WO2015200896A1 - Dispositifs poreux et leurs procédés de production - Google Patents

Dispositifs poreux et leurs procédés de production Download PDF

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Publication number
WO2015200896A1
WO2015200896A1 PCT/US2015/038181 US2015038181W WO2015200896A1 WO 2015200896 A1 WO2015200896 A1 WO 2015200896A1 US 2015038181 W US2015038181 W US 2015038181W WO 2015200896 A1 WO2015200896 A1 WO 2015200896A1
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Prior art keywords
peek
medical device
polymer
porous
solid
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English (en)
Inventor
Wei-Hsiang Chang
Stephen Lee Laffoon
Christopher S.D. Lee
David Lee SAFRANSKI
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Vertera Inc
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Vertera Inc
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Priority claimed from US14/587,856 external-priority patent/US9085665B1/en
Application filed by Vertera Inc filed Critical Vertera Inc
Publication of WO2015200896A1 publication Critical patent/WO2015200896A1/fr
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/26—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a solid phase from a macromolecular composition or article, e.g. leaching out
    • 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
    • A61L27/14—Macromolecular materials
    • A61L27/18—Macromolecular materials obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • 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
    • A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • A61L27/56—Porous materials, e.g. foams or sponges
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
    • A61L2300/40—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices characterised by a specific therapeutic activity or mode of action
    • A61L2300/44—Radioisotopes, radionuclides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2371/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers

Definitions

  • PCT International Patent Application
  • PCT/US2009/047286 entitled “Material and Method for Producing the Same,” filed on June 12, 2009;
  • PCT International Patent Application
  • PCT/US2013/055656 entitled “Systems and Methods for Making Porous Films, Fibers, Spheres, and Other Articles,” filed on August 20, 2013;
  • PCT International Patent Application
  • PCT/US2013/055655 entitled “Particulate Dispensing Apparatus,” filed on August 20, 2013;
  • the present disclosure relates generally to devices with porous surfaces and processes for creating porous polymers.
  • Polymers have been shown to have many advantageous mechanical and chemical properties such as imperviousness to water, low toxicity, chemical and heat resistance, and shape-memory properties. Additionally, polymers are often relatively low cost, easy to manufacture, and versatile in application. These characteristics have led to the use of polymers in many applications such as, for example, medical devices, electronics, optics, computing, and a wide-array of consumer products.
  • Adding pores to one or more surfaces of a polymer structure may provide further advantages, such as, for example, increasing friction at the one or more porous surfaces and providing better device integration in surgical applications by promoting adjacent tissue in-growth.
  • introducing porosity into polymers may, in some instances, weaken desired mechanical properties, such as shear strength at the porous surface.
  • shear strength at the porous surface.
  • One aspect of the present disclosure generally relates to producing a porous surface from a solid piece of polymer.
  • the present disclosure generally relates to producing a porous surface from a piece of polymer with shear strength that increases substantially linearly with processing time.
  • the present disclosure relates to a method for forming a solid polymer body with pores distributed through at least a portion of the solid polymer body, the method comprising: A) heating a surface of a solid piece of polymer to a processing temperature below a melting point of the polymer; and B) holding the processing temperature while displacing a porogen layer through the surface of the polymer to create a matrix layer of the solid polymer body comprising the polymer and the porogen layer.
  • This particular embodiment may further include a processing temperature that is about one to thirty-eight degrees Celsius less than the melting point of the polymer.
  • the present disclosure relates to a method for forming a solid polymer body with pores distributed through at least a portion of the solid polymer body, the method including: A) placing a surface of a solid piece of
  • PEEK polyetheretherketone
  • Particular aspects of the present disclosure relate to a method including: A) heating a surface of a solid polyetheretherketone (PEEK) body to a maximum processing temperature that is below a melting temperature of the surface of the solid PEEK body by a melting temperature differential; B) displacing a plurality of layers of a porogen through the surface and into a defined distance of the solid PEEK body, creating, thereby, a matrix layer including PEEK and the plurality of layers of the porogen, the matrix layer being integrally connected with the solid PEEK body; C) maintaining throughout the heating and displacing steps, a temperature of the surface of the solid PEEK body that is below the melting temperature by at least the melting temperature differential; and D) removing a portion of the plurality of layers of porogen from the matrix layer, creating, thereby, a porous PEEK layer integrally connected with a remaining portion of the solid PEEK body.
  • PEEK solid polyetheretherketone
  • a method including: A) heating a surface of a solid polyetheretherketone (PEEK) body to a maximum processing temperature that is below a melting temperature of the surface of the solid PEEK body by a melting temperature differential; B) displacing a plurality of layers of a porogen through the surface and into a defined distance of the solid PEEK body, creating, thereby, a matrix layer including PEEK and the plurality of layers of the porogen, the matrix layer being integrally connected with the solid PEEK body; C) maintaining throughout the heating and displacing steps, a temperature of the surface of the solid PEEK body that is below the melting temperature by at least the melting temperature differential; and D) removing a portion of the plurality of layers of porogen from the matrix layer, creating, thereby, a porous PEEK layer integrally connected with a remaining portion of the solid PEEK body, wherein the temperature differential is between one degree Celsius and thirty-eight degrees Celsius.
  • PEEK solid polyetheretherketone
  • a method for forming a solid thermoplastic body with pores distributed through at least a portion of the solid including: A) heating a surface of a solid piece of thermoplastic to a processing temperature below a melting point of the thermoplastic; B) holding the processing temperature below a melting point of the thermoplastic while displacing the surface of the thermoplastic through a granular porogen layer to create a matrix layer of the solid thermoplastic body including the thermoplastic and the porogen layer; and C) cooling the matrix layer to cease
  • a medical device for promoting tissue ingrowth including a solid thermoplastic body including: A) a body layer, the body layer including a thermoplastic with crystallites varying in size; and B) a porous surface layer of the body, the porous surface layer of the body including irregular, substantially spherical pores extending through the solid thermoplastic body for a defined distance, wherein the interfacial shear strength between the body layer and the porous surface layer is at least about 17 MPa.
  • a medical device for promoting tissue ingrowth including a solid thermoplastic body including: A) at least two porous surface layers that are on opposite faces of the solid thermoplastic body, the at least two porous surface layers including irregular, substantially spherical pores extending through the solid thermoplastic body for a defined distance; and B) a body layer that is between the at least two porous surface layers, the body layer including a thermoplastic with crystallites varying in size, wherein: i) the at least two porous surface layers include an increased percentage of hydroxyl groups in comparison to the body layer; ii) a carbon to oxygen atomic ratio of the at least two porous surface layers is substantially the same as a carbon to oxygen atomic ratio of the body layer; iii) the at least two porous surface layers have increased wettability in comparison to the body layer; and iv) the interconnectivity of the irregular, substantially spherical pores is about 99 %.
  • a method including: A) heating a surface of a solid polyetheretherketone (PEEK) body to a processing temperature that is above a glass transition temperature of PEEK; B) displacing a plurality of layers of a porogen through the surface and into a defined distance of the solid PEEK body; C) cooling the surface of the solid PEEK body at a predetermined rate; and D) removing a portion of the plurality of layers of porogen from the surface, creating, thereby, a porous PEEK layer integrally connected with a remaining portion of the solid PEEK body and including: i) an increased percentage of hydroxyl groups in comparison to a percentage of hydroxyl groups in the solid PEEK body; ii) a carbon to oxygen atomic ratio that is substantially the same as a carbon to oxygen atomic ratio of the solid PEEK body; and iii) an increased wettability in comparison to the solid PEEK body.
  • PEEK solid polyetheretherketone
  • medical device for promoting tissue ingrowth, the medical device including a thermoplastic body defining a porous surface formed from a plurality of substantially spherical pores, each of the pores extending a defined distance from the top face into the body, wherein: A) the porous surface has a particular wettability, wherein the particular wettability is greater than a wettability of the body; and B) an interconnectivity between the plurality of substantially spherical pores is at least 99 %.
  • a method for determining tissue ingrowth into a medical device including: A) providing a medical device including: i) a radiolucent material; ii) a porous surface; and iii) at least one tantalum marker for detecting the medical device in a radiograph, wherein a top of the tantalum marker is approximately flush with a top of the porous surface; and B) instructing one or more clinicians to: i) take a radiograph of the medical device, wherein the medical device is implanted in a patient; and ii) measure the distance between the patient's tissue and the top of the at least one tantalum marker, thereby determining the tissue ingrowth of the patient's tissue into the medical device.
  • FIG. 1 is an exemplary flow chart of an exemplary process for creating a porous polymer, according to one embodiment.
  • FIG. 2 illustrates an exemplary process for creating a porous polymer, according to one embodiment.
  • FIG. 3 is an exemplary graph showing results of a differential scanning calorimetry scan of polyetheretherketone (PEEK) showing exemplary endotherms of PEEK under particular conditions, according to one embodiment.
  • PEEK polyetheretherketone
  • FIG. 4 A is an exemplary plot graph showing exemplary shear strength properties of PEEK over time under particular conditions, according to one embodiment.
  • FIG. 4B is an exemplary bar graph showing exemplary shear strength over time under particular conditions, according to one embodiment.
  • FIG. 4C is an exemplary plot graph showing exemplary pressure verses time data of PEEK under certain conditions, according to one embodiment.
  • FIG. 4D is an exemplary bar graph showing exemplary pressure verses time data of PEEK under certain conditions, according to one embodiment.
  • FIG. 5 A is an exemplary plot graph showing exemplary shear strength properties of PEEK over time under particular conditions, according to one embodiment.
  • FIG. 5B is an exemplary bar graph showing exemplary shear strength properties of PEEK over time under particular conditions, according to one embodiment.
  • FIG. 5 C is an exemplary plot graph showing exemplary pressure verses time data of PEEK under certain conditions, according to one embodiment.
  • FIG. 5D is an exemplary bar graph showing exemplary pressure verses time data of PEEK under certain conditions, according to one embodiment.
  • FIG. 6A is an exemplary XPS Ols spectra of an injection molded porous polymer under certain conditions, according to one embodiment.
  • FIG. 6B is an exemplary XPS Ols spectra of surface porous polymer under certain conditions, according to one embodiment.
  • FIG. 6C is an exemplary XPS Ols spectra of surface porous polymer after gamma sterilization under certain conditions, according to one embodiment.
  • FIG. 6D is an exemplary table comprising exemplary XPS Ols spectra ratios under certain conditions, according to one embodiment.
  • FIG. 6E is an exemplary table comprising exemplary XPS Ols elemental ratios under certain conditions, according to one embodiment.
  • FIG. 7A is an exemplary table comprising exemplary contact angles of a porous polymer under certain conditions, according to one embodiment.
  • FIG. 7B is an exemplary table comprising exemplary roughness data of a polymer under certain conditions, according to one embodiment.
  • FIG. 8 A is an exemplary bar graph showing hydroxyl group percentages of a polymer verses processing temperature under certain conditions, according to one embodiment.
  • FIG. 8B is an exemplary bar graph showing hydroxyl group percentages of a polymer verses processing pressure under certain conditions, according to one embodiment.
  • FIG. 8C is an exemplary bar graph showing hydroxyl group percentages of a polymer verses processing substrate under certain conditions, according to one embodiment.
  • FIG. 8D is an exemplary bar graph showing hydroxyl group percentages of a polymer verses cooling rate under certain conditions, according to one embodiment.
  • FIG. 8E is an exemplary bar graph showing hydroxyl group percentages of a polymer verses processing temperature under certain conditions, according to one embodiment.
  • FIG. 9A is an exemplary bar graph showing exemplary porous layer dimensions of a polymer under certain conditions, according to one embodiment.
  • FIG. 9B is an exemplary bar graph showing exemplary porous layer properties of a polymer under certain conditions, according to one embodiment.
  • FIG. 10 is an exemplary bar graph showing exemplary expulsion load verses structure of a polymer under certain conditions, according to one embodiment.
  • FIG. 11 A is a top view of a non-limiting, exemplary embodiment of a medical device, according to one embodiment.
  • FIG. 1 IB is a sectional view of a non- limiting, exemplary embodiment of a medical device, according to one embodiment.
  • FIG. 11C is a side view of a non-limiting, exemplary embodiment of a medical device, according to one embodiment.
  • a term is capitalized is not considered definitive or limiting of the meaning of a term.
  • a capitalized term shall have the same meaning as an uncapitalized term, unless the context of the usage specifically indicates that a more restrictive meaning for the capitalized term is intended.
  • the capitalization or lack thereof within the remainder of this document is not intended to be necessarily limiting unless the context clearly indicates that such limitation is intended.
  • one or more references are incorporated by reference herein. Any incorporation by reference is not intended to give a definitive or limiting meaning of a particular term. In the case of a conflict of terms, this document governs.
  • the systems and methods herein are directed to a process for producing a porous polymer including: 1) heating a surface of a solid piece of polymer to a processing temperature; 2) holding the processing temperature while displacing a porogen layer through the surface of the polymer to create a matrix layer of the solid polymer body including the polymer and the porogen layer; 3) cooling the surface of the polymer; and 4) removing at least a portion of the porogen layer from polymer.
  • the processing temperature may be any suitable processing temperature, including a processing temperature below a melting point of the polymer.
  • different polymers may have different melting temperatures and some polymers may exhibit melting properties at more than one temperature.
  • this process results in a polymer with a porous surface layer on at least one surface of the polymer body.
  • the atomic ratio of carbon to oxygen in the porous surface layer is substantially the same as the atomic ratio of carbon to oxygen in the polymer body.
  • the porous surface layer has an increased percentage of hydroxyl groups in comparison to the polymer body. Accordingly, in one embodiment, the process is not be an addition reaction but instead is a reduction of a carbonyl and/or ether group to a hydroxyl group.
  • the increased percentage of hydroxyl groups in the porous surface layer results in a more hydrophilic surface in comparison to unprocessed, smooth polymer.
  • the wettability of the porous surface layer is greater than the wettability of the unprocessed polymer body.
  • This process may also result in interfacial shear strength between the porous layer and solid polymer body that increases with longer processing times that are above a predetermined processing temperature (Tp), but below a melting point of the polymer.
  • Tp predetermined processing temperature
  • pressure applied to exert polymer flow at a constant rate is significantly correlated statistically (i.e. p-value less than 0.05 as calculated by linear regression analysis) with processing time above a defined processing temperature of 330 degrees Celsius for up to 30 to 45 minutes.
  • This correlation is counter to expected results and indicates that polymer flow viscosity increases with increased processing time below PEEK'S melting point of 343 degrees Celsius (e.g., increased processing time at about one to 13 degrees below 343 degrees Celsius, or between about 330 and 342 degrees Celsius).
  • PEEK increases in viscosity over time for particular processing temperatures.
  • a sample of PEEK that is heated to a processing temperature of about 340 degrees Celsius has a viscosity of about 47,000 Pa*s at zero seconds, but increases to about 106,000 Pa*s at about 1800 seconds if this processing temperature is held substantially constant.
  • the porous surface layer may include any suitable features based on its intended application.
  • the porous surface layer in various embodiments, may be between about 0.55 mm and 0.85 mm thick. In a particular embodiment, the porous surface layer may be approximately 0.7 mm thick.
  • the struts, which define the shape of the pores in the porous surface layer may be spaced between about 0.21 mm and 0.23 mm apart with a thickness of between about 0.9 mm and 0.11 mm.
  • the porosity is between about 61 % and 66 % and the interconnectivity of the pores may be about 99 %.
  • the above-described process may be used to create a spinal implant of substantially cubic shape with a porous layer on the top and bottom surfaces with any of the exemplary physical or chemical properties discussed above.
  • the spinal implant may, because of the wettability of the porous layers, promote adhesion of proteins that then promote tissue ingrowth.
  • the spinal implant may, because of the topographical features of the porous layer, promote tissue ingrowth.
  • cylindrical markers may be inserted into the spinal implant so that the amount of tissue ingrowth may be visualized using standard electromagnetic-imaging techniques.
  • polymer flow or “polymer flow viscosity”, as used herein may refer to any flow of a particular polymer and may not necessarily mean flow of a polymer above a melting point of the particular polymer (although, in some embodiments, polymer flow, as discussed herein, may refer to flow of a particular polymer above a melting point of the particular polymer).
  • polymer flow and “polymer flow viscosity” refer to flow of a polymer below a melting point of the polymer. Alternately, polymer flow or polymer flow viscosity may be referred to as "polymer resistance to displacement" or the like.
  • the polymer in the above exemplary process is polyetheretherketone (PEEK).
  • the porogen in the above exemplary process is sodium chloride grains arranged in one or more layers, such that when the polymer is heated it at least partially flows between the gaps of the layers of the sodium chloride particles.
  • FIG. 1 an exemplary process for producing a porous polymer is shown.
  • This exemplary process begins at step 110 by heating a surface of a solid piece of polymer to a processing temperature below a melting point of the polymer.
  • the surface is heated in any suitable way, such as by conductive heating, microwave heating, infrared heating, or any other suitable heating method.
  • any surface of the solid piece of polymer may be heated.
  • a bottom surface is placed in contact with a porogen layer and heated such that the porogen layer is at least partially displaced within the bottom surface.
  • a top or side surface is placed in contact with a porogen layer and/or heated such that the porogen layer is at least partially displaced within the top or side surface.
  • a "surface" of the solid piece of polymer may be any suitable portion (or all surfaces) of the solid piece of polymer and, in at least one embodiment, is the entire piece of polymer.
  • the solid piece of polymer may be any suitable material.
  • the polymer is polyetheretherketone (PEEK).
  • the polymer is any other suitable thermoplastic with similar properties as PEEK, such as any polymer with multiple endotherms and/or broad endotherms and/or any polymer that exhibits flow above the glass transition.
  • the polymer may be, for example, carbon fiber reinforced PEEK, polymethylmethacrylate (PMMA), polycarbonate (PC),
  • polyphenylsulfone PPSU
  • polyphenylenesulfide PPS
  • polyethersulfone PES
  • polyparaphenylene also known as self-reinforcing polyphenylene or SRP
  • thermoplastic polyurethane TPU
  • the processing temperature may be any suitable temperature and may depend upon the melting point for the particular polymer.
  • the polymer is PEEK, with a melting point of about 343 degrees Celsius.
  • the processing temperature may be any suitable range below the melting point of PEEK (e.g., 343 degrees Celsius). In one or more embodiments, as discussed below, the processing temperature is about one (1) to 38 degrees below the melting point of PEEK (e.g., the processing temperature is approximately 305 to 342 degrees Celsius). In at least one embodiment, the processing temperature is about 330 degrees Celsius for PEEK. In another embodiment, the processing temperature is about 340 degrees Celsius for PEEK. As will be understood by one of ordinary skill in the art, the processing temperature, in particular embodiments, is the processing temperature of the polymer surface.
  • the process continues with holding the processing temperature while displacing a porogen layer through the surface of the polymer to create a matrix layer of the solid polymer body including the polymer and the porogen layer.
  • the porogen layer includes particles of one or more particular materials such as sodium chloride grains or other salts, sugars, polymers, metals, etc.
  • the particles of the porogen layer may be arranged in any suitable way.
  • the particles of the porogen layer are arranged in a regular lattice pattern, with each particle touching at least one other particle.
  • the particles of the porogen layer are arranged in an irregular geometric pattern and/or are packet down without a planned geometric pattern.
  • the particles of the porogen layer may be of any suitable size and shape.
  • the particles of the porogen layer may be pre-processed such that they are one or more specific shapes, such as substantially spherical, substantially cubic, etc.
  • the particles of the porogen layer are packed, irregular grains of a salt.
  • the porogen layer is displaced through the surface of the polymer by holding the processing temperature by applying pressure to the polymer to force the polymer (which may be viscous from heating, as discussed herein) through gaps between the porogen layer (e.g., the porogen is packed and arranged such that there are gaps between the particles).
  • the result is a matrix layer with polymer in gaps between the particles of the porogen layer.
  • pressure may be applied in one or more directions to the solid piece of polymer. In one or more such embodiments, pressure may be applied to all sides of the solid piece of polymer (e.g., to create a structure with more than one porous surface).
  • the porogen layer may be displaced through the surface of the polymer to any suitable depth.
  • the porogen layer is displaced through the surface of the polymer to a depth of approximately 0.2 mm to 2.0 mm.
  • the process continues with removing at least a portion of the porogen layer from the matrix layer to form a solid polymer with a porous layer.
  • the portion of the porogen layer to be removed may be removed in any suitable way and the method of removal may be dependent upon the composition of the porogen layer.
  • Exemplary methods of removing all or a portion of the porogen layer include (but are not limited to): leaching, washing, etching, vaporizing, volatilizing, etc.
  • some or all of the sodium chloride grains may be removed by leaching (e.g., dissolving all or a portion of the porogen layer with a particular solvent).
  • the desired final product may include a solid polymer portion, a matrix layer, and a porous layer.
  • only a portion of the porous layer may be removed (e.g., to a certain depth), leaving a structure including a solid polymer layer, a matrix layer (including the polymer and porogen) and a porous polymer layer.
  • the desired structure does not include any of the porogen layer and substantially all of the porogen layer is removed, resulting in a structure that includes a solid polymer and a porous polymer layer.
  • this step 130 may be omitted.
  • FIG. 2 depicts an exemplary process for producing a porous polymer under certain conditions.
  • FIG. 2 shows a polymer sample placed in contact with a packed array of porogen (sodium chloride) grains at step 1.
  • the porogen grains are arranged at a depth of approximately 0.2 to 2 mm.
  • the arrangement of porogen grains affects the arrangement of pores in a resulting porous layer of the polymer sample and thus, the depth may be any suitable depth depending on the desired depth of pores or of a resulting matrix layer.
  • porogen grains may be arranged at depths of approximately 0.05 mm to 5 mm or any suitable range in between.
  • the surface of the polymer in contact with the porogen grains is heated to a particular processing temperature under an initial pressure of about 2 PSI.
  • the particular processing temperature is below a melting point of the polymer.
  • PEEK exhibits melting temperatures at approximately 240 and 343 degrees Celsius.
  • the initial pressure may be any suitable initial pressure.
  • the initial pressure is about 0.1 to 10 PSI.
  • the initial pressure and the final pressure are the same (e.g., the same pressure is held constant throughout the entire process).
  • step 2 once the polymer surface is heated to the processing temperature, additional pressure is applied to the polymer.
  • the processing temperature and the additional pressure is held for a predetermined processing time and, as shown in step 3, the porogen is displaced within the surface of the polymer, creating a pore network (e.g., under particular conditions, the polymer flows between the porogen).
  • the processing time is for about zero (0) to 45 minutes. In one embodiment, the processing time is for about 30 minutes.
  • the additional pressure may be any suitable pressure.
  • the additional pressure is up to 250 PSI. In one or more embodiments, the additional pressure is between 50 and 250 PSI. In at least one embodiment, the additional pressure is about 150 PSI.
  • step 4 the additional pressure and heat are removed from the polymer and the polymer surface is cooled in a controlled fashion to manage solidification and crystallization.
  • step 5 the porogen grains are leached, leaving behind a thin porous surface layer that is integrally connected with the solid polymer body. Precise control of local temperature, pressure, and time may achieve desired pore layer characteristics.
  • step 6 the introduction of surface porosity may result in expansion of the total polymer structure, indicated by the change in height, Ah.
  • PEEK exhibits melting properties at two temperatures under particular conditions. As shown in FIG. 3, PEEK exhibits several thermal transitions in this differential scanning calorimetry (DSC) scan. The first (lowest temperature) transition is the glass transition, which is characterized by a shift in the heat capacity of the polymer. As shown, this glass transition occurs at approximately 145 degrees Celsius.
  • PEEK displays higher temperature transitions, characteristic of melting (e.g., endothemis).
  • endothemis characteristic of melting
  • the enthalpy of melting the increased heat energy required to overcome the crystalline order
  • the area of the endotherm is shown by the area of the endotherm.
  • PEEK shows a double melting behavior under these conditions with a small (lower temperature) endotherm and a large (higher temperature) endotherm.
  • the first endotherm is measured at approximately 240 degrees Celsius and the second endotherm is measured at approximately 343 degrees Celsius. This "double peak" behavior has been explained as a two-stage melting process occurring due to varying size crystallites.
  • melting occurs over a range of temperatures and the melting temperature (Tm) is generally determined from the temperature corresponding to the peak maximum of the second melting endotherm (e.g., 343 degrees Celsius, shown here).
  • Tm melting temperature
  • endothemis for samples of a polymer may vary based on crystallinity of the polymer; thus, samples of the same polymer may have slightly varying endotherms based on slightly different crystalline structures (e.g., one PEEK sample may have a first endotherm at 239.5 degrees Celsius and a second PEEK sample may have a first endotherm at 241 degrees Celsius).
  • FIGS. 4A and 4B show exemplary shear strength for PEEK measured over processing times of zero (0) to 30 minutes.
  • resulting interfacial shear strength between the porous layer and solid polymer body increases with longer processing times above a predetermined processing temperature (Tp).
  • Tp predetermined processing temperature
  • FIGS. 4 A and 4B show that shear strength between the porous layer and solid polymer body increases substantially linearly with increased processing times between zero (0) and 30 minutes at temperatures of Tp.
  • Tp in this instance is 330 degrees Celsius, which, as depicted in FIG. 3 and discussed above, is below the 343 degrees Celsius melting point of PEEK.
  • FIGS. 5A and 5B show exemplary shear strength for PEEK measured over processing times of about zero (0) to 40 minutes.
  • the shear strength of PEEK potentially begins to plateau between a processing time of around 30 to 40 minutes.
  • the shear strength of PEEK is significantly correlated statistically (i.e. p-value less than 0.05 as calculated by linear regression analysis) with processing time above a defined processing temperature of about 330 degrees Celsius (which is thirteen degrees lower than the melting temperature for PEEK of 343 degrees Celsius) for up to about 30 to 45 minutes.
  • FIGS. 4C and 4D show pressure data verses time above processing temperature (Tp), while holding a constant polymer flow rate (as discussed herein, polymer flow may refer to polymer flow below a melting temperature of the polymer).
  • the polymer flow rate may be any suitable rate, such as approximately two (2) mm/minute.
  • FIGS. 4C and 4D (and 5C and 5D) depict pressures trending in a negative direction, which indicates an increase in pressure acting in compression. It should be understood that an increase in pressure may be shown as positive or negative.
  • FIGS. 4C and 4D provide a potential explanation for the substantially linear increase in shear strength with increased processing time above a specified processing temperature as shown in FIGS. 4A and 4B (about 330 degrees Celsius in this instance, which is below the 343 degrees Celsius melting temperature of PEEK).
  • the increased shear strength may be due to an increase in polymer flow viscosity.
  • polymer flow viscosity typically decreases or remains constant as it is heated for longer periods of time.
  • pressure applied to exert polymer flow at a constant rate is shown in FIGS. 4C and 4D.
  • FIGS. 4C, 4D, 5C, and 5D show data based on holding a constant rate of polymer flow (e.g., polymer flow is held constant and pressure applied to hold the polymer flow constant over time is measured), but this process may operate in the reverse.
  • pressure is known and applied linearly to keep polymer flow constant.
  • wettability via hydroxy 1/carboxyl group % increases at the surface is shown to be independently controllable independent of substrate or porogen type and pressure applied to the interface. This potentially contradicts earlier work claiming dependence on surface energy of the substrate surface. To the contrary, shown herein are increases in hydroxyl % and wettability thereby that is independent of surface energetics of the substrate or pressures applied, and instead is heavily dependent on a controlled heating and cooling rate of the infiltrating and recrystallizing PEEK.
  • FIGS. 6A, 6B, and 6C show XPS Ols spectra of a polymer in an unprocessed state and processed in various ways, including at least substantially processed in accordance with the processes described herein.
  • unprocessed polymers e.g., PEEK
  • this peek may be explained by the presence of the carbon to oxygen single and double bonds as would be expected in PEEK (e.g., with ether and ketone groups, respectively), with more carbon to oxygen single bonds present than double bonds.
  • FIG. 6A unprocessed polymers
  • PEEK e.g., PEEK
  • the porous surface of processed polymers exhibit a different peak at 535 to 530 eV, with a noticeable shift to lower binding energy.
  • this peek may be explained by the presence of oxygen to hydrogen single bonds (e.g., hydroxyl groups) in addition to the carbon to oxygen single and double bonds as would be expected in PEEK, with the concentration of oxygen to hydrogen single bonds between that of the carbon to oxygen single and double bonds.
  • the porous surface of processed polymers after gamma sterilization e.g., PEEK
  • this peek may be explained by the presence of oxygen to hydrogen single bonds in addition to the carbon to oxygen single and double bonds as would be expected in PEEK, with the concentration of hydroxyl groups exceeding that of the carbon to oxygen single and double bonds.
  • FIGS. 6D and 6E show tables with atomic and molecular percentages from the XPS Ols spectra of a polymer in an unprocessed state and processed in various ways, including at least substantially processed in accordance with the processes described herein.
  • the carbon to oxygen atomic ratio does not change in processed polymers, but there is an increased percentage of hydroxyl groups after processing.
  • the unprocessed polymers comprise approximately 0 % hydroxyl groups, 70 % ether groups, and 30 % ketone groups.
  • the injection molded PEEK comprises 65.65 % ether groups and 34.34 % ketone groups but may comprise 60-70 % ether groups and 30-40 % ketone groups.
  • the extruded PEEK comprises 70.06 % ether groups and 29.93 % ketone groups but may comprise 65-75 % ether groups and 35-45 % ketone groups.
  • the processed polymers (e.g., porous PEEK and porous PEEK after gamma sterilization) comprise approximately 50 % hydroxyl groups, 30 % ether groups, and 20 % ketone groups.
  • the processed polymers e.g., porous PEEK and porous PEEK after gamma sterilization
  • the processed polymers comprise approximately 50 % hydroxyl groups, 30 % ether groups, and 20 % ketone groups.
  • the porous PEEK comprises 48.42 % hydroxyl groups, 31.48 % ether groups, and 20.09 % ketone groups but may comprise 40-60 % hydroxyl groups, 20-40 % ether groups, and 10-30 % ketone groups.
  • the porous PEEK after gamma sterilization comprises 50.50 % hydroxyl groups, 28.95 % ether groups, and 20.53 % ketone groups but may comprise 45-55 % hydroxyl groups, 25-35 % ether groups, and 15-25 % ketone groups.
  • the unprocessed (e.g., injection molded and extruded PEEK) and processed polymers (e.g., porous PEEK and porous PEEK after gamma sterilization) comprise similar carbon to oxygen atomic ratios (e.g., carbon to oxygen atomic ratio of 3.3 for the processed polymers and 3.4 for the unprocessed polymers).
  • the injection molded PEEK comprises 79.97 % carbon atoms and 20.02 % oxygen atoms but may comprise 75-85 % carbon atoms and 15-25 % oxygen atoms.
  • the extruded PEEK comprises 84.39 % carbon atoms and 15.6 % oxygen atoms but may comprise 80-90 % carbon atoms and 10-20 % oxygen atoms.
  • the porous PEEK comprises 79.82 % carbon atoms and 20.18 % oxygen atoms but may comprise 75-85 % carbon atoms and 15-22 % oxygen atoms.
  • the porous PEEK after gamma sterilization comprises 84.17 % carbon atoms and 15.83 % oxygen atoms but may comprise 80-90 % carbon atoms and 10-20 % oxygen atoms.
  • FIG. 7 A shows exemplary wettability data of a polymer in an unprocessed state and processed in various ways, including at least substantially processed in accordance with the processes described herein.
  • a decrease in the contact angle of a fluid (e.g., water) on the surface of a solid (e.g., PEEK) indicates an increase in the wettability of the solid.
  • the wettability of unprocessed PEEK is relatively low, with a contact angle of at least 70 degrees.
  • the wettability of PEEK that has only been thermally treated and did not come into contact with a salt porogen is also relatively low, with a contact angle of at least 70 degrees.
  • the wettability of PEEK that came into contact with a salt porogen is relatively high, with a contact angle below 52 degrees.
  • the wettability of PEEK that came into contact with a packed salt porogen with pressure is also relatively high, with a contact angle below 27 degrees.
  • the wettability of a porous polymer produced in accordance with the processes described herein is very high, with a contact angle of about 0 degrees.
  • FIG. 7B shows exemplary roughness data of salt crystals and a polymer after various processing.
  • a fluid may wick into pores of a porous surface.
  • the roughness of a surface may be thought to be the primary contributor to wettability.
  • the roughness for an extruded polymer (“EXTRUDED PEEK”), a polymer pressed against a single crystal salt (“PEEK THERMALLY TREATED 340C AGAINST SINGLE CRYSTAL SALT”), and a polymer thermally treated without salt (“PEEK THERMALLY TREATED 340C AIR”) are similar.
  • SALT CRYSTALS roughness of salt crystals
  • PEEK AGAINST PACKED SALT WITH PRESSURE The roughness for a polymer substantially processed in ways described herein, as shown in FIG. 7B as “SURFACE POROUS PEEK CAGE", has a higher roughness than the other samples shown.
  • surface porous polymers in various embodiments, have average roughness values greater than that of the porogen, salt crystals likely because the height/depth of the pore wall may increase the roughness (e.g., the roughness of SURFACE POROUS PEEK CAGE is greater than the other samples).
  • macroscopically flat samples either PEEK sheet pressed against packed flat salt or PEEK sheet pressed against single crystal salt, show roughness values similar to that of salt crystals and exhibit lower contact angles. As shown in FIG. 7B, extruded PEEK and PEEK thermally treated without salt have similar roughness values and exhibit similar contact angle values.
  • the contact angle for a polymer substantially processed in ways described herein (“SURFACE POROUS PEEK CAGE”) has a much lower contact angle (e.g., about zero degrees).
  • the lower contact angle of the polymer substantially processed in ways described herein, and therefore with increased wettability may be due to changes in composition of the porous polymers (e.g., chemical changes of the surface of the polymer) and an increased roughness of the surface (e.g., physical changes of the surface), opposed to an increase in roughness due only a physical change.
  • FIGS. 8A, 8B, 8C, 8D, 8E show exemplary hydroxyl group data of an exemplary porous polymer (e.g., PEEK) produced in accordance with the processes described herein.
  • PEEK porous polymer
  • increased hydroxyl/carboxyl % may indicate increased wettability.
  • heat treatment appears to be the main factor in the increase of hydroxyl %, and therefore, wettability.
  • the heating of the polymer to the processing temperatures discussed herein results in an increased percentage of hydroxyl groups in the porous surface of the polymer in comparison to the body of the polymer or an unprocessed polymer.
  • FIG. 8 A depicts a bar graph comparing hydroxyl group % of porous polymer heated in various ways.
  • surfaces that were heated to a temperature just below (e.g., approximately 340 degrees Celsius), at, or above about 343 Celsius (e.g., a melting temperature of PEEK), flowed onto a salt porogen, then cooled down had an increase in hydroxyl % (carboxyl %).
  • a temperature just below e.g., approximately 340 degrees Celsius
  • 343 Celsius e.g., a melting temperature of PEEK
  • devices made from a polymer (e.g., PEEK) on a hot press e.g., a hot press with a heating rate of approximately 100 to 200 degrees Celsius per minute) for four (4) minutes above 343 Celsius, and at a cooling rate of approximately 20 to 50 Celsius per minute with localized heating, showed an increase in hydroxyl/carboxyl % (as shown at "CageTop” and "CageBottom") over the body of the device or injected molded devices (e.g., "CageBulk” and "Injection Mold”).
  • devices made in an oven e.g., an oven with a heating rate of about 10 to 20 degrees Celsius per minute
  • cooled at a rate of about 5 to 10 Celsius per minute e.g., a rate of about 10 to 20 degrees Celsius per minute
  • FIG. 8B shows a bar graph representing hydroxyl group percentages for porous polymers cooled or recrystallized against different substrates, including salt (NaCl), CaCl 2 , CaBr 2 , Cal 2 , Aluminum, and the hydroxyl group % of the polymer when a device is created through injection molding (e.g., without the processes described herein).
  • salt NaCl
  • CaCl 2 CaCl 2
  • CaBr 2 CaBr 2
  • Cal 2 Aluminum
  • FIG. 8C shows a bar graph representing hydroxyl group percentages of porous polymers recrystallized again various substrates with pressure applied and without pressure applied.
  • the hydroxyl group percentage is increased with the use of salt in the process (e.g., "Pressure FlatSalt” and "No Pressure FlatSalt”), but potentially not as significantly as the heating and cooling process.
  • FIG. 8D shows a bar graph representing hydroxyl group percentages of porous polymers cooled at different rates (e.g., after heating as described herein). As shown in this embodiment, quenching, quenched then annealed, and slow cooling does not affect the hydroxy 1/carboxyl % of the porous polymer after heating and processing as described herein.
  • FIG. 8E shows a bar graph depicting hydroxyl group percentages of porous polymers heated at two different temperatures (180 degrees Celsius and 340 degrees Celsius) with and without single crystal salt contact.
  • a sample of a porous polymer that is not in contact with salt (e.g., "Air") heated to about 180 degrees Celsius (via a hot plate) shows hydroxyl group percentages of about 25 to 40.
  • the sample heated to 180 degrees Celsius, without salt contact may have a hydroxyl group percentage of about 32.1 or about 27.5 to 36.7.
  • a sample of porous polymer that is not in contact with salt (e.g., "Air”) heated to about 340 degrees Celsius (via a hot plate) shows hydroxyl group percentages of about 45 to 65.
  • the sample heated to 340 degrees Celsius, without salt contact may have a hydroxyl group percentage of about 54.9 or about 48.1 to 61.7.
  • FIG. 8E further depicts a sample porous polymer that is contact with salt (e.g., "Salt”) heated to about 180 degrees Celsius having hydroxyl group percentages of about 20 to 35.
  • the sample heated to about 180 degrees in contact with salt may have a hydroxyl group percentage of about 27.6 to about 22.4 to 32.8.
  • FIG. 8E also depicts a sample porous polymer that is contact with salt (e.g., "Salt”) heated to about 340 degrees Celsius having hydroxyl group percentages of about 40 to 60.
  • the sample heated to about 340 degrees in contact with salt may have a hydroxyl group percentage of about 50.8 to about 42.9 to 58.7.
  • FIGS. 9A and 9B show porous layer data of an exemplary porous polymer (e.g., PEEK) produced in accordance with the processes described herein as measured with a direct distance transformation method from microcomputed tomography scans at a consistent threshold.
  • the porous layer includes a plurality of substantially spherical pores extending through the solid body for a defined distance (e.g., from 0.5899 mm to 0.8478 mm).
  • the pore layer thickness e.g., the defined distance
  • the porogen structure depends upon the shape of the porogen material and the arrangement of the porogen. Thus, the pores may be irregular (e.g., not in a defined pattern) or regular (in a defined pattern).
  • the pores are separated by struts that define the shape of the pores.
  • the strut spacing e.g., pore size
  • the strut spacing is between about 0.2158 mm and 0.2355 mm.
  • the strut spacing is about 0.1 to 0.5 mm. In some embodiments, the strut thickness is between about 0.0945 mm and 0.1132 mm. In further embodiments, the strut thickness is between about 0.05 mm and 0.20 mm. In a particular embodiment, the strut spacing is approximately 0.2266 mm, and the strut thickness is approximately 0.1019 mm.
  • the porosity of the porous layer is between 62.57 % and 64.97 %. In a particular embodiment, the porosity is approximately 63.59 %. In a further embodiment, the porosity is approximately 0.1 to 65%. In one embodiment, interconnectivity between the pores is between 99.0754 % and 99.981 %, and in a particular embodiment, the interconnectivity is approximately 99.87 %. In still further embodiments, the interconnectivity is about 40.0 to 99.9 %. As will be understood by one of ordinary skill in the art, pore interconnectivity of approximately 99% indicates that substantially all pores are connected and all porogen has been leached/removed from the polymer (e.g., as described herein).
  • FIG. 10 shows expulsion force data of an exemplary device including a porous polymer (e.g., PEEK) produced in accordance with the processes described herein.
  • the expulsion force that may displace a device comprising a porous polymer as produced by processes discussed herein exceeds 150 N.
  • the expulsion force is at least 178 N and may be as high as 200 N, if the device also includes ridges in its porous surface structure.
  • the expulsion force that may displace a device comprising an unprocessed polymer does not exceed 140 N and may be as low as 60 N.
  • expulsion resistance force, as measured in Newtons
  • expulsion resistance is a function of a coefficient of friction and the normal force applied.
  • devices with porous surfaces created by processes described herein should have similar expulsion resistance, regardless of the size or shape of the device.
  • Materials created from the processes described herein may have a wide variety of uses.
  • the processes described herein may be beneficial in any application where it is desired to adhere a material to the second material with different properties (e.g., adhere a first polymer with a first stiffness to a second polymer with a second stiffness).
  • a material e.g., adhere a first polymer with a first stiffness to a second polymer with a second stiffness.
  • a soft polymer e.g., polyethylene, polyvinyl-alcohol, or polycarbonate-urethane
  • PEEK polyethylene, polyvinyl-alcohol, or polycarbonate-urethane
  • porous polymers may be used in medical devices and more particularly for orthopedic applications to promote tissue ingrowth.
  • Other exemplary uses may be aerospace, automotive, and other fields.
  • FIGS. 11 A, 1 IB, and 11C show one non-limiting, exemplary embodiment of a medical device comprising the materials created from the processes described herein.
  • the example is for discussion purposes only and should not be considered to be limiting of the types, shapes, sizes, etc. of devices that may be manufactured by the processes or have the features or properties described herein.
  • the processes described herein are used to create a spinal implant 1101 that is hexahedral in shape with at least one porous layer.
  • the spinal implant 1101 comprises two
  • the spinal implant 1101 may include an inner void 1105 that is in substantially the same shape as the two porous faces and extends from the surface (e.g., 1115) of one of the porous faces (e.g., 1109) through the surface (e.g., 1119) of the other porous face (e.g., 1113).
  • the spinal implant may be produced in different sizes and shapes to accommodate different patients, implant locations, etc. (e.g., larger implants for patients with larger anatomies, smaller implants for patients with smaller anatomies, larger implants for use in the lumbar vertebrae, smaller implants for use in the thoracic vertebrae, etc.).
  • the spinal implant may be substantially cylindrical in shape, substantially cubic in shape, substantially rectangular in shape with a pyramidal nose, substantially half-moon in shape, substantially solid with no voids, substantially hollow with multiple voids of varying shapes and sizes, include ridges on the porous surfaces of varying widths and heights, etc.
  • the spinal implant (or other device) may be made from a radiolucent material, such as PEEK.
  • the spinal implant further includes one or more markers 1107 for detection of tissue ingrowth (e.g., bone) into the implant.
  • the implant may include two tantalum markers 1107 that are substantially-cylindrical in shape (these markers, however, may be any suitable shape, such as rectangular, triangular, conical, etc.).
  • the markers are positioned so that they extend vertically through the implant with the circular end- surfaces of the marker, 1117 and 1121, substantially flush with the top of porous faces, 1115 and 1119, as shown in FIGS. 1 IB and 11C.
  • the end- surfaces of the marker, 1117 and 1121 are angled so that they are even with the top of porous faces, 1115 and 1119.
  • radiography or another electromagnetic-imaging technique is used to take a lateral view of the implanted spinal implant. By determining the position of the ends of the markers, 1117 and 1121, in the image and comparing them to the location of the edges of the tissue in the image, the amount of tissue ingrowth may be determined.
  • any tissue that extends past the ends of the markers should represent tissue ingrowth into the spinal implant.
  • multiple images of the same spinal implant taken at different times may be compared to determine the change in tissue ingrowth, rate of tissue ingrowth, etc.
  • a marker may be of any suitable material or construction.
  • the marker may be made of a radiolucent material, but include a radiopaque additive (e.g., barium sulfate or bismuth compounds).
  • the marker may be made form a suitable radiopaque metal.
  • a strength of the bond between the tissue and an implant may be calculated/inferred (e.g., any orthopedic implant, including, for example, the implant described above). In various embodiments, this could be used to determine, based on amount of measurable tissue ingrowth, when a person with a spinal implant may be able to safely resume load-bearing activities.
  • a clinician may be instructed to take a radiograph of a spinal implant that includes the above described markers and porous layer.
  • the clinician may be further instructed to measure the distance the tissue has grown into the implant, based on the distance the tissue has grown past the top (or bottom) of the markers. In this way, the distance the tissue has grown past the markers may be correlated to a strength of adhesion of the implant to the surrounding tissue (e.g., bone), which may give an indication of when the person with the implant may be able to perform certain activities, with a lower risk of further injury.

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Abstract

L'invention concerne un procédé de production d'un polymère doté d'une couche poreuse à partir d'une pièce solide de polymère. Dans divers modes de réalisation, le procédé consiste à chauffer une surface d'une pièce solide de polymère à une température de traitement et à maintenir la température de traitement tout en déplaçant une couche d'agent porogène sur toute la surface du polymère pour créer une couche de matrice du corps polymère solide comprenant le polymère et la couche d'agent porogène. Dans au moins un mode de réalisation, le procédé consiste également à enlever au moins une partie de la couche d'agent porogène de la couche de matrice de manière à créer une couche poreuse de la pièce de polymère solide.
PCT/US2015/038181 2014-06-26 2015-06-26 Dispositifs poreux et leurs procédés de production Ceased WO2015200896A1 (fr)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20070191962A1 (en) * 2004-10-12 2007-08-16 Benoist Girard Sas Prosthetic acetabular cup and method of manufacture
US20100151114A1 (en) * 2008-12-17 2010-06-17 Zimmer, Inc. In-line treatment of yarn prior to creating a fabric
US7964206B2 (en) * 2003-08-20 2011-06-21 Bioretec Oy Porous medical device and method for its manufacture
US20120323339A1 (en) * 2009-12-23 2012-12-20 Beatriz Olalde Graells Porous peek article as an implant
US20130345827A1 (en) * 2010-11-11 2013-12-26 Zimmer, Inc. Orthopedic implant with porous polymer bone contacting surface

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7964206B2 (en) * 2003-08-20 2011-06-21 Bioretec Oy Porous medical device and method for its manufacture
US20070191962A1 (en) * 2004-10-12 2007-08-16 Benoist Girard Sas Prosthetic acetabular cup and method of manufacture
US20100151114A1 (en) * 2008-12-17 2010-06-17 Zimmer, Inc. In-line treatment of yarn prior to creating a fabric
US20120323339A1 (en) * 2009-12-23 2012-12-20 Beatriz Olalde Graells Porous peek article as an implant
US20130345827A1 (en) * 2010-11-11 2013-12-26 Zimmer, Inc. Orthopedic implant with porous polymer bone contacting surface

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