US3677795A - Method of making a prosthetic device - Google Patents
Method of making a prosthetic device Download PDFInfo
- Publication number
- US3677795A US3677795A US821080A US3677795DA US3677795A US 3677795 A US3677795 A US 3677795A US 821080 A US821080 A US 821080A US 3677795D A US3677795D A US 3677795DA US 3677795 A US3677795 A US 3677795A
- Authority
- US
- United States
- Prior art keywords
- pyrolytic carbon
- substrate
- carbon
- coating
- coated
- 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.)
- Expired - Lifetime
Links
- 238000004519 manufacturing process Methods 0.000 title description 4
- 239000002296 pyrolytic carbon Substances 0.000 abstract description 79
- 239000000758 substrate Substances 0.000 abstract description 47
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 abstract description 40
- 238000000034 method Methods 0.000 abstract description 31
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 29
- 229910052799 carbon Inorganic materials 0.000 abstract description 23
- 238000006243 chemical reaction Methods 0.000 abstract description 21
- 239000007789 gas Substances 0.000 abstract description 21
- 239000001294 propane Substances 0.000 abstract description 20
- 239000000463 material Substances 0.000 abstract description 19
- 230000008021 deposition Effects 0.000 abstract description 15
- 239000000203 mixture Substances 0.000 abstract description 12
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 11
- 229910052710 silicon Inorganic materials 0.000 abstract description 11
- 239000010703 silicon Substances 0.000 abstract description 11
- 229910052715 tantalum Inorganic materials 0.000 abstract description 10
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 abstract description 10
- 238000002513 implantation Methods 0.000 abstract description 9
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 abstract description 8
- 239000011261 inert gas Substances 0.000 abstract description 8
- 229910052750 molybdenum Inorganic materials 0.000 abstract description 8
- 239000011733 molybdenum Substances 0.000 abstract description 8
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 abstract description 8
- 229910052721 tungsten Inorganic materials 0.000 abstract description 8
- 239000010937 tungsten Substances 0.000 abstract description 8
- 239000001273 butane Substances 0.000 abstract description 7
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 abstract description 7
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 abstract description 7
- 229930195733 hydrocarbon Natural products 0.000 abstract description 6
- 150000002430 hydrocarbons Chemical class 0.000 abstract description 6
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 abstract description 5
- 238000010438 heat treatment Methods 0.000 abstract description 5
- 229910052726 zirconium Inorganic materials 0.000 abstract description 5
- 239000004215 Carbon black (E152) Substances 0.000 abstract description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 abstract description 4
- 239000010936 titanium Substances 0.000 abstract description 4
- 229910052719 titanium Inorganic materials 0.000 abstract description 4
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052782 aluminium Inorganic materials 0.000 abstract description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052796 boron Inorganic materials 0.000 abstract description 3
- 229910052735 hafnium Inorganic materials 0.000 abstract description 3
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052758 niobium Inorganic materials 0.000 abstract description 3
- 239000010955 niobium Substances 0.000 abstract description 3
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 abstract description 3
- 230000001453 nonthrombogenic effect Effects 0.000 abstract description 3
- 239000011236 particulate material Substances 0.000 abstract description 3
- 229910052720 vanadium Inorganic materials 0.000 abstract description 3
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 abstract 1
- 238000000576 coating method Methods 0.000 description 45
- 239000011248 coating agent Substances 0.000 description 38
- 239000008280 blood Substances 0.000 description 14
- 210000004369 blood Anatomy 0.000 description 14
- HTTJABKRGRZYRN-UHFFFAOYSA-N Heparin Chemical compound OC1C(NC(=O)C)C(O)OC(COS(O)(=O)=O)C1OC1C(OS(O)(=O)=O)C(O)C(OC2C(C(OS(O)(=O)=O)C(OC3C(C(O)C(O)C(O3)C(O)=O)OS(O)(=O)=O)C(CO)O2)NS(O)(=O)=O)C(C(O)=O)O1 HTTJABKRGRZYRN-UHFFFAOYSA-N 0.000 description 11
- 239000001307 helium Substances 0.000 description 11
- 229910052734 helium Inorganic materials 0.000 description 11
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 11
- 229960002897 heparin Drugs 0.000 description 11
- 229920000669 heparin Polymers 0.000 description 11
- 241000282414 Homo sapiens Species 0.000 description 9
- 239000002245 particle Substances 0.000 description 9
- 239000000654 additive Substances 0.000 description 8
- 229960000686 benzalkonium chloride Drugs 0.000 description 8
- CADWTSSKOVRVJC-UHFFFAOYSA-N benzyl(dimethyl)azanium;chloride Chemical compound [Cl-].C[NH+](C)CC1=CC=CC=C1 CADWTSSKOVRVJC-UHFFFAOYSA-N 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 230000000996 additive effect Effects 0.000 description 7
- 238000000197 pyrolysis Methods 0.000 description 7
- 206010053567 Coagulopathies Diseases 0.000 description 6
- 230000035602 clotting Effects 0.000 description 6
- 229910002804 graphite Inorganic materials 0.000 description 6
- 239000010439 graphite Substances 0.000 description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- 229910010271 silicon carbide Inorganic materials 0.000 description 6
- 210000001519 tissue Anatomy 0.000 description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 5
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 229910021383 artificial graphite Inorganic materials 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000005055 methyl trichlorosilane Substances 0.000 description 4
- JLUFWMXJHAVVNN-UHFFFAOYSA-N methyltrichlorosilane Chemical compound C[Si](Cl)(Cl)Cl JLUFWMXJHAVVNN-UHFFFAOYSA-N 0.000 description 4
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 4
- 239000011780 sodium chloride Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 230000015556 catabolic process Effects 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- -1 polyethylene Polymers 0.000 description 3
- 239000003039 volatile agent Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 208000010392 Bone Fractures Diseases 0.000 description 2
- 206010028980 Neoplasm Diseases 0.000 description 2
- 230000002965 anti-thrombogenic effect Effects 0.000 description 2
- 239000003146 anticoagulant agent Substances 0.000 description 2
- 229940127219 anticoagulant drug Drugs 0.000 description 2
- 235000015241 bacon Nutrition 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 2
- 229910052580 B4C Inorganic materials 0.000 description 1
- 241000282472 Canis lupus familiaris Species 0.000 description 1
- 229920004934 Dacron® Polymers 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 206010017076 Fracture Diseases 0.000 description 1
- 241000124008 Mammalia Species 0.000 description 1
- 208000006670 Multiple fractures Diseases 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 208000007536 Thrombosis Diseases 0.000 description 1
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- INAHAJYZKVIDIZ-UHFFFAOYSA-N boron carbide Chemical compound B12B3B4C32B41 INAHAJYZKVIDIZ-UHFFFAOYSA-N 0.000 description 1
- 201000011510 cancer Diseases 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- GKTWGGQPFAXNFI-HNNXBMFYSA-N clopidogrel Chemical compound C1([C@H](N2CC=3C=CSC=3CC2)C(=O)OC)=CC=CC=C1Cl GKTWGGQPFAXNFI-HNNXBMFYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 235000011389 fruit/vegetable juice Nutrition 0.000 description 1
- 210000003709 heart valve Anatomy 0.000 description 1
- 239000007943 implant Substances 0.000 description 1
- 230000036512 infertility Effects 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 230000007794 irritation Effects 0.000 description 1
- 210000003734 kidney Anatomy 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 229910052863 mullite Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000013618 particulate matter Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 230000002285 radioactive effect Effects 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000001356 surgical procedure Methods 0.000 description 1
- 230000002885 thrombogenetic effect Effects 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
- A61L27/02—Inorganic materials
- A61L27/08—Carbon ; Graphite
-
- 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
- A61F2/04—Hollow or tubular parts of organs, e.g. bladders, tracheae, bronchi or bile ducts
- A61F2/06—Blood vessels
-
- 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
- A61F2/24—Heart valves ; Vascular valves, e.g. venous valves; Heart implants, e.g. passive devices for improving the function of the native valve or the heart muscle; Transmyocardial revascularisation [TMR] devices; Valves implantable in the body
- A61F2/2403—Heart valves ; Vascular valves, e.g. venous valves; Heart implants, e.g. passive devices for improving the function of the native valve or the heart muscle; Transmyocardial revascularisation [TMR] devices; Valves implantable in the body with pivoting rigid closure members
-
- 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
- A61L33/00—Antithrombogenic treatment of surgical articles, e.g. sutures, catheters, prostheses, or of articles for the manipulation or conditioning of blood; Materials for such treatment
- A61L33/02—Use of inorganic materials
- A61L33/025—Carbon; Graphite
-
- 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
- A61F2310/00161—Carbon; Graphite
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S623/00—Prosthesis, i.e. artificial body members, parts thereof, or aids and accessories therefor
- Y10S623/901—Method of manufacturing prosthetic device
Definitions
- the hydrocarbon gas mixture may contain a carbide-forming element selected from the group consisting of silicon, zirconium, titanium, tantalum, boron, tungsten, niobium, vanadium, molybdenum, aluminum, or hafnium.
- This invention relates generally to prosthetic devices and more particularly to prosthetic devices for use within a living body.
- Prosthetic devices such as intravascular prostheses
- One example is the artificial heart valve which is used fairly extensively today, and more complex circulatory assist devices are currently under development.
- Artificial kidneys are another class of prosthetic devices becoming more and more available.
- the surfaces of these devices which come in contact with blood and tissue should be completely compatible therewith, whether the contact be made by implantation or insertion within the body or by passage therethrough of blood at locations exterior of the body.
- Two of the most common materials for intravascular prosthesis are metals, for applications where high strength and good wearability are important, and plastics for applications wherein flexibility is needed.
- Metals are thrombogenic and are subject to corrosion.
- Plastics, without some treatment, are also thromobogenic and are subject to degradation.
- Stainless steel and tantalum are among the most popular metals used today, whereas polyethylene, Tefion and the polycarbonates are examples of plastics considered suitable.
- prosthetic devices having improved characteristics can be made by coating suitable substrates of the desired shape and size with dense pyrolytic carbon.
- Dense pyrolytic carbon has been found not only to significantly increase the strength of the substrate upon which it is coated, but also to resist wear and deterioration even if implanted within a living body for long periods of time. While reference is hereinafter generally made to use of the prosthetic devices in combination with a human body, wherein of course the primary use is considered likely to occur, it should also be recognized that the improved prosthetic devices may likewise be used in other living mammals. For example, it may be desirable to use pins which include the indicated pyrolytic carbon coatings for use in repairing or setting broken bones in horses or dogs.
- the pyrolytic carbon For use on complex shapes and in order to obtain maximum strength, it is desirable that the pyrolytic carbon be nearly isotropic. Anisotropic carbons, though thromobo-resistant, tend to delaminate when complex shapes are cooled after coating at high temperatures. Thus, for coating complex shapes (i.e., those having radii of curvature less than one-quarter inch), the pyrolytic carbon should have a BAF (Bacon Anisotropy Factor) of not more than about 1.3. For noncomplex shapes, higher values of BAF up to about 2.0 may be used. The BAF is an accepted measure of preferred orientation of the layer planes in the carbon crystalline structure. The technique of measurement and a complete explanation of the scale of measurement is set forth in an article by G. E.
- the thickness of the outer pyrolytic carbon coating should be sufficient to impart the necessary stress and strain fracture strengths to the particular substrate being coated. For example, if a fairly weak substrate is being employed, for instance one made of artificial graphite, it may be desirable to provide a thicker coating of pyrolytic carbon to strengthen the composite prosthetic device. Moreover, although an outer coating which is substantially entirely isotropic pyrolytic carbon has adequate structural strength, the codeposition of silicon or some similar carbide-forming additive improves the strength of the carbon coating. As described in more detail hereinafter, silicon in an amount up to about 20 weight percent can be dispersed as SiC throughout the pyrolytic carbon without detracting from the desirable thrombo-resistant properties of the pyrolytic carbon.
- the density of the pyrolytic carbon is considered to be an important feature in determining the additional strength which pyrolytic carbon coating will provide the substrate.
- the density is further important in assuring that the pyrolytic carbon surface which will be exposed to body tissue or to blood in the environment wherein it will be used is smooth and substantially impermeable. Such surface characteristics are believed to reduce the tendency of blood to coagulate on the surface of the prosthetic device. It is considered that the pyrolytic carbon. should at least have a density of about 1.5 grams per cm.
- a further characteristic of the carbon which also affects the strength contribution thereof is the crystallite height or apparent crystallite size.
- the apparent crystallite size is herein termed L and can be obtained directly using an X-ray dilfractometer.
- the pyrolytic carbon coatings for use in prosthetic devices should have a crystalline size no greater than about 200 A. In general, it may be said that the desirable characteristics of the pyrolytic carbon for use in prosthetic devices are greater when the apparent crystallite size is small and that preferably the apparent crystallite size isbetween about and about 50 A.
- the substrate material for the prosthetic device will be completely encased in pyrolytic carbon, or at least will have its surfaces covered with pyrolytic carbon which would otherwise be in contact with either body tissue or the blood, choice of the material from which to form the substrate is not of utmost importance.
- the particular prosthetic device is a pin or a small tube or a portion of a valve for implantation within the human body, it is likely that the prosthetic device would be completely covered with pyrolytic carbon.
- prosthetic device is also used to include a part of an apparatus which is used exterior of the body, for example, as a part of an auxiliary blood pump; and for such a part it may be necessary to coat only the surfaces which come in contact with the blood.
- the substrate material may in many instances be completely surrounded by pyrolytic carbon, it is considered very important that the substrate material be compatible with pyrolytic carbon, and more particularly suitable for the process for coating with pyrolytic carbon. Although, as previously indicated, it is desirable that the substrate material have good structural strength to resist possible failure during its end use, substrate materials which do not have high structural stengths may be employed by using the pyrolytic carbon deposited thereupon to supply the required additional structural strength for the prosthetic device.
- pyrolytic carbon is, by definition, deposited by the pyrolysis of a carbon-containing substance, the substrate material is subjected to the fairly high temperatures necessary for pyrolysis. Generally, hydrocarbons are employed as the carbon-containing substance to be pyrolyzed, and temperatures of at least about 1000 C. are needed.
- Some examples of the deposition of pyrolytic carbon to produce coated articles having increased stability under high temperature and neutron irradiation conditions are set forth in US. Pat. 3,298,921. The process illustrated and described in this US. patent employ methane as the source of carbon and utilize temperatures generally in the range from about 1500 to 2300 C.
- pyrolytic carbon having the desired properties with regard to the instant invention at somewhat lower temperatures by using other hydrocarbons, for example, propane or butane, generally it is considered that the substrate material should remain substantially unaffected by temperatures of at least about 1000 C., and preferably by even higher temperatures.
- the coefficients of thermal expansion of the substrate and of the pyrolytic carbon deposited thereupon should be relatively close to each other if the pyrolytic carbon is to be deposited directly upon the substrate and a firm bond therebetween is to be established.
- the deposition of an intermediate low density pyrolytic carbon layer the employment of which might provide somewhat greater leeway in matching the coefficients of thermal expansion, it is preferable to deposit the pyrolytic carbon directly upon the substrate and therefore avoid the necessity for such an additional intermediate layer.
- Pyrolytic carbon having the desired characteristics can be deposited having a thermal coefficient of expansion in the range of between about 3 and about 6 l0- C.
- substrate materials are chosen which have the aforementioned stability at high temperatures and which have thermal coefficients of expansion within or slightly above this general range.
- suitable substrate materials include artificial graphite, boron carbide, silicon carbide, tantalum, molybdenum, tungsten, and various ceramics, such as mullite.
- the pyrolytic carbon coating is applied to the substrate using a suitable apparatus for this purpose.
- a suitable apparatus for this purpose.
- an apparatus is utilized which maintains the substrate in motion while the coating process is carried out to assure that the coating is uniformly distributed on the desired surface of the substrate.
- a rotating drum coater or a vibrating table coater may be employed.
- a fluidized bed coater is preferably used. By coating in this manner, the desired smoothness and uniformity of the carbon surface is obtained.
- the charatceristics of the carbon which are deposited may be varied by varying the conditions under which pyrolysis is carried out. For example, in a fluidized bed coating process wherein a mixture of a hydrocarbon gas, such as methane, and an inert gas, such as helium or argon, is used, variance in the volume percent of methane, the total flow rate of the fluidizing gas stream, and the temperature at which pyrolysis is carried out all affect the characteristics of the pyrolytic carbon which is deposited.
- a hydrocarbon gas such as methane
- an inert gas such as helium or argon
- Control of these various operational parameters not only allows deposition of pyrolytic carbon having the desired density, apparent crystallite size, and isotropy, but also permits regulation of the desired thermal coefiicient of expansion which the pyrolytic carbon has.
- This control also allows one to grade a coating in order to provide a variety of exterior surfaces. For example, a highly oriented surface coating is believed to provide enhanced thromboresistance which may be desirable for certain applications.
- a substrate material which has a thermal coefficient expansion of between about 3 and about 6X 10 C.
- the carbon deposition conditions are controlled so that the pyrolytic carbon has a coefficient within the same range.
- the pyrolysis conditions are controlled so that the pyrolytic carbon which is deposited has a coefiicient of expansion matched to within about plus or minus 50 percent of the substrate materials thermal coefficient of expansion, and preferably to within about plus or minus 20 percent thereof.
- the thermal coefiicient of expansion of the pyrolytic carbon most preferably is about equal to or less than that of the substrate. Under these conditions, good adherence to the substrate is established and maintained during the life of the prosthetic devices. Inasmuch as many of these devices may be employed for implantation within the human body, it is extremely important that long life of the device without degradation be assured.
- the coating may be substantially entirely pyrolytic carbon, or it may contain a carbide-forming additive, such as silicon, which has been found to increase the overall structural strength of the coating.
- a carbide-forming additive such as silicon
- Silicon in an amount of up to about 20 weight percent, based upon total weight of silicon plus carbon, may be included without detracting from the desirable properties of the pyrolytic carbon, and when silicon is used as an additive, it is generally employed in an amount between about and weight percent.
- Examples of other carbide-forming elements which might be used as additives in equivalent weight percents include boron, tungsten, tantalum, niobium, vanadium, molybdenum, aluminum, zirconium, titanium and hafnium. Generally, such an element would not be used in an amount greater than 10 atom percent, based upon total atoms of carbon plus the element.
- the carbide-forming additive is codeposited with the pyrolytic carbon by selecting a volatile compound of the element in question and supplying this compound to the deposition region.
- the pyrolytic carbon is deposited from a mixture of an inert gas and a hydrocarbon or the like, and in such an instance, the inert gas may be conveniently employed to carry the volatile compound to the deposition region.
- the fluidizing gas may be bubbled through a bath of methyltrichlorosilane or some other suitable volatile liquid compound.
- the particular element employed is converted to the carbide form and appears dispersed as a carbide throughout the resultant product.
- the presence of such a carbide-forming additive does not significantly change the crystalline structure of the pyrolytic carbon deposited from that which would be deposited under the same conditions in the absence of such an additive.
- Pyrolytic carbon having the physical properties mentioned hereinbefore is considered to be particularly advantageous for constituting the surface for a prosthetic device because it is antithrombogenic and is inert to the metabolic processes, enzymes, and other juices found within living bodies.
- the antithrombogenic properties of pyrolytic carbon are believed to be dependent upon its sterility and the removal of all the oxygen therefrom.
- the device Before use, the device may be sterilized, for example, by heating in a suitable vacuum for about six hours at about 130 C.
- the prosthetic devices can be sterilized in benzalkonium chloride and then treated with a suitable anticoagulant which safeguards against the occurrence of thrombosis.
- An anticoagulant such as haparin can be used.
- Application may be simply made by soaking the prosthetic device in benzalkonium chloride and then in a heparin solution.
- a suitable heparin solution may be prepared by mixing 2 cc. of heparin to 30 cc. of saline, saline being a solution of sodium chloride in water.
- a pyrolytic carbon-coated device may be secured in the proper location within the body, for example, by joining with Dacron cloth and appropriately suturing using standard suturing methods.
- Short tubes are constructed of artificial graphite each having a length of 9 mm., an internal diameter of 7 mm. and a wall thickness of 0.5 mm.
- the artificial graphite employed has a coeflicient of thermal expansion of about 4X'10- C. when measured at 50 C.
- the short tubes are coated with pyrolytic carbon using a fluidized bed coating apparatus.
- the fluidized bed apparatus includes a reaction tube having a diameter of about 3.8 cm. that is heated to a temperature of about 1350 C. A flow of helium gas sufiicient to levitate the relatively small tubes is maintained upward through the apparatus.
- the small short tubes are coated together with a charge of zirconium dioxide particles of about 50 grams, which particles have diameters in the range of about to 250 microns. The particles are added along with the short tubes to provide a deposition surface area of the desired amount relative to the size of the region of the reaction tube wherein pyrolysis occurs inasmuch as the relative amount of available surface area is another factor which influences the characteristics of the resultant pyrolytic carbon.
- propane is admixed with the helium to provide an upwardly flowing gas stream having a total flow rate of about 6000 cc. per minute and having a partial pressure of propane of about 0.4 (total pressure one atmosphere).
- the propane decomposes under these conditions and deposits a dense isotropic pyrolytic carbon coating upon all of the articles in the fluidized bed. Under these coating conditions, the carbon deposition rate is about five microns per minute.
- the propane gas flow is continued until an isotropic pyrolytic carbon coating about 200 microns thick is deposited on the outside of the tubes. At this time, the propane gas flow is terminated, and the coated articles are cooled fairly slowly in the helium gas and then removed from the reaction tube coating apparatus.
- the short tubes are examined and tested.
- the thickness of the pyrolytic carbon coating on the interior of the tubes measures about 200 microns.
- the density of the isotropic carbon uniformly is found to be about 2.0 grams per cm.
- the BAF is found to be about 1.1.
- the apparent crystallite size is measured and found to be about 30 to 40 A.
- Mechanical tests of the coated short tubes are made to determine their strength in comparison to additional uncoated graphite tubes.
- the crushing load of the uncoated graphite tubes, loaded parallel to the diameter, is found to be about four pounds.
- the crushing load of the coated tubes is about twenty-five pounds, about six times higher.
- Another of the coated tubes is sterilized by heating to about 1000 'C.
- the pyrolytic carbon-coated graphite substrate articles are considered to be excellently acceptable for use as prosthetic devices within the body of human beings.
- EXAMPLE II A number of short tubes having the same dimensions as those used in Example I but made of tantalum are provided. Tantalum has a thermal coefiicient of expansion of about 6.5 Xl C., measured at 20 C.
- the short tubes are coated in the fluidized bed reaction tube employed in Example I. In order to match the pyrolytic carbon coefficient of thermal expansion to that of the tan talum substrate, a coating temperature of 1600 C. is employed using a 15 percent propane85 percent helium gas stream having a total flow rate of about 6000 cc. per minute.
- the short tubes are levitated together with a similar 50 gram charge of particles of zirconium dioxide at atmospheric pressure.
- Deposition of pyrolytic carbon is carried out for about 20 minutes, after which period a layer of isotropic pyrolytic carbon about 150 microns thick coats the outer surface of each of the tubes. At the end of this time the propane flow is discontinued, and the coated tubes are cooled and removed from the reaction tube.
- the density of the isotropic pyrolytic carbon deposited is about 1.6 grams per cm.
- the BAF is about 1.0.
- the apparent crystallite size is between about 50 to 60 A.
- the thermal coefficient of expansion of the pyrolytic carbon measures about 5x10 C. at about 20 C.
- Mechanical testing of the coated tubes shows that the strength and wearability is acceptable and that the coating is firmly afiixed to the substrate.
- One of the coated short tubes is sterilized and treated as in Example I excepting that the treatment with benzalkonium chloride and heparin is omitted.
- the tube is tested with blood, and there is no sign of clotting after contact therewith for twenty-four hours.
- the carbon-coated tantalum articles are considered to be excellently acceptable for use as a part of a prosthetic device for implantation within a human body.
- EXAMPLE III A number of short tubes having the same dimensions as those used in Example I but made of tungsten are provided. Tungsten has a thermal coefficient of expansion of about 4.4 10- C., measured at 27 C. The short tubes are coated in the fluidized bed reaction tube employed in Example I. In order to match the pyrolytic carbon coefficient of thermal expansion to that of the tungsten substrate, a coating temperature of 1600 C. is employed using a percent propane85 percent helium gas stream having a total flow rate of about 600 cc. per minute. The short tubes are levitated together with a similar 50 gram charge of particles of zirconium dioxide.
- Deposition of pyrolytic carbon is continued for about minutes, at which time a layer of isotropic pyrolytic carbon about 150 microns thick coats the outer surface of each of the tubes.
- the propane flow is discontinued, and the coated tubes are cooled and removed from the reaction tube.
- the density of the isotropic pyrolytic carbon deposited is about 1.6 grams per cc.
- the BAP is about 1.0.
- the apparent crystallite size is between about 50 to 60 A.
- the thermal coefficient of expansion of the pyrolytic carbon measures about 5 10 C. at about 20 C.
- Mechanical testing of the coated tubes shows that the strength and wearability is acceptable and that the coating is firmly afiixed to the substrate.
- One of the coated short tubes is sterilized and treated as in Example I with benzalkonium chloride and heparin and tested with blood. There is no sign of clotting after contact therewith for twenty-four hours.
- the carbon-coated tungsten articles are considered to be excellently acceptable for use as a part of a prosthetic device for implantation within a human body.
- EXAMPLE IV A number of short tubes having the same dimensions as those used in Example I but made of molybdenum are provided. Molybdenum has a thermal coeflicient of expansion of about 5.3 10 0, measured at 20 C.
- the short tubes are coated in the fluidized bed reaction tube employed in Example I. In order to match the pyrolytic carbon coefiicient of thermal expansion to that of the molybdenum substrate, a coating temperature of 1350 C. is employed using a 30 percent propane-70 percent helium gas stream having a total flow rate of about 5500 cc. per minute.
- the short tubes are levitated together with a similar 50 gram charge of particles of zirconium dioxide.
- Deposition of pyrolytic carbon occurs, and after about 30 minutes a layer of isotropic pyrolytic carbon about 150 microns thick coats the outer surface of each of the tubes. At the end of this time, the propane flow is discontinued, and the coated tubes are cooled and removed from the reaction tube.
- the density of the isotropic pyrolytic carbon deposited is about 2.0 grams per cm.*.
- the BAF is about 1.1.
- the apparent crystallite size is between about 30 and 40 A.
- the thermal coeliicient of expansion of the pyrolytic carbon measures about 5 l0- C. at about 20 C.
- Mechanical testing of the coated tubes shows that the strength and wearability is acceptable and that the pyrolytic carbon coating is firmly bonded to the substrate.
- One of the coated short tubes is sterilized and treated as in Example I with benzalkonium chloride and heparin and is tested with blood. There is no sign of clotting after contact therewith for twenty-four hours.
- the carbon-coated molybdenum short tubes are considered to be excellently acceptable for use as a part of a prosthetic device for implantation within a human body.
- EXAMPLE V A number of graphite tubes having the same characteristics and dimensions as those used in Example I are introduced into a reaction tube which is about 6.3 cm. in diameter, together with an ancillary charge of grams of zirconium oxiode spheroids having an average particle size of about 400 microns.
- a fluidizing flow of helium is fed upward through the reaction tube as the temperature of the small tubes and particles is raised to about 1350" C. When this temperature is reached, propane is admixed with the helium to provide a total gas flow of about 8000 cc. per minute, having a partial pressure of propane of about 0.4 atm. (total pressure of 1 atm.).
- All of the helium is bubbled through a bath of methyltrichlorosilane at about room temperature.
- the propane and the methyltrichlorosilane pyrolyze to deposit a mixture of isotropic carbon and silicon carbide on the small tubes, and the coating process is continued until a coating about 12 mils (300 microns) thick is obtained, a time of about an hour.
- the resultant coated tubes are allowed to cool to ambient temperature, and they are then removed from the reaction tube.
- Examination of the istotropic carbon-silicon carbide coating shows that it has a coefficient of thermal expansion of about 6x10- C. and a density of 2 grams per cmfi.
- the coating contains about weight percent silicon (based upon total weight of silicon plus carbon) in the form of silicon carbide.
- the isotropic carbon has a BAF of about 1.1 and an apparent crystallite size of about 35 A.
- Mechanical testing of the coating tubes shows that the strength and wearability are fully acceptable and that there is a firm bond between the coating and the graphite substrate.
- One of the coated tubes is sterilized and treated as in Example I, using benzalkonium chloride and heparin, and it is then tested with blood. There is no sign of clotting after contact with blood for twenty-four hours.
- the tubes which are coated with pyrolytic carbon containing the silicon carbide additive are considered to be excellently acceptable for use as a part of a prosthetic device and suitable for implantation within a human body.
- Pyrolytic carbon-coated substrates containing radioactive isotopes for internally treating diseases, such as cancer or tumors are illustrative of another form of improved prosthetic device that may be produced.
- Various features of the invention are set forth in the following claims.
- a method of making a prosthetic device which method comprises forming a substrate of a material stable at temperatures of at least about 1350 C., heating said substrate together with particulate material to provide additional deposition surface area to a temperature of between about 1350 C. and about 1600 C. in a reaction chamber, flowing a mixture of propane or butane and an inert gas through said reaction chamber at atmospheric pressure, said propane or butane constituting between about volume percent and about 40 volume percent of said mixture, so that said substrate becomes coated with isotropic pyrolytic carbon having a BAF between 1.0 and 2.0, having an apparent crystallite size of about 50 A. or less and having a density of at least about 1.5 grams per cm. and continuing said gas flow until the thickness of said isotropic carbon deposit is at least about 50 microns, whereby a device is produced which has excellent compatibility with body tissue and is nonthrombogenic.
- a method in accordance with claim 1 wherein said particulate matter is about equivalent to a charge of about 50 grams of ZrO particles between about and 25-0 microns in size per 11 sq. cm. of reaction chamber cross sectional area.
- said gas mixture includes a volatile compound containing a carbide-forming element.
- liquid compound is methyltrichlorosilane.
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- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Veterinary Medicine (AREA)
- Public Health (AREA)
- General Health & Medical Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- Transplantation (AREA)
- Cardiology (AREA)
- Chemical & Material Sciences (AREA)
- Oral & Maxillofacial Surgery (AREA)
- Vascular Medicine (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Epidemiology (AREA)
- Heart & Thoracic Surgery (AREA)
- Biomedical Technology (AREA)
- Pulmonology (AREA)
- Medicinal Chemistry (AREA)
- Dermatology (AREA)
- Gastroenterology & Hepatology (AREA)
- Hematology (AREA)
- Surgery (AREA)
- Materials For Medical Uses (AREA)
- External Artificial Organs (AREA)
- Ceramic Products (AREA)
- Carbon And Carbon Compounds (AREA)
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US82108069A | 1969-05-01 | 1969-05-01 |
Publications (1)
Publication Number | Publication Date |
---|---|
US3677795A true US3677795A (en) | 1972-07-18 |
Family
ID=25232444
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US821080A Expired - Lifetime US3677795A (en) | 1969-05-01 | 1969-05-01 | Method of making a prosthetic device |
Country Status (6)
Country | Link |
---|---|
US (1) | US3677795A (de) |
JP (1) | JPS5014837B1 (de) |
CA (1) | CA948352A (de) |
DE (1) | DE2021320C3 (de) |
FR (1) | FR2041786A6 (de) |
GB (1) | GB1282685A (de) |
Cited By (69)
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US3791852A (en) * | 1972-06-16 | 1974-02-12 | Univ California | High rate deposition of carbides by activated reactive evaporation |
US3877080A (en) * | 1972-10-30 | 1975-04-15 | Atlantic Res Corp | Acicular silicon carbide dispersion in pyrolytic graphite matrix for use in biomedical implants |
US3885073A (en) * | 1970-08-21 | 1975-05-20 | Atlantic Res Corp | Pre-stressed pyrolytic graphite-refractory carbide microcomposites |
US3897582A (en) * | 1970-08-21 | 1975-07-29 | Atlantic Res Corp | Braking elements |
US3900668A (en) * | 1971-07-09 | 1975-08-19 | Atlantic Res Corp | Internal components for gas turbines of pyrolytic graphite silicon carbide codeposit |
US3900675A (en) * | 1970-08-21 | 1975-08-19 | Atlantic Res Corp | Rocket nozzle comprising pyrolytic graphite-silicon carbide microcomposite inserts |
US3924034A (en) * | 1970-08-21 | 1975-12-02 | Atlantic Res Corp | Process of making pyrolytic graphite-silicon carbide microcomposites |
US3925133A (en) * | 1970-08-21 | 1975-12-09 | Atlantic Res Corp | Method for making reinforced pyrolytic graphite-silicon carbide microcomposites |
US3935354A (en) * | 1970-08-21 | 1976-01-27 | Olcott Eugene L | Shaped articles of pyrolytic graphite-silicon carbide microcomposites |
US3969130A (en) * | 1973-02-05 | 1976-07-13 | General Atomic Company | Carbon-coated articles and method of making same |
US3972818A (en) * | 1974-08-22 | 1976-08-03 | General Atomic Company | Blood filter using glassy carbon fibers |
US4126924A (en) * | 1977-02-07 | 1978-11-28 | General Atomic Company | Socket and joint prostheses |
US4127659A (en) * | 1976-01-02 | 1978-11-28 | Avco Corporation | Silicon carbide filaments and method |
US4164794A (en) * | 1977-04-14 | 1979-08-21 | Union Carbide Corporation | Prosthetic devices having coatings of selected porous bioengineering thermoplastics |
US4194027A (en) * | 1975-04-21 | 1980-03-18 | General Atomic Company | Method of coating with homogeneous pyrocarbon |
US4300244A (en) * | 1979-09-19 | 1981-11-17 | Carbomedics, Inc. | Cardiovascular grafts |
US4338358A (en) * | 1978-06-12 | 1982-07-06 | U.S. Philips Corporation | Method of producing cuvettes for the flameless atomic absorption spectroscopy |
US4534761A (en) * | 1981-08-14 | 1985-08-13 | Bentley Laboratories, Inc. | Implant device |
US4537791A (en) * | 1984-03-27 | 1985-08-27 | Cordis Corporation | Carbon coating of grafts or catheters |
US4617024A (en) * | 1982-03-26 | 1986-10-14 | Ernst Leitz Wetzlar Gmbh | Auditory ossicle prosthesis and process for its manufacture |
US4668579A (en) * | 1984-02-01 | 1987-05-26 | The United States Of America As Represented By The Secretary Of The Air Force | Interstitially protected oxidation resistant carbon-carbon composite |
US4846834A (en) * | 1986-05-27 | 1989-07-11 | Clemson University | Method for promoting tissue adhesion to soft tissue implants |
US4871366A (en) * | 1986-05-27 | 1989-10-03 | Clemson University | Soft tissue implants for promoting tissue adhesion to same |
US5037438A (en) * | 1989-07-25 | 1991-08-06 | Richards Medical Company | Zirconium oxide coated prosthesis for wear and corrosion resistance |
US5049409A (en) * | 1985-03-20 | 1991-09-17 | Sharp Kabushiki Kaisha | Method for metal or metal compounds inserted between adjacent graphite layers |
US5084151A (en) * | 1985-11-26 | 1992-01-28 | Sorin Biomedica S.P.A. | Method and apparatus for forming prosthetic device having a biocompatible carbon film thereon |
US5147590A (en) * | 1990-05-02 | 1992-09-15 | Siemens Aktiengesellschaft | Method of making the electrode |
US5152794A (en) * | 1989-07-25 | 1992-10-06 | Smith & Nephew Richards Inc. | Zirconium oxide and nitride coated prothesis for reduced microfretting |
US5180394A (en) * | 1989-07-25 | 1993-01-19 | Davidson James A | Zirconium oxide and nitride coated prosthesis for wear and corrosion resistance |
US5258022A (en) * | 1989-07-25 | 1993-11-02 | Smith & Nephew Richards, Inc. | Zirconium oxide and nitride coated cardiovascular implants |
US5273778A (en) * | 1985-03-20 | 1993-12-28 | Sharp Kabushiki Kaisha | Method for producing graphite intercalation compound |
US5282850A (en) * | 1989-07-25 | 1994-02-01 | Smith & Nephew Richards, Inc. | Artificial heart components with wear resistant coatings of reduced thrombogenicity |
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US5370694A (en) * | 1989-07-25 | 1994-12-06 | Smith & Nephew Richards, Inc. | Zirconium oxide and nitride coated endoprostheses for tissue protection |
US5370684A (en) * | 1986-12-12 | 1994-12-06 | Sorin Biomedica S.P.A. | Prosthesis of polymeric material coated with biocompatible carbon |
US5387247A (en) * | 1983-10-25 | 1995-02-07 | Sorin Biomedia S.P.A. | Prosthetic device having a biocompatible carbon film thereon and a method of and apparatus for forming such device |
US5496359A (en) * | 1989-07-25 | 1996-03-05 | Smith & Nephew Richards, Inc. | Zirconium oxide and zirconium nitride coated biocompatible leads |
US5509933A (en) * | 1989-12-21 | 1996-04-23 | Smith & Nephew Richards, Inc. | Medical implants of hot worked, high strength, biocompatible, low modulus titanium alloys |
US5514410A (en) * | 1994-09-08 | 1996-05-07 | Carbon Implants, Inc. | Pyrocarbon and process for depositing pyrocarbon coatings |
US5562730A (en) * | 1989-12-21 | 1996-10-08 | Smith & Nephew Richards, Inc. | Total artificial heart device of enhanced hemocompatibility |
US5573401A (en) * | 1989-12-21 | 1996-11-12 | Smith & Nephew Richards, Inc. | Biocompatible, low modulus dental devices |
EP0761244A2 (de) * | 1995-09-12 | 1997-03-12 | BIOTRONIK Mess- und Therapiegeräte GmbH & Co Ingenieurbüro Berlin | Verfahren zum Anlagern und Immobilisieren von Heparin auf anorganischen Substratoberflächen von kardiovaskulären Implantaten |
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US5628790A (en) * | 1989-07-25 | 1997-05-13 | Smith & Nephew, Inc. | Zirconium oxide zirconium nitride coated valvular annuloplasty rings |
US5674280A (en) * | 1989-12-21 | 1997-10-07 | Smith & Nephew, Inc. | Valvular annuloplasty rings of a biocompatible low elastic modulus titanium-niobium-zirconium alloy |
US5683442A (en) * | 1989-12-21 | 1997-11-04 | Smith & Nephew, Inc. | Cardiovascular implants of enhanced biocompatibility |
US5820707A (en) * | 1995-03-17 | 1998-10-13 | Teledyne Industries, Inc. | Composite article, alloy and method |
US5868879A (en) * | 1994-03-17 | 1999-02-09 | Teledyne Industries, Inc. | Composite article, alloy and method |
US5954724A (en) * | 1997-03-27 | 1999-09-21 | Davidson; James A. | Titanium molybdenum hafnium alloys for medical implants and devices |
US6596084B1 (en) | 1999-05-20 | 2003-07-22 | Medicalcv, Inc. | Pyrolytic carbon coating apparatus having feed gas actuator |
US6777029B2 (en) | 2002-04-27 | 2004-08-17 | Carbomedics Inc. | Method for determining product coating rates for fluidized beds |
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US20060233944A1 (en) * | 2005-04-19 | 2006-10-19 | Zimmer Technology, Inc. | Method for producing a zirconia-layered orthopedic implant component |
US20070154514A1 (en) * | 2005-12-30 | 2007-07-05 | Demakas John J | Therapeutic Structures |
US20090054985A1 (en) * | 2007-08-21 | 2009-02-26 | Anderson Jeffrey P | Titanium alloy with oxidized zirconium for a prosthetic implant |
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US8133553B2 (en) | 2007-06-18 | 2012-03-13 | Zimmer, Inc. | Process for forming a ceramic layer |
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Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
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US3737919A (en) * | 1971-03-16 | 1973-06-12 | Univ Minnesota | Pivoted disc-type heart valve |
US4101984A (en) * | 1975-05-09 | 1978-07-25 | Macgregor David C | Cardiovascular prosthetic devices and implants with porous systems |
DE2811591C2 (de) * | 1978-03-17 | 1986-08-14 | Sigri GmbH, 8901 Meitingen | Gallengangendoprothese |
IT1159433B (it) * | 1983-07-25 | 1987-02-25 | Sorin Biomedica Spa | Procedimento ed apparecchiatura per la fabbricazione di lembi valvolari per protesi valvolari cardiache e protesi valvolare cardiaca provvista di tali lembi |
FR2676355A1 (fr) * | 1991-05-14 | 1992-11-20 | De Crepy Bruno | Prothese chirurgicale pour chirurgie vasculaire. |
JP7081718B2 (ja) | 2019-03-13 | 2022-06-07 | 日本製鉄株式会社 | 電縫鋼管溶接監視方法、電縫鋼管製造方法、電縫鋼管溶接監視装置、及び電縫鋼管製造装置 |
-
1969
- 1969-05-01 US US821080A patent/US3677795A/en not_active Expired - Lifetime
-
1970
- 1970-04-17 CA CA080,404A patent/CA948352A/en not_active Expired
- 1970-04-23 GB GB09493/70A patent/GB1282685A/en not_active Expired
- 1970-04-30 FR FR7015896A patent/FR2041786A6/fr not_active Expired
- 1970-04-30 DE DE2021320A patent/DE2021320C3/de not_active Expired
- 1970-05-01 JP JP45036916A patent/JPS5014837B1/ja active Pending
Cited By (91)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3885073A (en) * | 1970-08-21 | 1975-05-20 | Atlantic Res Corp | Pre-stressed pyrolytic graphite-refractory carbide microcomposites |
US3897582A (en) * | 1970-08-21 | 1975-07-29 | Atlantic Res Corp | Braking elements |
US3900675A (en) * | 1970-08-21 | 1975-08-19 | Atlantic Res Corp | Rocket nozzle comprising pyrolytic graphite-silicon carbide microcomposite inserts |
US3924034A (en) * | 1970-08-21 | 1975-12-02 | Atlantic Res Corp | Process of making pyrolytic graphite-silicon carbide microcomposites |
US3925133A (en) * | 1970-08-21 | 1975-12-09 | Atlantic Res Corp | Method for making reinforced pyrolytic graphite-silicon carbide microcomposites |
US3935354A (en) * | 1970-08-21 | 1976-01-27 | Olcott Eugene L | Shaped articles of pyrolytic graphite-silicon carbide microcomposites |
US3900668A (en) * | 1971-07-09 | 1975-08-19 | Atlantic Res Corp | Internal components for gas turbines of pyrolytic graphite silicon carbide codeposit |
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Also Published As
Publication number | Publication date |
---|---|
DE2021320C3 (de) | 1982-03-04 |
FR2041786A6 (de) | 1971-02-05 |
GB1282685A (en) | 1972-07-19 |
DE2021320B2 (de) | 1979-06-07 |
JPS5014837B1 (de) | 1975-05-30 |
CA948352A (en) | 1974-06-04 |
DE2021320A1 (de) | 1970-11-12 |
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