' S
The l~ of this laye~ was plc~;ously t~ .";. ~d by S~iM obscrvations and is ca S ~. Ii et a~ [6] mo~ d the d~ ,lo~ ,t ~!t of ~ o"ydpdite dcposits on gel-derived titania, as a ~ . of time, after iU~ cl~;on in ~5iFn~ t~d Body Pluid. I~ tbc initial 2~ ~itages they dete~d ~It~rc~ Ciyildt~,s all ovcr the surface which ~ - e d in ~un:lbcr and size until, cvcntually, all thc sur~cc was covered by a 10 ~ m coating. Duchc~ne et a~ [5~ ~po~hd the fn~n~tinn of small dcposits on titas~iunl discs after 1~ay CAY~JSU~j to a Simulated Physiological Solutiou. ~ro weeks of ~ clclnial ;.. ,n~ ~ ? jnr~ we~c needcd to produce a~ apatite layer w-ith a ~h~ cc of 1~0 Han~wa et a~ [3] also ~polhd that apatite is naturally formed on Ll~iu~l~ wbe iul~l is h~el~d in a solution whose pH is similar to tbat of thc bioliquid. Theyt~,d a tl .~C~; of 7 mn of the apatite film grown on Ti~ 4V which malce6 it imros6itll~ for this layer to cxhibit ~ny l,.o~.tics of calcium l,h..~ te in this e.l~ilu~c.,l The prcscnt re6ults indicate t~at a calcium r~ with aII apatite-like structure is Daturally fonned on thc surfaces of polLchcd titaT.uuln ~lloys. I~e ll.:~L .~r sc of this layer malces it a sL~itablc surface for bonc ;---h-- l;~ ,r~5 of at least 1 llm are needed for thc calawn l-hr~ h- ~ to sho~ up~ll;cs and cause bone ;...1~..i;~..
~, The nto~rhn'~y of calcium phosphate yle~p;~ depeIlds o~ thc mcta1 s~t~tr- and its surface c~ s It is possible to p~oduce a ~aturally formcd calciuun ~kos~h-~
coa~g by ;."...r,,~ , mctals such ~s titan~um alloys and s~ir-lecc stcel in HBSS.
Ti~ 4V 4000 sce~ls to be the surface that is most favouIable to produce a 0 cnntinl-ous a~d more adhe.~ t ~ te-like coating ~;apable of bone in~luchon LE 2. Dete~nina~on orcalcium p' -sp' ~te depth di~ tio~ on a tita~i~m alloy bul~l~ate using ~-my photoel~hon ~pect~
d~tcs the .~ ~~ r - - of the depth Cli~t~ t~ of sct~d cl~ s in a ~11m, p~;os~ho,u~ d oxygen - ~-4--1~ g coating on a tit~nillm alloy Sa~SlplC
g dcpth ~.~,r,L,.g X-ray Pbot~-1~rt~on Sp.,cl~oscop~, (XPS or ESCA).
'~J~
The samples we~ titanium aUoy plates that h~d bee~ surfacc trcated acco~d~ to the c~eA~ of E~cample 1 to prodl~cc a calcium ~h~s~ coat~ ~hcn ;.. ~ ,~cd m ~jfir~ ulio..S Or s;~ trd body nuids. The salnples were mn-l~tcd dire~y tO
20 a Sl~l~ XPS ~iamplc holder using a sp~g clip ~..;.. ~,. - ....~, with no pre-treahnent.
Thc outer coat~Dg sur~acc was ~ ~~r;. ;r"~ lly ~hJ~ e that no clccllosla~ic ~dl~ problems v.rere ~ tl cd during ~-ray ~rladiation or ion beam etching. All a~alysis v"ere carried out usmg a Su~faoe Scicnce L~lu~ s (SSI) M-probc opc,rating at a base p~e~ul~ of 3~10-9 tO~r.
25 A~
sulvey ~;tlUIU was ~ ûm the "as rc~;~,~3~ surface, to d(t ~ r t~e sulrface co.llposition of thc coating and therefore d~ the Pl~n~nt~ to be .llollilol~d for thc dcpth profile. The XPS de~th profile was o~ h~r~ by ~ t;~ argon ion ~t~e ;nt (ovcr ~n area of approx. 2 x 2 mm) and data ~ icit;~n (from a~l area of30 approx. 300 llm di~eter centre~ in the etched crater). F,~Pntc analysed were carbo~, oxygen, ~~ m~ rh~horusl magnesium and tiPnil~n- Etc~ timc per stcp wa~ variable ~o~ 15 to 120 seconds per cycle and the etc~ ~ate was 3 nm/min using a total sputter time of 4470 s~o~lc ~SJ~
~hc surf~oe rh-~mi~l C~ (il2 atomic percent) of the 'tas ~ dn ooatm~
carbon 44.9%, o~cygen 33.8%, cal~iu~ 10.5%, ~ k~,o~s 8.8%, ~ t~ ll 2.0%
aI~d tit~nil~m 09~o (figur~ 7). Ihe depdl profile o~ the coating rcvcaled a gradual 5 t~n~hnn of c:~c~um and yl.n5r~ om thc coati~g to the su~~ tr;~ ; the ~ nld1 j~l.. of these ~Tem~ntc in thc ~ur~ce toxide la~er), and thus a chpmi~l bonding between coa~ng a~d subs~r~t~ (fi~ure 8). The calcium - o~ygen ~ o~l~h~ uu:~ laye~
(ca~ ml llh~ k ~) i6 tdlm ted aS belllg l~r C ~ -Iy 90 nm, ~lminC a sputter ~ateof 3 nm per mimlte ~ TiT~d on ~ t nt~ F- ~On ;fT~ film On ~ ' and that ~L
10 ~t;u1. . ~ is dcfmed .~ the poi~ wh~c the titauium rcaches approx. ~0% of its inal valuc. A thiJ~ layer of lit~ ,", oxide 5~"~rAt-.~ the calcium 1-~-05~T~t~ layer from the alloy snhStrtqtr- The i~ betwee~ the calciu~ phrS~ TI; aDd t.l i.....
shows ~ges in the oxygcn, ~h~h~oùs~ calcium .~d tit~ tJ~ 5 Thc XPS
pe~ birK~ing ~n~I~ of calcium and ~ )hn~u~ d~e;~ at the I f~~: with the 15 ti~ whcre a ~jt~njlnn û~ide layer is foumd. A~ tL~ egion is lLkely to occur at the bo~ and oxygen has been ~ep' t ~ f~n the calcium E,hosph-~r- to form tih~ u dio~cide at the int~ ~. Metallic titanium is pre6cnt below tbe L~tc~hase Fegion. Mv~ ~ ci ~ ~ is dctect~d a~ 2 - 4 atomic percent thrû~ghout the cal~ .h ~
l~ycr and i..c~eases slightly in co~r ~ation ~ith dcpth towardc the interface with thc iu~ll (oxide). Grbon is found in the b~ of the ti~n;u~n Thc cal~ tc layer t~at ~s fonncd ûn thc titanium alloy c~ ;~t~o iS chf~ y bound to the su~ ta its surface o~ude layer.
EXAMP~E 3. P~epara~on of b~omhnetIc caIci~m phosphate c(iali~gs OD ~etallic 2s Implant~
Ihis e~mrlc illustr~tes a DCW t~o-step rb~i~t l.Gd~lt for prcpar~Dg aII implant w~th a ~fic surfacG ro~ghn~cc., rr.s..l~ [ in a me~allic su~facc that allows f~ct p~ ;n~ of bin~ lci~ phn~rh~te (Ca-P) coatings ~om in vi~o super--saturated r '~fir -i~!n sol~ (SCS). The specific surfa~e lo~ esults in the 30 following advantages: (i) the l,;u..~ coatings directly induccd f~om SCS are ~b~ IIy bouDd t~ mctallic subs~ and show higher bone-bondin~ sbility, (ii) the ro~tin~ can be produced onto c~npleY-sh~pcd and/or maclo-porolls i~nrlq~tc, and (iii) it is ~ controllable and cost-effective way to aC4ulr~ Ca-P ~o~tin~
BO ~91 CA 02205107 1997-05-12 Mmniab a~d A~ethods A nc~ly dcveloped two step rbpmir~l h~ .lcltwaS ~"F,, r~ -~ on thc m~tallic i~plant ~"~t~ lc, i.e. c~c.wally pu~e tita~ium (rp.Ti), ~ 116A14V aDd po~ous t~nt~ n CIa), to produce a ~fic surface 5~ zh-n~ss~ ~ur~g this treannent, two selies s of ~h~mi.~ol r~ae. ~ W~ ~d for titanium (cp.r~ d Ti6~1~V) ~d p-lt~l~m implant m~t~l5~ ~ ,cli~ , that resulted ~n the p~ i of t~c speciS~
~c ~ for the pl~dtil)ll of the coating. For the fo~met, tbc samples were treatbdwi~ a ~e of HCI and H2SO4, followed by j"""r,~ n in a NaOH s~iutinn The pOlOUs t~nt~ samples were t~bated with a mixture of HCI, H~S04 and HF, followed 10 by i,~~ - s,oJ~ m ~2~2 Two ki~ds of SCSs with di~ t ~a and P c4~r~ alions, f~st r~ fioatinn solution (FCS) and coln~erc;al Ha~}~s' b~ salt solution,ffIBSS), were used for ~~
p c~ti~ rO prolhote thc C~--P t~ m OD the metallic s~ ~s, a pqr~l~ ;f;r".l;"" (~re-Ca) ~lu~dulb ~a6 p~ r~ o~ half the t~eated samples before 15 ;---- .." Fi~ ~ ~ the SCS. The Pre-Ca was carried out by ;. ~f ~-h~ ~;~ the samples in 05N
Na~HPO4 ovc~night and then t.~ r~ e them into saturated Ca(OH)~ fo~ S h The ~CS
solution volume used for imm~on was 15 ml per cm2 of sample 6urface arca. I~e samples vvele ,a~u~l ed in sealed poly~ly~buc v~als at 37CC in a calibrated water-bath.
~nniT~e elcctroD mic~03copy (S~M) togcther ~vith cnc~gy dispe~se X-ray ~
20 analyses, ~-ray di~ ion (XR~ ared (D?.) s~ Lo~o~lletry werc used to t~ the ob~ P c~
~esults T~e l~ cli~ Ca-P coatings were fast l)r~ d on the treated ~p.ri and Ti6A14 samples by ~ ~sio.~ iQ both FCS and HBSS no matter whcthcr the Pre-Ca p~ucc~h 25 wa~ ~.fo~ cd or llot. But the P~c-Ca ~ o.~t~ 0uld /lr~m~t~ y ~peed-up tbe t~t~ ate of the Ca-P coatings as listed in table 2.
Figure 9 show6 that a h:~mim~ Ca-P coating, ~,~ "ntely 16~ thick, was formed o~ treated ~:p.Ti after 16 hours of ~ iO~ vi~ Prc~a. ~e coating got thicker with ~ n~ time asiT~irato~d by ~D~ (~Igure 10) and XRI) (figurc 11) 30 ~sults. Tbc p.~, -;yitatiOn ~ate of thc Ca-P coating irl ~IBSS is slower than tbat in FCS.
But thc coati~g ~om HBSS (figure 12) ~vas mu~ denser than that ~m F~:S. The coating from HBSS ma~nly ~ ;ct~l of apatite (~Igure 13). Riomi~Pt;r Ca-P c~
~40391 CA 02205107 1997-05-12 could ~o be precipitated on pO~ S Ta samples (f;gure 14) after the Lc~t.. ~ nt. Ihe sur~ce ~o~tent ~hangc of t~e sample was Art~rteA by E~X as show~ L~ fi~ure 15. lt is ~ h, that no ~ pi~ftiO~ was o~ ,d on aIIy untIeated s~nples after 2 wceks of ;~ r..~ CS or TIBSS, eve~ with Pre-Ca. The for~nation of a spe~fic ht~jllm s alld t~nt~l~lm o~de laye~ their llc7tm~nt~ is pr~bably the ma~n r~son for the i~lu~ p~cipitation of Ca-P c~ ~i~ by means of in vitro ;---- ~ s in~l in SCS. Tbe p~u~i of thc h~ ~ for titanium impl~ and tf~ h~ could not be c - ~.1. ~er.~, o~ no Ca-P ooating was acquihcd.
Co. ~
10 This bi'~ tt;r calcium I~hosF~h~te coating study has show~ tha~:-. Ihe neuvly du~,lopcd tw~step trcatment is an cffective mcthod to prepare ~ ;oc,~
- mctallic implaIIt s~lrfaccs allo~ing f~st yle~ip~ of adherent b;QY~ PI;r Ca-P
C4 ~ y in v~o in.~ .. iu SCS. The rh~nie~l Ieagents nccded for thc treatme~t of tit~n~ n ~pl~nt . ~ and t~nt~h~n a~e di~ t from eac~ oth~.
15 . The p~ of Ca-P coat~gs could be r1-~ n~tiC~IIy accele~ated by means of pre-calcify~ the treated samples befo~c thc ;~ n--~.
. Ihe ~ ;nn ~ate and ~ -l-4Sjtinn of tbe Ca-P coati~gs can be ~ t~d by controlli~g ~c c~ -Q-~J~I~ of the SCSs (EiCS o~ ~BSS) for ;~ r~;on Table 1- Surface rou~Dess me~ure~ents results zo Surface fiuisb R8 (~Im) Rz ~1~) ~ (l~m) ~-6AI-4V 1200 grit 0,47 0.01 3.74~0.04 5.13~0.08 rl-~Al~V4000grit 0.~~0.03 1.91~0.31 2.46~0~4 ~ 4V 1 llm 0.03+0.00 o ~s~o.ns 0.48~0.03 n-Al-2~Fe 1200 g~it 0.4~0.03 2.g7_0~5 3.47_0.48 2s 15~ 25~e 4000 gr~t 0.23-0.01 1.97~0.18 2.46~034 Ti-AI-2.5Fc ~ ~un 0.04~0.01 0.28+0.11 0.36+019 316 L 1200 gnt 0.3+0.06 2.32-0.47 2.96+0.03 316 L 4000 grlt 0.04+û.01 0.35+0.1 0.46 ~ 0.1 ~040391 CA 02205107 1997-05-12 11 , Table 2 - Iist Of Ca2~ d HPo42- c~ t;~,c, precipihtion rate aod ~f Ca-P coa~neS OII cp.n ~d T~ 4V.
C~t~io.~ ~mM) Ca2~ 3.0 1 26 Hpo42 1.87 0.78 ~" rate of ~o Pre-C~ 0.5 ~ mlwk S cûa~ Prc~ ~r 3 ~wk ('~ s;tic~ of coating apatitc, OCPapa~dtc ~ ptions Figur~ 1 - Ca ~- ~.~.dLiul~ as a functiQn of time Figure 2 - P CO~ LiOI- as a fi~nction of time 0 F~gure 3 - SEM ph~l -;~ ~ographs of the metal s~facc~ after imme~sio~ IBSS. A: -6AI-4V 1200; B: Ti 6Al-4V 4000, C: Ti~ 4V 1 ~m; D~ 1-25Fe 1 llm, E: Ti-AI-25Fe 4000; F - st~jnl~cc cteel 1200 Fgure 4 - AFl~ ~l-ot~ og~aph of a r~ 5Fe 1 ,~n sample aftcr I ~,.sio~ in ~BSS. In~,l~g J~ .;ri~o~j9~ ~om field n to 3. S~ nin~ le~gth ~m field 3:
15 ~Im.
F~gun; S - ~MA spec~a ~c4uhc~ on a Ti-6Al-4V 41)00 sample bcfore (A) and after Figure ~ - XRD ~ acquired on a non-h .,.scd (A) ~nd ;~ 3) li-6~1-4V 1 ~m ~e ~o Fgure 7. Sur~ace chP~nieAl cr. ~ (in atomic perccnt) of the "as ~ ,1 coating. Tc 8. Dept~ profile of the coating, ~om coating to ~ t~.
Figure ~ nni~ electrorl rnicrograph of the Ca-P coatinK (CP) pr~ ~ o~ cp.Ti ~i) afte~ lfi hou~s ûf i~ r ~ -~.. in E~CS with Pre-Ca ~ure 10. ED~ spectra of the cp.Ti 6~1rfaces Don-trea~ed, treated and ;",. -r"~'~1 ill FCS
with Pre-Ca for ~lifrG~c~ hou~s. Thc ~h~ APr of O kQ pea~ is cle~rll~ seen afterthe l.e~t~ c .-. ~e Ca and P co~tPDts i. ~ d with the i~lGIc--- of ;~
time.
re 11. XRD pattP~s of the cp.Ti suIfaces after dlrrc~ t hûuss of i~T~m~hr~ iD. FCS
with Pre-Ca. The counts of apatitc peaks get higher with incl~ascd ;...~ ,.6io t~mes. Octa calcium ph~;rh~t~ (OCP) starts to be formcd at around 8 hours.
CA 02205l07 l997-05-l2 Figurc 1~ nr:~ dectro~ h of a de~sc Ca-P ~oatmg (CP~ on c~.Ti from ~SS a~ 1 weck Of inlmr ~ with Pre-Ca The laycr betwec:u coating aDd ~.uL~ r~ the til~;ul~l ~dc layer (OL), ~smed as a Iesult of the s ~lgure 13 Ihi~-film XRD patte~ of a densc Ca-P coating ~ il. d by j~mPrcinn in~iS with Pre-(::a fa~ 1 week.
~gu~ 14. S~-~s-nni~ elect~ ph of porous i ~ Tn CTa) after 2 day6 ;...~ ~ ~ cioJ~
S with Pre-Ca. I~e coating is fosmed ~ol.gLwl t~e porous Tng~P~gl Figu~ 15. EDX spec~a of (a) noII-trcated, (b) tIeated, and (c) Pre-Ca treated, 2 day 0 FCS ;.. ~c.~ed po~ous ~ n~ ~ra) sa~plc.
Litera~u~e rc~e. ~
1. Y. Fujishiro, T. Sato and A. Oku~i, rco~tjng of h~d~u~y~alitL on metal platcs using thc~ iccor~7~ioD of calaum -EDTA c}lelste in l,~h~c ~ ~ sol-~jnn~ under hydrothennal c~ t1OD~", J. Ma~er. ~ ter in Med, 6, pp. 172-176, 1995 2. S.R. Radin and P. DUC~ C~ 1. BianL Ua~er. Res." 27, pp. 35, 1993 3. T Hanaw~, "T~tanium ~d its o~de film: a ~~!bch~qt~- for fo~g apatite", in Proc.
of the ~one Riow~t~ql T~lt~.lf~ W(!rlrshnp Toronto, Dec. 19~Q, J.E. Davie6 ed.J
Uni~r. Toronto Press, pp. 49-61, 1991 4. ~. Leit~o, M.A. Barbosa and K. dc Groot, "In vitr~ rRI~;ri~ali~f~ of 0~ ~3~1ic z0 i~plant m~t~ql~n~ J. M~ter. Sc: ~ate~ in Med, 6, pp. 84~852, 1995 5. P D~ c, S. Radin and K. lshilcawa, "~e ~te of dciuIn rh~
- ;~ ioL. o~ metal and Q~nR~~ and the ~ t~r~n~hip to l);o~ivily", in Bo~c ~on~ g Rjomqt~iRI~, P. Pucheyne, r. Kokubo ~ CA. Ya~ Blitters~ill~ (eds), Reed ~tb~re C~ vu~ic~tio~Ns~ pp. 213-218, 1~g2 zS 6. Ii, P, P~D Thesis, Leiden I~ ity (1993)
Claims (11)
1. An implantable device of a material having a surface roughness with an average peak distance (Ra value) between 10 and 1,000 nm.
2. An implantable device according to claim 1 having a surface roughness with anaverage peak distance between 20 and 500 nm.
3. An implantable device according to claim 1 or 2 having a surface roughness with an average depth between 20 and 1,000 nm.
4. An implantable device according to any one of claims 1-3, wherein the surfaceis coated with a layer of a calcium phosphate having a thickness of 50 nm - 100 µm, in particular of between 1000 nm and 50 µm.
5. An implantable device according to any one of claims 1-4, wherein said material is a metal, a metal alloy, a ceramic material, a natural or synthetic polymer, or a composite of any of these materials.
6. A process for producing an implantable device, comprising subjecting a porous or non-porous material to a surface treatment until a surface roughness with an average peak distance (Ra value) between 10 and 1,000 nm is obtained.
7. A process according to claim 6, wherein said surface treatment comprises a mechanical treatment such as a sanding or scouring step, e.g. using a diamond paste.
8. A process according to claim 6, wherein said surface treatment comprises a chemical treatment involving subjecting the surface to acidic, alkaline and/or oxidising solutions.
9. A process according to any one of claims 6-8, wherein the roughened surface is subsequently subjected to precipitation of calcium phosphate from a solution containing calcium and phosphate ions.
10. A process according to claim 9, wherein said solution has a pH of 4-10, preferably 6-8.
11. Use of a device according to any one of claims 1-5, or produced according to any one of claims 6-8, as a bone substitute, a joint prosthesis, a dental implant, amaxillofacial implant, a vertebral surgery aid, a transcutaneous device or any other hard-tissue-related device.
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CA002205107A Abandoned CA2205107A1 (en) | 1996-05-10 | 1997-05-12 | Implant material and process for producing it |
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Cited By (1)
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US6207218B1 (en) | 1998-09-15 | 2001-03-27 | Isotis B.V. | Method for coating medical implants |
Families Citing this family (112)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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SE9701647D0 (en) * | 1997-04-30 | 1997-04-30 | Nobel Biocare Ab | Calcium-phonsphate coated implant element |
JP3072373B1 (en) * | 1999-07-05 | 2000-07-31 | 工業技術院長 | Artificial dental root having pollutant, germ adhesion suppressing function and acid resistance, and manufacturing method |
US20060194008A1 (en) * | 1999-09-22 | 2006-08-31 | Princeton University | Devices with multiple surface functionality |
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US6805898B1 (en) * | 2000-09-28 | 2004-10-19 | Advanced Cardiovascular Systems, Inc. | Surface features of an implantable medical device |
US7083642B2 (en) * | 2000-12-22 | 2006-08-01 | Avantec Vascular Corporation | Delivery of therapeutic capable agents |
US7018418B2 (en) * | 2001-01-25 | 2006-03-28 | Tecomet, Inc. | Textured surface having undercut micro recesses in a surface |
US6620332B2 (en) | 2001-01-25 | 2003-09-16 | Tecomet, Inc. | Method for making a mesh-and-plate surgical implant |
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JP2002322013A (en) * | 2001-04-25 | 2002-11-08 | Univ Nagoya | Precursor of active substance, active substance produced by using the precursor, and method for producing the active substance |
US7776085B2 (en) * | 2001-05-01 | 2010-08-17 | Amedica Corporation | Knee prosthesis with ceramic tibial component |
US7695521B2 (en) | 2001-05-01 | 2010-04-13 | Amedica Corporation | Hip prosthesis with monoblock ceramic acetabular cup |
US20050177238A1 (en) * | 2001-05-01 | 2005-08-11 | Khandkar Ashok C. | Radiolucent bone graft |
AU2002324443A1 (en) * | 2001-06-14 | 2003-01-02 | Amedica Corporation | Metal-ceramic composite articulation |
SE519531C2 (en) * | 2001-07-04 | 2003-03-11 | Nobel Biocare Ab | Implants including pore arrangements coated with calcium phosphate |
WO2003009777A2 (en) * | 2001-07-26 | 2003-02-06 | Avantec Vascular Corporation | Delivery of therapeutic capable agents |
EP1448246B2 (en) | 2001-11-19 | 2015-09-09 | Scil Technology GmbH | Method for producing a homogeneously coated device having osteoinductive and osteoconductive properties |
WO2003072496A1 (en) * | 2002-02-26 | 2003-09-04 | Hyun-Man Kim | Calcium phosphate colloids, dots, islands, thin films or granules and its preparation |
EP1358859A1 (en) * | 2002-04-29 | 2003-11-05 | Politecnico Di Milano | Bone prostheses having multilayer interface |
GB0210786D0 (en) * | 2002-05-10 | 2002-06-19 | Plasma Coatings Ltd | Orthopaedic and dental implants |
US6794273B2 (en) * | 2002-05-24 | 2004-09-21 | Fujitsu Limited | Semiconductor device and manufacturing method thereof |
US20100185294A1 (en) * | 2002-06-04 | 2010-07-22 | Arthrosurface Incorporated | Nanorough Alloy Substrate |
SE523236C2 (en) * | 2002-07-19 | 2004-04-06 | Astra Tech Ab | An implant and a method of treating an implant surface |
SE523288C2 (en) * | 2002-07-19 | 2004-04-06 | Astra Tech Ab | An implant and a method of treating an implant surface |
JP4358741B2 (en) * | 2002-09-10 | 2009-11-04 | スキール テヒノロギー ゲーエムベーハー | Metal implants coated with osteoinductive protein under low oxygen concentration |
WO2004058098A2 (en) * | 2002-12-17 | 2004-07-15 | Amedica Corporation | Total disc implant |
GB0304168D0 (en) * | 2003-02-24 | 2003-03-26 | Benoist Girard Sas | Surface treatment of metal |
US20040167632A1 (en) * | 2003-02-24 | 2004-08-26 | Depuy Products, Inc. | Metallic implants having roughened surfaces and methods for producing the same |
US8388624B2 (en) | 2003-02-24 | 2013-03-05 | Arthrosurface Incorporated | Trochlear resurfacing system and method |
US8251700B2 (en) * | 2003-05-16 | 2012-08-28 | Biomet 3I, Llc | Surface treatment process for implants made of titanium alloy |
US7067169B2 (en) | 2003-06-04 | 2006-06-27 | Chemat Technology Inc. | Coated implants and methods of coating |
US20040267376A1 (en) * | 2003-06-25 | 2004-12-30 | Kabushiki Kaisha Kobe Seiko Sho (Kobe Steel, Ltd) | Ceramic member for medical implant and its production method |
US7419680B2 (en) * | 2003-10-01 | 2008-09-02 | New York University | Calcium phosphate-based materials containing zinc, magnesium, fluoride and carbonate |
US9199005B2 (en) * | 2003-10-01 | 2015-12-01 | New York University | Calcium phosphate-based materials containing zinc, magnesium, fluoride and carbonate |
DK1529497T3 (en) * | 2003-11-04 | 2009-12-14 | Friadent Gmbh | Dental implant component |
EP1529498B9 (en) * | 2003-11-05 | 2014-09-10 | Dentsply Implants Manufacturing GmbH | Multi part non metal implant |
WO2005074530A2 (en) * | 2004-01-30 | 2005-08-18 | Georgette Frederick S | Metallic bone implant having improved implantability and method of making the same |
SE530060C2 (en) * | 2004-09-01 | 2008-02-19 | Nobel Biocare Ab | Implants for dental prosthetics and the procedure and systems for making the implant |
US7473278B2 (en) * | 2004-09-16 | 2009-01-06 | Smith & Nephew, Inc. | Method of surface oxidizing zirconium and zirconium alloys and resulting product |
US8750983B2 (en) | 2004-09-20 | 2014-06-10 | P Tech, Llc | Therapeutic system |
US7785648B2 (en) * | 2004-09-22 | 2010-08-31 | New York University | Adherent apatite coating on titanium substrate using chemical deposition |
US7235592B2 (en) * | 2004-10-12 | 2007-06-26 | Zimmer Gmbh | PVA hydrogel |
WO2006050365A2 (en) * | 2004-10-28 | 2006-05-11 | The Regents Of The University Of Michigan | Methods for production of synthetic hydroxyapatite nanorods |
CA2532388A1 (en) * | 2005-01-07 | 2006-07-07 | Inframat Corporation | Coated medical devices and methods of making and using |
AU2006216655B2 (en) | 2005-02-23 | 2012-05-31 | Zimmer Technology, Inc. | Blend hydrogels and methods of making |
EP1853394A4 (en) * | 2005-02-24 | 2009-09-30 | Biomet 3I Llc | Surface treatment methods for implants made of titanium or titanium alloy |
RU2007143317A (en) * | 2005-04-22 | 2009-05-27 | Хайбрид Плэстикс, Инк. (Us) | BIOMIMETIC SUBSTANCES CONTAINING POLYEDRAL OLIGOMERIC SILESESQUIOXANES |
US7901462B2 (en) * | 2005-06-23 | 2011-03-08 | Depuy Products, Inc. | Implants with textured surface and methods for producing the same |
US7571295B2 (en) * | 2005-08-04 | 2009-08-04 | Intel Corporation | Memory manager for heterogeneous memory control |
US20070098799A1 (en) * | 2005-10-28 | 2007-05-03 | Zimmer, Inc. | Mineralized Hydrogels and Methods of Making and Using Hydrogels |
WO2007059038A2 (en) | 2005-11-14 | 2007-05-24 | Biomet 3I, Inc. | Deposition of discrete nanoparticles on an implant surface |
US8262730B2 (en) * | 2005-12-07 | 2012-09-11 | Zimmer, Inc. | Methods of bonding or modifying hydrogels using irradiation |
ES2606666T3 (en) | 2005-12-15 | 2017-03-27 | Smith & Nephew, Inc. | Medical implant hardened by diffusion |
US20070141108A1 (en) * | 2005-12-20 | 2007-06-21 | Zimmer, Inc. | Fiber-reinforced water-swellable articles |
JP2007177244A (en) * | 2005-12-22 | 2007-07-12 | Zimmer Inc | Perfluorocyclobutane crosslinked hydrogel |
US8252058B2 (en) * | 2006-02-16 | 2012-08-28 | Amedica Corporation | Spinal implant with elliptical articulatory interface |
US20070198093A1 (en) * | 2006-02-17 | 2007-08-23 | Amedica Corporation | Spinal implant with offset keels |
US8110242B2 (en) * | 2006-03-24 | 2012-02-07 | Zimmer, Inc. | Methods of preparing hydrogel coatings |
EP1847278A1 (en) * | 2006-04-13 | 2007-10-24 | Camlog Biotechnologies AG | Bio-dissolvable salt coatings of implants for the protection against organic impurities |
US20080124373A1 (en) * | 2006-08-02 | 2008-05-29 | Inframat Corporation | Lumen - supporting devices and methods of making and using |
US20080069854A1 (en) * | 2006-08-02 | 2008-03-20 | Inframat Corporation | Medical devices and methods of making and using |
NO325290B1 (en) * | 2006-10-10 | 2008-03-17 | Gunnar Rolla | Titanium implant and method of manufacture thereof |
WO2008051555A2 (en) | 2006-10-24 | 2008-05-02 | Biomet 3I, Llc. | Deposition of discrete nanoparticles on a nanostructured surface of an implant |
EP2136717B1 (en) | 2006-12-11 | 2013-10-16 | Arthrosurface Incorporated | Retrograde resection apparatus |
KR100930279B1 (en) * | 2007-06-20 | 2009-12-09 | 재단법인서울대학교산학협력재단 | Calcium Phosphate Ultra Thin Films and Preparation Method thereof |
US20090008365A1 (en) * | 2007-07-06 | 2009-01-08 | Depuy Products, Inc. | Microtextured Implants and Methods of Making Same |
EP2022447A1 (en) * | 2007-07-09 | 2009-02-11 | Astra Tech AB | Nanosurface |
KR100775537B1 (en) * | 2007-07-19 | 2007-11-28 | (주)오스테오필 | Method of fabricating implant with improved surface properties and implant fabiricated by the same method |
US20090187197A1 (en) * | 2007-08-03 | 2009-07-23 | Roeber Peter J | Knit PTFE Articles and Mesh |
US20090036996A1 (en) * | 2007-08-03 | 2009-02-05 | Roeber Peter J | Knit PTFE Articles and Mesh |
US7731988B2 (en) | 2007-08-03 | 2010-06-08 | Zimmer, Inc. | Multi-polymer hydrogels |
US20090043398A1 (en) * | 2007-08-09 | 2009-02-12 | Zimmer, Inc. | Method of producing gradient articles by centrifugation molding or casting |
US8062739B2 (en) * | 2007-08-31 | 2011-11-22 | Zimmer, Inc. | Hydrogels with gradient |
US7947784B2 (en) * | 2007-11-16 | 2011-05-24 | Zimmer, Inc. | Reactive compounding of hydrogels |
US8034362B2 (en) | 2008-01-04 | 2011-10-11 | Zimmer, Inc. | Chemical composition of hydrogels for use as articulating surfaces |
ES2545781T3 (en) | 2008-01-28 | 2015-09-15 | Biomet 3I, Llc | Superficial implant with greater hydrophilicity |
US8361381B2 (en) | 2008-09-25 | 2013-01-29 | Smith & Nephew, Inc. | Medical implants having a porous coated surface |
US9592043B2 (en) * | 2009-03-31 | 2017-03-14 | Covidien Lp | Multizone implants |
US20100268227A1 (en) | 2009-04-15 | 2010-10-21 | Depuy Products, Inc. | Methods and Devices for Bone Attachment |
US8696759B2 (en) * | 2009-04-15 | 2014-04-15 | DePuy Synthes Products, LLC | Methods and devices for implants with calcium phosphate |
WO2016154393A1 (en) | 2009-04-17 | 2016-09-29 | Arthrosurface Incorporated | Glenoid repair system and methods of use thereof |
WO2010121250A1 (en) | 2009-04-17 | 2010-10-21 | Arthrosurface Incorporated | Glenoid resurfacing system and method |
EP2429429B1 (en) | 2009-04-17 | 2018-07-25 | Arthrosurface Incorporated | Glenoid resurfacing system |
US8475536B2 (en) * | 2010-01-29 | 2013-07-02 | DePuy Synthes Products, LLC | Methods and devices for implants with improved cement adhesion |
EP2542165A4 (en) | 2010-03-05 | 2015-10-07 | Arthrosurface Inc | Tibial resurfacing system and method |
US8641418B2 (en) | 2010-03-29 | 2014-02-04 | Biomet 3I, Llc | Titanium nano-scale etching on an implant surface |
TWI543754B (en) * | 2010-06-24 | 2016-08-01 | Univ Kaohsiung Medical | Surface treatment of dental implants with tissue integration |
DE102010025533B4 (en) | 2010-06-29 | 2014-09-04 | Heraeus Medical Gmbh | Procedure for bone growth promoting coating |
US9381112B1 (en) | 2011-10-06 | 2016-07-05 | William Eric Sponsell | Bleb drainage device, ophthalmological product and methods |
US8632489B1 (en) | 2011-12-22 | 2014-01-21 | A. Mateen Ahmed | Implantable medical assembly and methods |
EP2804565B1 (en) | 2011-12-22 | 2018-03-07 | Arthrosurface Incorporated | System for bone fixation |
ES2671740T3 (en) | 2012-03-20 | 2018-06-08 | Biomet 3I, Llc | Treatment surface for an implant surface |
WO2014008126A1 (en) | 2012-07-03 | 2014-01-09 | Arthrosurface Incorporated | System and method for joint resurfacing and repair |
US9492200B2 (en) | 2013-04-16 | 2016-11-15 | Arthrosurface Incorporated | Suture system and method |
US9962265B2 (en) | 2014-03-07 | 2018-05-08 | Arthrosurface Incorporated | System and method for repairing articular surfaces |
US10624748B2 (en) | 2014-03-07 | 2020-04-21 | Arthrosurface Incorporated | System and method for repairing articular surfaces |
US11607319B2 (en) | 2014-03-07 | 2023-03-21 | Arthrosurface Incorporated | System and method for repairing articular surfaces |
DK3685866T3 (en) * | 2014-05-02 | 2023-11-06 | The Royal Institution For The Advancement Of Learning / Mcgill Univ | STRUCTURALLY POROUS BIOMATERIAL AND IMPLANT FORMED THEREOF |
US20150366668A1 (en) * | 2014-06-23 | 2015-12-24 | Community Blood Center | Cellular-scale surface modification for increased osteogenic protein expression |
CN108096640A (en) * | 2016-11-24 | 2018-06-01 | 重庆润泽医药有限公司 | A kind of porous material |
US10537658B2 (en) | 2017-03-28 | 2020-01-21 | DePuy Synthes Products, Inc. | Orthopedic implant having a crystalline gallium-containing hydroxyapatite coating and methods for making the same |
US10537661B2 (en) | 2017-03-28 | 2020-01-21 | DePuy Synthes Products, Inc. | Orthopedic implant having a crystalline calcium phosphate coating and methods for making the same |
WO2019028344A1 (en) | 2017-08-04 | 2019-02-07 | Arthrosurface Incorporated | Multicomponent articular surface implant |
GB2609338B (en) | 2019-03-12 | 2023-06-14 | Arthrosurface Inc | Humeral and glenoid articular surface implant systems and methods |
Family Cites Families (35)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3984914A (en) * | 1974-07-24 | 1976-10-12 | Robert Schwartz | Oral implant |
JPS5214095A (en) * | 1975-07-23 | 1977-02-02 | Sumitomo Chemical Co | Implant in bone |
US4687487A (en) * | 1978-07-21 | 1987-08-18 | Association Suisse Pour La Recherches Horlogere | Joint implant |
SE416175B (en) * | 1979-03-07 | 1980-12-08 | Per Ingvar Branemark | FOR IMPLANTATION IN BODY TISSUE Separate Bone Tissue, Dedicated Material |
DE3223925C2 (en) * | 1982-06-26 | 1986-07-31 | Feldmühle AG, 4000 Düsseldorf | Implantable elbow joint |
GB8318483D0 (en) * | 1983-07-08 | 1983-08-10 | Zimmer Deloro Surgical Ltd | Skeletal implants |
US4636526A (en) * | 1985-02-19 | 1987-01-13 | The Dow Chemical Company | Composites of unsintered calcium phosphates and synthetic biodegradable polymers useful as hard tissue prosthetics |
FR2585576B1 (en) * | 1985-07-30 | 1992-01-03 | Bioetica Sa | BONE MATRIX REPLACEMENT PROMOTING OSTEOGENESIS |
JPH0669482B2 (en) * | 1985-08-08 | 1994-09-07 | 住友化学工業株式会社 | Intraosseous implant manufacturing method |
US4818559A (en) * | 1985-08-08 | 1989-04-04 | Sumitomo Chemical Company, Limited | Method for producing endosseous implants |
DD246028A1 (en) * | 1986-02-12 | 1987-05-27 | Karl Marx Stadt Tech Hochschul | CERAMIZED METAL IMPLANT |
GB2189815B (en) * | 1986-03-24 | 1990-10-10 | Permelec Electrode Ltd | Titanium composite materials coated with calcium phosphate compound and process for production thereof |
US5344457A (en) * | 1986-05-19 | 1994-09-06 | The University Of Toronto Innovations Foundation | Porous surfaced implant |
JPS6399867A (en) * | 1986-10-17 | 1988-05-02 | ペルメレツク電極株式会社 | Composite material coated with calcium phosphate and its production |
US4879136A (en) * | 1987-02-24 | 1989-11-07 | Dentsply G.M.B.H. | Method of applying opaque dental ceramic material to a metal structure |
JPS6486975A (en) * | 1987-09-29 | 1989-03-31 | Permelec Electrode Ltd | Preparation of calcium phosphate compound coated composite material |
DE3865421D1 (en) * | 1987-12-23 | 1991-11-14 | Sumitomo Chemical Co | COATING LIQUID CONTAINING HYDROXYAPATITE AND METHOD FOR PRODUCING A HYDROXYAPATITE COVER USING THE SAME. |
US5180426A (en) * | 1987-12-28 | 1993-01-19 | Asahi Kogaku Kogyo K.K. | Composition for forming calcium phosphate type setting material and process for producing setting material |
US4880610A (en) * | 1988-04-20 | 1989-11-14 | Norian Corporation | In situ calcium phosphate minerals--method and composition |
US5219361A (en) * | 1988-09-16 | 1993-06-15 | Clemson University | Soft tissue implant with micron-scale surface texture to optimize anchorage |
EP0388576B1 (en) * | 1989-03-23 | 1993-09-15 | Institut Straumann Ag | Metallic implant |
JP2830262B2 (en) * | 1990-01-08 | 1998-12-02 | 住友化学工業株式会社 | Method for forming hydroxyapatite film |
US5164187A (en) * | 1990-04-05 | 1992-11-17 | Norian Corporation | Hydroxyapatite prosthesis coatings |
JP2978203B2 (en) * | 1990-04-20 | 1999-11-15 | 日本特殊陶業株式会社 | Method for producing ceramic body having bioactive surface layer |
SE468153B (en) * | 1990-10-08 | 1992-11-16 | Astra Meditec Ab | SET FOR TREATMENT OF TITAN OR TITAN ALLOY IMPLANT |
US5205921A (en) * | 1991-02-04 | 1993-04-27 | Queen's University At Kingston | Method for depositing bioactive coatings on conductive substrates |
US5478237A (en) * | 1992-02-14 | 1995-12-26 | Nikon Corporation | Implant and method of making the same |
US5358529A (en) * | 1993-03-05 | 1994-10-25 | Smith & Nephew Richards Inc. | Plastic knee femoral implants |
NL9301941A (en) * | 1993-11-09 | 1995-06-01 | Klaas De Groot | Method of applying a coating of a bioactive material to implants. |
US5607480A (en) * | 1993-11-10 | 1997-03-04 | Implant Innovations, Inc. | Surgically implantable prosthetic devices |
US5947893A (en) * | 1994-04-27 | 1999-09-07 | Board Of Regents, The University Of Texas System | Method of making a porous prothesis with biodegradable coatings |
DE69536061D1 (en) * | 1994-11-30 | 2010-05-12 | Biomet 3I Llc | Preparation of an implant surface |
CA2223596A1 (en) * | 1995-06-06 | 1996-12-12 | Osteogenics Inc. | Biocompatible hydroxyapatite formulations and uses therefor |
JPH0956805A (en) * | 1995-08-24 | 1997-03-04 | Millennium Biologics Inc | Improved sintering method for thin film manufacturing of calcium phosphate material |
US5730598A (en) * | 1997-03-07 | 1998-03-24 | Sulzer Calcitek Inc. | Prosthetic implants coated with hydroxylapatite and process for treating prosthetic implants plasma-sprayed with hydroxylapatite |
-
1997
- 1997-05-12 ES ES97201424T patent/ES2185861T3/en not_active Expired - Lifetime
- 1997-05-12 DE DE69720316T patent/DE69720316T2/en not_active Expired - Fee Related
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- 1997-05-12 AT AT97201424T patent/ATE226453T1/en not_active IP Right Cessation
- 1997-05-12 CA CA002205104A patent/CA2205104A1/en not_active Abandoned
- 1997-05-12 CA CA002205107A patent/CA2205107A1/en not_active Abandoned
- 1997-05-12 US US08/855,835 patent/US6069295A/en not_active Expired - Fee Related
- 1997-05-12 AT AT97201425T patent/ATE235927T1/en not_active IP Right Cessation
- 1997-05-12 ES ES97201425T patent/ES2196252T3/en not_active Expired - Lifetime
-
1999
- 1999-04-23 US US09/299,043 patent/US6146686A/en not_active Expired - Fee Related
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6207218B1 (en) | 1998-09-15 | 2001-03-27 | Isotis B.V. | Method for coating medical implants |
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DE69716505T2 (en) | 2003-06-26 |
ATE235927T1 (en) | 2003-04-15 |
DE69720316T2 (en) | 2004-04-01 |
CA2205104A1 (en) | 1997-11-10 |
US6069295A (en) | 2000-05-30 |
DE69720316D1 (en) | 2003-05-08 |
DE69716505D1 (en) | 2002-11-28 |
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ATE226453T1 (en) | 2002-11-15 |
US6146686A (en) | 2000-11-14 |
ES2196252T3 (en) | 2003-12-16 |
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