surgical implant, coating for a polymeric surgical implant and method for producing a polymeric surg

专利摘要:
Surgical Implant The present invention relates to a surgical implant comprising: a substrate having an outer surface and a plurality of layers disposed on the outer surface of the substrate. the substrate comprises a polymeric material and the plurality of layers comprises: an activated substrate surface layer; a valve metal layer; and a porous valve metal oxide layer, wherein the valve metal layer is disposed between the activated substrate layer and the porous valve metal oxide layer. The description provides a method for producing a polymeric surgical implant. the outer substrate surface is treated by one or more processes comprising: plasma activation; electron beam irradiation; UV light; and low energy air + ion beam irradiation; produce an activated substrate surface layer. a plurality of layers are applied over the activated substrate surface layer. The surface is converted by a spark anodizing process into an alkaline bath containing Ca and P ions into a valve metal oxide layer.
公开号:BR112013030971B1
申请号:R112013030971
申请日:2012-06-01
公开日:2019-10-22
发明作者:Voisard Cyril；Bouduban Nicolas；Gedet Philippe
申请人:Synthes Gmbh；
IPC主号:

专利说明:

[001] The present invention relates to surgical implants based on polymeric material with multilayer coatings that result in improved compatibility with soft and hard tissue. BACKGROUND OF THE INVENTION [002] Bone anchors made from polymeric materials such as polyether ether ketone (PEEK) are interesting since they are fully compatible with standard imaging techniques such as X-rays, computed tomography (CT) or magnetic resonance imaging (MRI). In particular, no artifacts are generated when using CT or MRI that would alter diagnostics. In the case of X-rays, PEEK anchors are not visible. PEEK is, however, known to have poor bone integration and, therefore, there is a need to overcome this disadvantage.
[003] The surface of polymers as polymers in the PAEK family is often not compatible with soft or hard tissues such as bones. The implants produced from these materials can integrate poorly and, finally, in dysfunction. The risk of migration or detachment from the polymer-tissue interface can be a significant consideration in a polymer-based device and, therefore, the polymer surface is often modified to improve bone integration. One method to achieve this modification is to spray a thick coating of a titanium oxide powder with, for example, vacuum plasma spray (VPS), since the titanium oxide bioactivity is much greater than that of polymers like PAEK or PEEK. However, these techniques (like VPS)
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2/33 may not ensure good anchoring between the titanium oxide surface and the fabric and the high process temperature may contribute to the deterioration of the polymer's properties. In addition, applying a thick VPS coating to complex geometries can be challenging due to the spray shading effect and the relatively wide thickness (eg 200 pm) that can leverage any thin structure that the implant surface could have. Furthermore, the so-called splash structure of plasma spray coatings may not exhibit an adequate pore structure since the pores are thin and elongated and the total porosity is limited. [004] Additionally, titanium layers made by physical vapor deposition (PVD) can be dense and thin, for example, approximately 1 micrometer or less, and thus, in some circumstances, thin PVD layers of titanium may not be satisfactory for implants.
[005] The modalities of the present invention overcome one or more of these challenges.
BRIEF SUMMARY OF THE INVENTION [006] In one aspect, the present invention provides a surgical implant comprising a substrate that has an outer surface and a plurality of layers arranged on the outer surface of the substrate where the substrate comprises a polymeric material and in which the plurality of layers comprises: (i) an activated substrate surface layer; (ii) a valve metal layer; and (iii) a porous valve metal oxide layer, wherein the valve metal layer is disposed between the activated substrate layer and the porous valve metal oxide layer.
[007] In one embodiment, the substrate comprises a thermoplastic polymeric material. In one embodiment, the polymeric substrate material of the surgical implant is polyethylene. In one mode, the
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3/33 The surgical implant substrate comprises a reinforced poly (aryl-ether-ketone) (PAEK). In an additional embodiment, the poly (aryl ether ketone) (PAEK) is independently selected from the group consisting of poly ether ketone (PEK), poly ether ketone (PEEK), poly ether ketone ketone (PEKK), poly ether ket ket ketone (PEEKK) ) and polyether ketone ether ketone ketone (PEKEKK).
[008] In one embodiment, the valve metal layer is formed from a metal selected independently from the group consisting of titanium, tungsten, aluminum, hafnium, niobium, tantalum and zirconium. In another embodiment, the porous valve metal oxide layer includes an amorphous calcium phosphate composition.
[009] In some embodiments, the plurality of layers further comprises a buffer layer, the buffer layer disposed between the activated substrate surface layer and the valve metal layer.
[0010] In one embodiment, the buffer layer comprises a plurality of alternating layers of a first material and a second material.
[0011] In some embodiments, the buffer layer comprises a plurality of alternating layers of a first material and a second material. In a further embodiment, the first material comprises a metal material and the second material comprises a nitride or a carbide of the metal material. In one embodiment, the first material comprises Ti and / or Cr and the second material comprises TiN and / or CrN and / or TiC and / or CrC.
[0012] In a buffer layer embodiment, each alternating layer of the plurality of alternating layers of the first material and the second material has a thickness in the range of 10 nm to 100 nm. In some embodiments, the buffer layer has a thickness in the range of 100 nm to 1,000 nm.
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4/33 [0013] In some embodiments, the buffer layer comprises a crystalline or amorphous material. In an additional modality, the crystalline or amorphous material is selected independently from the group consisting of T1O2, Ta2Os, Nb20s, ZrO2, S1O2, RUO2 or MoO2, MoOa, VO, VO2, V2O3, V2O5, CrO, Cr2O3, CrOs and combinations of themselves.
[0014] In some embodiments, the buffer layer comprises a plurality of alternating layers of a first material, a second material and a third material. In an additional embodiment, the first material comprising an oxide of a first metal material; the second material comprising a nitride or a carbide of a second metal material, wherein the second metal material can be the same or different from the first metal material; and the third material comprising a third metal material in which such a third metal material can be the same or different from the first metal material and / or the second metal material. In one embodiment, in particular, the first material is Ta2Os, the second material is AIN and the third material is Au, resulting in a buffer layer comprising a plurality of alternating layers of Ta ₂ O5 / AIN / Au.
[0015] In some embodiments of the surgical implant according to the present invention, the porous valve metal oxide layer is coated with a silver salt layer. In one embodiment of the surgical implant according to the present invention, the substrate comprises a radio-opaque material selected independently from the group consisting of Zr, ZrO2, ZnO, Ba, BaSCX Ta, Ta2Os, Au, Nb, Nb20s, Bi and BÍ2O3 .
[0016] In some embodiments of the surgical implant according to the present invention, the plurality of layers additionally comprises a layer of polysilane disposed between the layer of
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5/33 activated substrate surface and the valve metal layer.
[0017] In other embodiments of the surgical implant according to the present invention, the plurality of layers further comprises a conductive layer formed of a non-oxidizable conductive metal. In one embodiment, the non-oxidizable conductive metal is selected independently from the group consisting of Au, Pt, Pd and combinations thereof. In another embodiment, the conductive layer has a thickness in the range of 100 nm to 1,000 nm.
[0018] In some exemplary modalities, the surgical implant according to the present invention has a shape selected independently from the group consisting of: screw, pin, nails, plates, nails, bone anchors, clips, plate with pyramids or stakes or keels, 3D anatomical plate, complex bone replacement structure and frame.
[0019] In one embodiment, the porous valve metal oxide layer has pores with sizes ranging from about 0.1 pm to about 10 pm; and a pore density in the range of: about 10,000 pores / mm ² to about 500,000 pores / mm ² .
[0020] In another aspect, the present invention provides an outer coating layer for a polymeric surgical implant such as a poly (aryl ether-ketone) (PAEK) surgical implant comprising a plurality of layers. In some exemplary embodiments, an outer coating layer has pores ranging in size from about 0.1 pm to about 10 pm. In other embodiments, the outer coating layer has pores with a pore density in the range of about 10,000 pores / mm ² to about 500,000 pores / mm ² . In some embodiments, the outer coating layer additionally comprises the elements or ions of Ti, O, Ca and P.
[0021] In yet another aspect, the present invention provides
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6/33 a method for producing a polymeric surgical implant, such as a poly (aryl ether-ketone) surgical implant (PAEK), according to any of the exemplary modalities described herein. In an exemplary embodiment, the method comprises (A) treating the outer substrate surface by one or more processes that comprise: (i) activation of plasma; (ii) electron beam irradiation; (iii) ultraviolet light; and (iv) low energy Ar + ion beam irradiation; to thereby produce an activated substrate surface layer; (B) applying a plurality of layers over the activated substrate surface layer in which at least one layer comprises a layer of valve metal applied at a thickness of about 1 nm to about 20 pm; and (C) converting a surface of the valve metal layer through an anodizing process to thereby form the porous valve metal oxide layer that is about 2 pm to about 10 pm thick. In one embodiment, the anodizing process corresponds to a spark anodizing process carried out in an alkaline bath containing Ca and P ions in a porous valve metal oxide layer in which the porous valve metal oxide layer contains phosphate amorphous calcium. In another embodiment, the anodizing process corresponds to a color anodizing process carried out in an acidic medium. Such a color anodizing process could create a colored surface. [0022] In some embodiments, the method for producing the polymeric surgical implant, in particular poly (aryl ether ketone) material (PAEK), further comprises the step of applying a buffer layer over the activated substrate surface layer before application of the valve metal layer. In further embodiments, the step of applying the buffer layer comprises applying a plurality of alternating layers of a first layer of material and a second layer of material. In a modali
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7/33, the plurality of layers is applied substantially to cover the activated substrate surface layer.
[0023] In an exemplary embodiment of the method for producing the polymeric surgical implant, the polymer is a PAEK polymer selected independently from a group consisting of PAEK, polyether ketone (PEK), polyether ether ketone (PEEK), polyether ketone ketone ( PEKK), polyether ether ketone ketone (PEEKK) and polyether ether ketone ketone (PEKEKK).
[0024] In some modalities of the method to produce the polymeric surgical implant, such as surgical poly (aryl ether ketone) implant (PAEK), the valve metal layer is applied through a process selected independently of the group consisting of: cathodic arc deposition, magnetron ion bombardment physical vapor deposition, pulsed laser deposition, electron beam physical vapor deposition, high intensity magnetron ion bombardment, filtered vapor arc deposition, deposition and immersion ion implantation in metal plasma, vacuum arc implantation of metal vapor and plasma assisted chemical vapor deposition. In other modalities of the method for producing the polymeric surgical implant, such as a surgical poly (aryl ether-ketone) implant (PAEK), the valve metal layer is applied by dip coating or spin coating in a solution containing Ti compounds.
BRIEF DESCRIPTION OF THE VARIOUS VIEWS OF THE DRAWINGS [0025] The aforementioned summary, as well as the following detailed description of the surgical implant modalities of the present invention, will be better understood when read in conjunction with the attached drawings of exemplary modalities. It must be understood, however, that the invention is not limited to the precise provisions and instrumentalities shown.
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8/33 [0026] In the drawings:
[0027] Figure 1 is a perspective view of a schematic section through an exemplary embodiment of a surgical implant in accordance with the present invention;
[0028] Figure 2 is a schematic section through another exemplary embodiment of a surgical implant in accordance with the present invention;
[0029] Figure 3A is a cross-sectional view of a surgical implant comprising a buffer layer disposed between the activated substrate surface layer and the valve metal layer in accordance with an exemplary embodiment of the present invention;
[0030] Figure 3B is a cross-sectional view of a surgical implant comprising a buffer layer disposed between the activated substrate surface layer and the valve metal layer as shown in Figure 3A with the buffer layer highlighted;
[0031] Figure 3C is a cross-sectional view of the buffer layer of Figure 3A or Figure 3B comprising a plurality of alternating layers of a first material and a second material;
[0032] Figure 3D is a cross-sectional view of another exemplary embodiment of a surgical implant according to the present invention that illustrates a conductive layer 15 as part of the plurality of layers arranged on the outer surface of the substrate;
[0033] Figure 4 illustrates an exemplary bone anchor produced from a PEEK-like polymer with bone integrating surface treatment;
[0034] Figure 5 illustrates a perspective view of an implant
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9/33 surgical for use after removing an intervertebral disc from a human spine where the outer surface 20 and the inner surface 21 have been activated according to an exemplary embodiment of the present invention;
[0035] Figure 6A illustrates surgical implant 30 for reconstruction of a skullcap according to the modalities described here; and [0036] Figure 6B illustrates a surgical implant 30 in relation to a human skull for reconstruction of a skullcap according to the modalities described here.
DETAILED DESCRIPTION [0037] Reference will now be made in detail to the various modalities of this description, examples of which are illustrated in the attached drawings of Figures 1 to 6. Whenever possible, the same numerical references will be used by all drawings to refer to equal or similar parts.
[0038] In one aspect, the present invention provides a surgical implant that comprises a substrate that has an outer surface and a plurality of layers arranged on the outer surface of the substrate. The substrate comprises a polymeric material and wherein the plurality of layers comprises: (i) an activated substrate surface layer; (ii) a valve metal layer; and (iii) a porous valve metal oxide layer, wherein the valve metal layer is disposed between the activated substrate layer and the porous valve metal oxide layer.
[0039] Typically, an exemplary substrate for use in the surgical implant according to the present invention comprises a polymeric material. The polymeric material can be a thermoplastic polymeric material, for example, polyethylene. In another example, the polymeric material may be a poly (aryl-ether-ketone) (PAEK) material.
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In one embodiment, poly (aryl-ether-ketone) (PAEK) includes polyether ketone (PEK), polyether ether ketone (PEEK), polyether ketone ketone (PEKK), polyether ether ketone ketone (PEEKK), polyether ketone ether ketone (PEKEKK) and combinations thereof. In one embodiment, poly (aryl-ether-ketone) (PAEK) is polyether ether ketone (PEEK). In another embodiment, poly (aryl-ether-ketone) (PAEK) is polyether ketone-ketone (PEKK).
[0040] In some embodiments, the substrate comprises a reinforced poly (aryl-ether-ketone) (PAEK). In one embodiment, the reinforcement comprises short glass fibers, long glass fibers, carbon fibers or combinations thereof.
[0041] In some embodiments, the substrate comprises a radio-opaque material selected independently from the group consisting of Zr, ZrO2, ZnO, Ba, BaSCX Ta, Ta2Os, Au, Nb, Nb20s, Bi and B2O3. In one embodiment, the radio-opaque material is BaSCU. Exemplary radio-opaque materials suitable for use in the present invention can be found in US Patent Application Publication No. 2007/0191708 the description of which is incorporated herein entirely by reference.
[0042] In one embodiment, the substrate comprises a poly (aryl-ether-ketone) material (PAEK) or a thermoplastic material such as polyethylene, each having a thickness in the range of about 1 mm to about 5 cm . In another embodiment, the substrate comprising a poly (aryl-ether-ketone) material (PAEK) or a thermoplastic material such as polyethylene, has a thickness in the range of about 1 mm to about 5 cm. In another embodiment, the PAEK material or a thermoplastic material such as polyethylene has a thickness in the range of about 0.1 cm to 1 cm, from about 0.2 cm to about 1 cm, from about 0.3 cm to about 1 cm, about 0.4 cm to about 1 cm, about 0.5 cm to about 1 cm, about 0.6 cm to about 1
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11/33 cm, from about 0.7 cm to about 1 cm, from about 0.8 cm to about 1 cm, from about 0.9 cm to about 1 cm, from about 0.1 cm to about 2 cm, from about 0.2 cm to about 2 cm, from about 0.3 cm to about 2 cm, from about 0.4 cm to about 2 cm, from about 0 .5 cm to about 2 cm, about 0.6 cm to about 2 cm, about 0.7 cm to about 2 cm, about 0.8 cm to about 2 cm, about from 0.9 cm to about 2 cm, from about 0.1 cm to about 3 cm, from about 0.2 cm to about 3 cm, from about 0.3 cm to about 3 cm, from about 0.4 cm to about 3 cm, from about 0.5 cm to about 3 cm, from about 0.6 cm to about 3 cm, from about 0.7 cm to about 3 cm, from about 0.8 cm to about 3 cm, from about 0.9 cm to about 3 cm, from about 0.1 cm to about 4 cm, from about 0.2 cm to about about 4 cm, about 0.3 cm to about 4 cm, about 0.4 cm to about 4 cm, about 0.5 cm to about 4 cm, about 0.6 cm about 4 cm, about 0.7 cm about 4 cm, about 0.8 cm to about 4 cm, about 0.9 cm to about 4 cm, about 0.1 cm to about 5 cm, about 0, 2 cm to about 5 cm, from about 0.3 cm to about 5 cm, from about 0.4 cm to about 5 cm, from about 0.5 cm to about 5 cm, from about 0.6 cm to about 5 cm, about 0.7 cm to about 5 cm, about 0.8 cm to about 5 cm and about 0.9 cm to about 5 cm.
[0043] In one embodiment, the activated substrate surface layer has a surface thickness between about 1 atomic layer at about 1 pm. In one embodiment, the activated substrate surface layer has a surface thickness in a selected range regardless of the group consisting of from about 0.1 pm to about 1 pm, from about 0.2 pm to about 2 pm, from about 0.3 pm to about 3 pm, from about 0.4 to about 4 pm, from about 0.5 to about 5 pm, from about 0.6 pm to about 6 pm, from about 0.7 pm to about 7 pm, from about 0.8 pm to about 8 pm,
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12/33 from about 0.9 pm to about 9 pm, from about 0.1 pm to about 0.2 pm, from about 0.1 pm to about 0.3 pm, from about 0 , 1 pm to about 0.4 pm, from about 0.1 to about 0.5 pm, from about 0.1 pm to about 0.6 pm, from about 0.1 pm to about 0.7 pm, from about 0.1 pm to about 0.8 pm, from about 0.1 pm to about 0.9 pm, from about 0.2 pm to about 0.3 pm, from about 0.2 pm to about 0.4 pm, from about 0.2 pm to about 0.5 pm, from about 0.2 pm to about 0.6 pm, from about 0, 2 pm to about 0.7 pm, from about 0.2 pm to about 0.8 pm, from about 0.2 pm to about 0.9 pm, from about 0.3 pm to about 0.4 pm, from about 0.3 pm to about 0.5 pm, from about 0.3 to about 0.6 pm, from about 0.3 pm to about 0.7 pm, from about 0.3 pm to about 0.8 pm, about 0.3 to about 0.9 pm, about 0.4 pm to about 0.5 pm, about 0.4 pm at about 0.6 pm, from about 0.4 pm to about 0.7 pm, from about 0.4 pm to about 0.8 pm, about 0.4 p from about 0.9 pm, from about 0.5 pm to about 0.6 pm, from about 0.5 pm to about 0.7 pm, from about 0.5 pm to about 0, 8 pm, from about 0.5 pm to about 0.9 pm, from about 0.7 pm to about 0.8 pm and from about 0.7 pm to about 0.9 pm.
[0044] In some embodiments, the valve metal layer is selected independently from the group consisting of titanium, tungsten, aluminum, hafnium, niobium, tantalum and zirconium.
[0045] In some embodiments, the valve metal layer has a thickness of about 1 nm to about 20 pm. In one embodiment, the valve metal layer has a thickness in a selected range regardless of about the group consisting of about 1,000 nm to about 20,000 nm, about 2,000 nm to about 20,000 nm, about 3,000 nm to about 20,000 nm, from about 4,000 nm to about 20,000 nm, from about 5,000 nm to about 20,000 nm, from about 6,000 nm to about 20,000 nm, from cer
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13/33 ca from 7,000 nm to about 20,000 nm, from about 8,000 nm to about 20,000 nm, from about 9,000 nm to about 20,000 nm, from about 10,000 nm to about 20,000 nm, from about 11,000 nm to about 20,000 nm, from about 12,000 nm to about 20,000 nm, from about 13,000 nm to about 20,000 nm, from about 14,000 nm to about 20,000 nm, from about 15,000 nm to about 20,000 nm , from about 16,000 nm to about 20,000 nm, from about 17,000 nm to about 20,000 nm, from about 18,000 nm to about 20,000 nm, from about 19,000 nm to about 20,000 nm, from about 1,000 nm at about 2,000 nm, from about 1,000 nm to about 3,000 nm, from about 1,000 nm to about 4,000 nm, from about 1,000 nm to about 5,000 nm, from about 1,000 nm to about 6,000 nm, from about 1,000 nm to about 7,000 nm, from about 1,000 nm to about 8,000 nm, from about 1,000 nm to about 9,000 nm, from about 1,000 nm to about 10,000 nm, from about 1,000 nm to about 11,000 nm, about from 1,000 nm to about 12,000 nm, from about 1,000 nm to about 13,000 nm, from about 1,000 nm to about 14,000 nm, from about 1,000 nm to about 15,000 nm, from about 1,000 nm to about 16,000 nm, from about 1,000 nm to about 17,000 nm, from about 1,000 nm to about 18,000 nm and from about 1,000 nm to about 19,000 nm.
[0046] In some embodiments, the porous valve metal oxide layer has a thickness of about 2 pm to about 10 pm. In one embodiment, the porous valve metal oxide layer has a thickness that is in a selected range regardless of the group consisting of 2,000 nm to 3,000 nm, 3,000 nm to 4,000 nm, 4,000 nm to 5,000 nm, from 5,000 nm to 6,000 nm, 6,000 nm to 7,000 nm, 7,000 nm to 8,000 nm, 8,000 nm to 9,000 nm, 9,000 nm to 10,000 nm.
[0047] In one embodiment, the valve metal oxide layer
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The porous layer has pores ranging in size from about 0.1 pm to about 10 pm. In another embodiment, from about 0.1 pm to about 0.2 pm, from about 0.1 pm to about 0.3 pm, from about 0.1 pm to about 0.4 pm, from about 0.1 pm to about 0.5 pm, about 0.1 pm to about 0.6 pm, about 0.1 pm to about 0.7 pm, about 0.1 pm to about 0.8 pm, from about 0.1 pm to about 0.9 pm, from about 0.2 pm to about 1.2 pm, from about 0.2 pm to about 1 , 3 pm, from about 0.2 pm to about 1.4 pm, from about 0.2 pm to about 1.5 pm, from about 0.2 pm to about 1.6 pm, from about 0.2 pm to about 1.7 pm, about 0.2 pm to about 1.8 pm, about 0.2 pm to about 1.9 pm, about 0.3 pm to about 2.2 pm, from about 0.3 pm to about 2.3 pm, from about 0.3 pm to about 2.4 pm, from about 0.3 pm to about 2 , 5 pm, from about 0.3 pm to about 2.6 pm, from about 0.3 pm to about 2.7 pm, from about 0.3 pm to about 2.8 pm, from about 0.3 pm to about 2.9 pm, from about 0.4 pm to about 3.2 pm, from about 0.4 pm to about 3.3 pm, from about 0.4 pm to about 3.4 pm, from about 0.4 pm to about 3.5 pm, from about 0.4 pm to about 3.6 pm, from about 0.4 pm to about 3.7 pm, from about 0.4 pm to about 3.8 pm, from about 0.4 pm to about 3.9 pm, about 0, 5 pm to about 4.2 pm, from about 0.5 pm to about 4.3 pm, from about 0.5 pm to about 4.4 pm, from about 0.5 pm to about 4.5 pm, from about 0.5 pm to about 4.6 pm, from about 0.5 pm to about 4.7 pm, from about 0.5 pm to about 4.8 pm, from about 0.5 pm to about 4.9 pm, from about 0.6 pm to about 5.2 pm, from about 0.6 pm to about 5.3 pm, from about 0, 6 pm to about 5.4 pm, from about 0.6 pm to about 5.5 pm, from about 0.6 pm to about 5.6 pm, from about 0.6 pm to about 5.7 pm, from about 0.6 pm to about 5.8 pm, from about 0.6 pm to about 5.9 pm, from about 0.7 pm to about 6.2 pm, from about 0.7 pm to about 6.3 pm, from about 0.7 pm to about 6.4 pm, from about
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0.7 pm to about 6.5 pm, from about 0.7 pm to about 6.6 pm, from about 0.7 pm to about 6.7 pm, from about 0.7 pm to about 6.8 pm, about 0.7 pm to about 6.9 pm, about 0.8 pm to about 7.2 pm, about 0.8 pm to about 7.3 pm, from about 0.8 pm to about 7.4 pm, from about 0.8 pm to about 7.5 pm, from about 0.8 pm to about 7.6 pm, from about 0.8 pm to about 7.7 pm, from about 0.8 pm to about 7.8 pm, from about 0.8 pm to about 7.9 pm, from about 0.9 pm to about 8.2 pm, about 0.9 pm to about 8.3 pm, about 0.9 pm to about 8.4 pm, about 0.9 pm to about 8.5 pm, from about 0.9 pm to about 8.6 pm, from about 0.9 pm to about 8.7 pm, from about 0.9 pm to about 8.8 pm, from about 0.9 pm to about 8.9 pm, from about 1 pm to about 9.2 pm, from about 1 pm to about 9.3 pm, from about 1 pm to about 9.4 pm , from about 1 pm to about 9.5 pm, from about 1 pm to about 9.6 pm, from about 1 pm to about 9.7 pm , from about 1 pm to about 9.8 pm, from about 1 pm to about 9.9 pm, from about 2 pm to about 9.2 pm, from about 2 pm to about 9, 3 pm, from about 2 pm to about 9.4 pm, from about 2 pm to about 9.5 pm, from about 2 pm to about 9.6 pm, from about 2 pm to about 9.7 pm, from about 2 pm to about 9.8 pm, from about 2 pm to about 9.9 pm, from about 3 pm to about 9.3 pm, from about 3 pm to about 9.3 pm, about 3 pm to about 9.4 pm, about 3 pm to about 9.5 pm, about 3 pm to about 9.6 pm, about 3 pm to about 9.7 pm, from about 3 pm to about 9.8 pm, from about 3 pm to about 9.9 pm, from about 4 pm to about 9.2 pm, from about from 4 pm to about 9.3 pm, from about 4 pm to about 9.4 pm, from about 4 pm to about 9.5 pm, from about 4 pm to about 9.6 pm, from about 4 pm to about 9.7 pm, from about 4 pm to about 9.8 pm, from about 4 pm to about 9.9 pm, from about 5 pm to about 9.2 pm, from about 5 pm to about d and 9.3 pm, from about 5 pm to about
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16/33 from 9.4 pm, from about 5 pm to about 9.5 pm, from about 5 pm to about 9.6 pm, from about 5 pm to about 9.7 pm, from about from 5 pm to about 9.8 pm, from about 5 pm to about 9.9 pm, from about 6 pm to about 9.2 pm, from about 6 pm to about 9.3 pm, from about 6 pm to about 9.4 pm, from about 6 pm to about 9.5 pm, from about 6 pm to about 9.6 pm, from about 6 pm to about 9.7 pm, from about 6 pm to about 9.8 pm, from about 6 pm to about 9.9 pm, from about 7 pm to about 9.2 pm, from about 7 pm to about 9 , 3 pm, from about 7 pm to about 9.4 pm, from about 7 pm to about 9.5 pm, from about 7 pm to about 9.6 pm, from about 7 pm to about from 9.7 pm, from about 7 pm to about 9.8 pm, from about 7 pm to about 9.9 pm, from about 8 pm to about 9.2 pm, from about 8 pm about 9.3 pm, about 8 pm to about 9.4 pm, about 8 pm to about 9.5 pm, about 8 pm to about 9.6 pm, about 8 pm to about 9.7 pm, from about 8 pm to about 9.8 pm, from about 8 pm to about 9.9 pm, from about 9 pm to about 9.2 pm, from about 9 pm to about 9.3 pm, from about 9 pm to about 9.4 pm, from about 9 pm to about 9.5 pm, from about 9 pm to about 9.6 pm, from about 9 pm to about 9.7 pm , from about 9 pm to about 9.8 pm and from about 9 pm to about 9.9 pm.
[0048] In another embodiment, the porous valve metal oxide layer has a pore density in the range of about 10,000 pores / mm ² to about 500,000 pores / mm ² . In another embodiment, the porous valve metal oxide layer has a pore density that is in a selected range regardless of the group consisting of about 10,000 pores / mm ² to about 50,000 pores / mm ² , about ros / mm ² , about ros / mm ² , about ros / mm ² , about
10,000 pores / mm ² a
10,000 pores / mm ² a
10,000 pores / mm ² a
10,000 pores / mm ² to about 100,000 about 150,000 about 250,000 about 300,000 poPetition 870190048981, from 05/24/2019, p. 21/47
17/33
/ mm ² , of about 10,000 pores / mm ² at about in 350,000 powder- / mm ² , of about 10,000 pores / mm ² at about in 400,000 powder- / mm ² , of about 10,000 pores / mm ² at about in 450,000 powder- / mm ² , of about 50,000 pores / mm ² at about in 100,000 powder- / mm ² , of about 50,000 pores / mm ² at about in 150,000 powder- / mm ² , of about 50,000 pores / mm ² at about in 250,000 powder- / mm ² , of about 50,000 pores / mm ² at about in 300,000 powder- / mm ² , of about 50,000 pores / mm ² at about in 350,000 powder- / mm ² , of about 50,000 pores / mm ² at about in 400,000 powder- / mm ² , of about 50,000 pores / mm ² at about in 500,000 powder- / mm ² , of about 150,000 pores / mm ² at about in 150,000 powder- / mm ² , of about 150,000 pores / mm ² at about in 250,000 powder- / mm ² , of about 150,000 pores / mm ² at about in 300,000 powder- / mm ² , of about 150,000 pores / mm ² at about in 350,000 powder- / mm ² , of about 150,000 pores / mm ² at about in 400,000 powder- / mm ² , of about 150,000 pores / mm ² at about in 450,000 powder- / mm ² , of about 150,000 pores / mm ² at about in 450,000 powder- / mm ² , of about 200,000 pores / mm ² at about in 250,000 powder- / mm ² , of about 200,000 pores / mm ² at about in 300,000 powder- / mm ² , of about 200,000 pores / mm ² at about in 350,000 powder- / mm ² , of about 200,000 pores / mm ² at about in 400,000 powder- / mm ² , of about 200,000 pores / mm ² at about in 450,000 powder- / mm ² , of about 200,000 pores / mm ² at about in 450,000 powder- / mm ² , of about 250,000 pores / mm ² to fence in 300,000 powder- / mm ² , of about 250,000 pores / mm ² to fence in 350,000 powder- / mm ² , of about 250,000 pores / mm ² to fence in 400,000 powder- / mm ² , of about 250,000 pores / mm ² to fence in 450,000 powder- / mm ² , of about 250,000 pores / mm ² to fence in 450,000 powder- / mm ² , of about 300,000 pores / mm ² to fence in 350,000 powder- / mm ² , of about 300,000 pores / mm ² to fence in 400,000 powder-
Petition 870190048981, of 05/24/2019, p. 22/47
18/33 ros / mm ² , about ros / mm ² , about ros / mm ² , about ros / mm ² , about ros / mm ² , about ros / mm ² , about in
300,000 pores / mm ² a
300,000 pores / mm ² a
350,000 pores / mm ² a
350,000 pores / mm ² a
350,000 pores / mm ² a
400,000 pores / mm ² at about 450,000 po about 450,000 po about 400,000 po about 450,000 po about 450,000 po about 450,000 po / 450,000 poles / mm ² and from about 450,000 pores / mm ² to about 500,000 poles / mm ² .
[0049] In some embodiments, the plurality of layers further comprises a buffer layer. In one embodiment, the buffer layer is disposed between the activated substrate surface layer and the valve metal layer.
[0050] In some embodiments, the buffer layer has a thickness in the range of 100 nm to 1,000 nm. In additional embodiments, the buffer layer has a thickness that is in a selected range regardless of the group consisting of 100 nm to 200 nm, 100 nm to 300 nm, 100 nm to 400 nm, 100 nm to 500 nm , from 100 nm to 600 nm, from 100 nm to 700 nm, from 100 nm to 800 nm, from 100 nm to 900 nm, from 200 nm to 300 nm, from 200 nm to 400 nm, from 200 nm to 500 nm, 200 nm to 600 nm, 200 nm to 700 nm, 200 nm to 800 nm, 200 nm to 900 nm, 200 nm to 100 nm, 300 nm to 400 nm, 300 nm to 500 nm, from 300 nm to 600 nm, from 300 nm to 700 nm, from 300 nm to 800 nm, from 300 nm to 900 nm, from 300 nm to 100 nm, from 400 nm to 500 nm, from 400 nm to 600 nm, from 400 nm to 700 nm, 400 nm to 800 nm, 400 nm to 900 nm, 400 nm to 100 nm, 500 nm to 600 nm, 500 nm to 700 nm, 500 nm to 800 nm, 500 nm at 900 nm, from 500 nm to 100 nm, from 600 nm to 700 nm, from 600 nm to 800 nm, from 600 nm to 900 nm, from 600 nm to 100 nm, from 700 nm to 800 nm, from 700 nm to 900 nm, 700 nm to 100 nm, 800 nm to 900 nm, 800 nm to 100 n m and from 900 nm to 1,000 nm.
Petition 870190048981, of 05/24/2019, p. 23/47
[0051] In one embodiment, the buffer layer comprises a plurality of alternating layers of a first material and a second material. In one embodiment, the first material comprises a metal material and the second material comprises a nitride or a carbide of the metal material. In a specific embodiment, the first material comprises Ti and / or Cr. In another embodiment, the second material comprises TiN and / or CrN and / or TiC and / or CrC.
[0052] In one embodiment, each alternating layer of the plurality of alternating layers of the first material has a thickness in the range of 10 nm to 100 nm. In another embodiment, each alternating layer of the plurality of alternating layers of the first material has a thickness that is in a range selected independently from the group consisting of 10 nm to 20 nm, 10 nm to 30 nm, 10 nm to 40 nm , from 10 nm to 50 nm, from 10 nm to 60 nm, from 10 nm to 70 nm, from 10 nm to 80 nm, from 10 nm to 90 nm, from 20 nm to 30 nm, from 20 nm to 40 nm, from 20 nm to 50 nm, from 20 nm to 60 nm, from 20 nm to 70 nm, from 20 nm to 80 nm, from 20 nm to 90 nm, from 20 nm to 100 nm, from 30 nm to 40 nm, from 30 nm to 50 nm, 30 nm to 60 nm, 30 nm to 70 nm, 30 nm to 80 nm, 30 nm to 90 nm, 30 nm to 100 nm, 40 nm to 50 nm, 40 nm to 60 nm, 40 nm to 70 nm, 40 nm to 80 nm, 40 nm to 90 nm, 40 nm to 100 nm, 50 nm to 60 nm, 50 nm to 70 nm, 50 nm at 80 nm, from 50 nm to 90 nm, from 50 nm to 100 nm, from 60 nm to 70 nm, from 60 nm to 80 nm, from 60 nm to 90 nm, from 60 nm to 100 nm, from 70 nm to 80 nm, 70 nm to 90 nm, 70 nm to 100 nm, 80 nm to 90 nm, 80 nm to 100 nm and 90 nm to 100 nm.
[0053] In one embodiment, each alternating layer of the plurality of alternating layers of the second material has a thickness in the range of 10 nm to 100 nm. In another embodiment, each alternating layer of the plurality of alternating layers of the second material has a thickness that is in a selected range independently.
Petition 870190048981, of 05/24/2019, p. 24/47
20/33 te of the group consisting of 10 nm to 20 nm, 10 nm to 30 nm, 10 nm to 40 nm, 10 nm to 50 nm, 10 nm to 60 nm, 10 nm to 70 nm , from 10 nm to 80 nm, from 10 nm to 90 nm, from 20 nm to 30 nm, from 20 nm to 40 nm, from 20 nm to 50 nm, from 20 nm to 60 nm, from 20 nm to 70 nm, from 20 nm to 80 nm, from 20 nm to 90 nm, from 20 nm to 100 nm, from 30 nm to 40 nm, from 30 nm to 50 nm, from 30 nm to 60 nm, from 30 nm to 70 nm, from 30 nm to 80 nm, 30 nm to 90 nm, 30 nm to 100 nm, 40 nm to 50 nm, 40 nm to 60 nm, 40 nm to 70 nm, 40 nm to 80 nm, 40 nm to 90 nm, 40 nm to 100 nm, 50 nm to 60 nm, 50 nm to 70 nm, 50 nm to 80 nm, 50 nm to 90 nm, 50 nm to 100 nm, 60 nm at 70 nm, from 60 nm to 80 nm, from 60 nm to 90 nm, from 60 nm to 100 nm, from 70 nm to 80 nm, from 70 nm to 90 nm, from 70 nm to 100 nm, from 80 nm to 90 nm, from 80 nm to 100 nm and from 90 nm to 100 nm.
[0054] In one embodiment, each alternating layer of the plurality of alternating layers of the first material and the second material has a thickness in the range of 10 nm to 100 nm. In another embodiment, each alternating layer of the plurality of alternating layers of the first material and the second material has a thickness that is in a selected range regardless of the group consisting of 10 nm to 20 nm, 10 nm to 30 nm, 10 nm to 40 nm, 10 nm to 50 nm, 10 nm to 60 nm, 10 nm to 70 nm, 10 nm to 80 nm, 10 nm to 90 nm, 20 nm to 30 nm, 20 nm at 40 nm, from 20 nm to 50 nm, from 20 nm to 60 nm, from 20 nm to 70 nm, from 20 nm to 80 nm, from 20 nm to 90 nm, from 20 nm to 100 nm, from 30 nm to 40 nm, 30 nm to 50 nm, 30 nm to 60 nm, 30 nm to 70 nm, 30 nm to 80 nm, 30 nm to 90 nm, 30 nm to 100 nm, 40 nm to 50 nm, 40 nm to 60 nm, 40 nm to 70 nm, 40 nm to 80 nm, 40 nm to 90 nm, 40 nm to 100 nm, 50 nm to 60 nm, 50 nm to 70 nm , from 50 nm to 80 nm, from 50 nm to 90 nm, from 50 nm to 100 nm, from 60 nm to 70 nm, from 60 nm to 80 nm, from 60 nm to 90 nm, from 60 nm to 100 nm, from 70 nm to 80
Petition 870190048981, of 05/24/2019, p. 25/47
21/33 nm, from 70 nm to 90 nm, from 70 nm to 100 nm, from 80 nm to 90 nm, from 80 nm to 100 nm and from 90 nm to 100 nm.
[0055] In another embodiment, the buffer layer comprises a crystalline or amorphous material. In such modality, the crystalline or amorphous material is selected independently from the group consisting of T1O2, Ta2Os, Nb20s, ZrO ₂ , S1O2, RuO ₂ or MoO2, MoOa, VO, VO2, V2O3, V2O5, CrO, Cr ₂ O ₃ , CrOse combinations thereof.
[0056] In yet another embodiment, the buffer layer comprises the plurality of alternating layers of a first material, a second material and a third material. In one embodiment, the buffer layer comprises 1 to 10 groups of three alternating layers. In an additional embodiment, the first material comprising an oxide of a first metal material; the second material comprising a nitride of a second metal material, wherein the second metal material can be the same or different from the first metal material; and the third material comprising a third metal material in which such a third metal material can be the same or different from the first metal material and / or the second metal material. In a particular embodiment, the first material is Ta ₂ O5, the second material is AIN and the third material is Au, resulting in a buffer layer that comprises a plurality of alternating layers of Ta2Os / AIN / Au.
[0057] In some embodiments according to the present invention, the plurality of layers disposed on the substrate further comprises an adhesive layer disposed between the activated substrate surface layer and the valve metal layer. In such an embodiment, the adhesive layer is a polysilane layer derived from methylacryloxypropyl trimethoxysilane.
[0058] In other embodiments of the surgical implant according to the present invention, the plurality of layers comprises additives
Petition 870190048981, of 05/24/2019, p. 26/47
22/33 a conductive layer formed of a conductive non-oxidizable metal. In one embodiment, the non-oxidizable conductive metal is selected independently from the group consisting of Au, Pt, Pd and combinations thereof. In one embodiment, the conductive layer is located between the buffer layer and the valve metal layer. In another embodiment, the conductive layer has a thickness: in the range of 100 nm to 1,000 nm; 100 nm to 500 nm; and 200 nm to 300 nm.
[0059] In some embodiments, the surgical implant includes a coating of a silver salt located in the porous valve metal oxide layer. In such an embodiment, the silver salt is AgNOa.
[0060] In some exemplary embodiments of a surgical implant according to the present invention, the surgical implant comprises a substrate that has an outer surface and a plurality of layers arranged on the outer surface of the substrate, where the substrate comprises a material of poly (aryl ether ketone) (PAEK) or a thermoplastic material like polyethylene. In one embodiment, the plurality of layers substantially covers the entire outer surface of the substrate. For the purposes of this modality, covering substantially means that at least 95% of the outer surface of the substrate is covered by the plurality of layers.
[0061] Implantable medical devices are manufactured for a variety of medical / clinical applications including to replace a lost biological structure, to support a damaged biological structure or to improve an existing biological structure. The implants and / or the surfaces of the implants that come into contact with the body / body tissues vary in their compositions. Some of the implants can be made from biomedical materials like titanium, silicone or apatite depending on the functionality of the implant
Petition 870190048981, of 05/24/2019, p. 27/47
Desired 23/33. In some cases, implants contain electronic components, for example, artificial pacemakers and cochlear implants and / or are bioactive as devices for applying subcutaneous drugs in the form of implantable pills or stents to elute drugs. [0062] Surgical implants exist for medical / clinical applications in the area of orthopedics, neurosurgery, cardiology and cardiothoracic surgery, among others. Non-limiting examples of surgical implants include: cardiovascular implants, for example, heart valve prostheses and tubular vascular prostheses; neurosurgical implants, for example, bypass and hydrocephalic components; specimens of intracranial aneurysm; bone and joint replacements, for example, total or partial thigh joint prostheses and total knee joint prostheses; osteosynthesis and spinal devices, for example, metal bone screws, metal bone plates, medullary pins, metallic skeletal pins and wires and total intervertebral spinal disc prostheses; oral maxillofacial surgery implants; and spinal and pelvic systems like the Universal Spine System, Harrington System and conventional systems.
[0063] Consequently, surgical implants include a wide range of products of different compositions, structural complexity and medical / clinical applications. Thus, implants for use in accordance with exemplary embodiments of the present invention may vary in size, shape and other physical and chemical characteristics that depend on the context of use.
[0064] Consequently, in one embodiment, the surgical implant according to the present invention has a shape selected independently from the group consisting of: screw, pin, nails, plates, nails, bone anchors, clips, plate with pyramids or stakes or keels, anatomical 3D plate, complex bone replacement structure and frame.
Petition 870190048981, of 05/24/2019, p. 28/47
24/33 [0065] A person skilled in the art will appreciate that the properties, for example, scale, shape, chemical composition, etc., of suitable implants, can be selected to obtain a desired result, for example, organ repair, organ replacement or organ addition.
[0066] In another aspect, the present invention provides a coating for a poly (aryl ether ketone) (PAEK) or thermoplastic surgical implant material, such as polyethylene, which comprises a plurality of layers. In another example, the coating has an outer coating layer that has pores in the range of about 0.1 pm to about 10 pm. In another embodiment, the outer coating layer has pores of selected sizes regardless of the group consisting of a range of: from about 0.1 pm to about 1 pm, from about 0.2 pm to about 2 pm, from about 0.3 pm to about 3 pm, from about 0.4 to about 4 pm, from about 0.5 to about 5 pm, from about 0.6 pm to about 6 pm, from about 0.7 pm to about 7 pm, from about 0.8 pm to about 8 pm, from about 0.9 pm to about 9 pm, from about 0.1 pm to about 0 , 2 pm, about 0.1 pm to about 0.3 pm, about 0.1 pm to about 0.4 pm, about 0.1 to about 0.5 pm, about from 0.1 pm to about 0.6 pm, from about 0.1 pm to about 0.7 pm, from about 0.1 pm to about 0.8 pm, from about 0.1 pm at about 0.9 pm, from about 0.2 pm to about 0.3 pm, from about 0.2 pm to about 0.4 pm, from about 0.2 pm to about 0, 5 pm, from about 0.2 pm to about 0.6 pm, from about 0.2 pm to about 0.7 pm, from about 0.2 pm to about 0.8 pm, from ce from 0.2 pm to about 0.9 pm, from about 0.2 pm to about 10 pm, from about 0.3 pm to about 0.4 pm, from about 0.3 pm to about 0.5 pm, about 0.3 to about 0.6 pm, about 0.3 pm to about 0.7 pm, about 0.3 pm to about 0.8 pm , from about 0.3 to about 0.9 pm, from
Petition 870190048981, of 05/24/2019, p. 29/47
25/33 about 0.3 pm to about 10 pm, about 0.4 pm to about 0.5 pm, about 0.4 pm to about 0.6 pm, about 0, 4 pm to about 0.7 pm, from about 0.4 pm to about 0.8 pm, from about 0.4 pm to about 0.9 pm, from about 0.4 pm to about 10 pm, from about 0.5 pm to about 0.6 pm, from about 0.5 pm to about 0.7 pm, from about 0.5 pm to about 0.8 pm, from from 0.5 pm to about 0.9 pm, from about 0.5 pm to about 10 pm, from about 0.7 pm to about 0.8 pm, from about 0.7 pm to about from 0.9 pm and from about 0.7 pm to about 10 pm.
[0067] In other embodiments, the outer coating layer has pores with a pore density ranging from about 10,000 pores / mm ² to about 500,000 pores / mm ² . In another embodiment, the outer coating layer has pores with a pore density selected independently of the group consisting of a range of: from about 10,000 pores / mm ² to about 50,000 pores / mm ² , from about 10,000 pores / mm ² to about 100,000 pores / mm ² , from about 10,000 pores / mm ² to about 150,000 pores / mm ² , from about
10,000 pores / mm ² The fence in 250,000 pores / mm ² , from fence in 10,000 pores / mm ² The fence in 300,000 pores / mm ² , from fence in 10,000 pores / mm ² The fence in 350,000 pores / mm ² , from fence in 10,000 pores / mm ² The fence in 400,000 pores / mm ² , from fence in 10,000 pores / mm ² The fence in 450,000 pores / mm ² , from fence in 50,000 pores / mm ² The fence in 100,000 pores / mm ² , from fence in 50,000 pores / mm ² The fence in 150,000 pores / mm ² , from fence in 50,000 pores / mm ² The fence in 250,000 pores / mm ² , from fence in 50,000 pores / mm ² The fence in 300,000 pores / mm ² , from fence in 50,000 pores / mm ² The fence in 350,000 pores / mm ² , from fence in 50,000 pores / mm ² The fence in 400,000 pores / mm ² , from fence in 50,000 pores / mm ² The fence in 500,000 pores / mm ² , from fence in 150,000 pores / mm ² The fence in 150,000 pores / mm ² , from fence in
Petition 870190048981, of 05/24/2019, p. 30/47
26/33
150,000 pores / mm ² The fence in 250,000 pores / mm ² , from fence in 150,000 pores / mm ² The fence in 300,000 pores / mm ² , from fence in 150,000 pores / mm ² The fence in 350,000 pores / mm ² , from fence in 150,000 pores / mm ² The fence in 400,000 pores / mm ² , from fence in 150,000 pores / mm ² The fence in 450,000 pores / mm ² , from fence in 150,000 pores / mm ² The fence in 450,000 pores / mm ² , from fence in 200,000 pores / mm ² The fence in 250,000 pores / mm ² , from fence in 200,000 pores / mm ² The fence in 300,000 pores / mm ² , from fence in 200,000 pores / mm ² The fence in 350,000 pores / mm ² , from fence in 200,000 pores / mm ² The fence in 400,000 pores / mm ² , from fence in 200,000 pores / mm ² The fence in 450,000 pores / mm ² , from fence in 200,000 pores / mm ² The fence in 450,000 pores / mm ² , from fence in 250,000 pores / mm ² The fence in 300,000 pores / mm ² , from fence in 250,000 pores / mm ² The fence in 350,000 pores / mm ² , from fence in 250,000 pores / mm ² The fence in 400,000 pores / mm ² , from fence in 250,000 pores / mm ² The fence in 450,000 pores / mm ² , from fence in 250,000 pores / mm ² The fence in 450,000 pores / mm ² , from fence in 300,000 pores / mm ² The fence in 350,000 pores / mm ² , from fence in 300,000 pores / mm ² The fence in 400,000 pores / mm ² , from fence in 300,000 pores / mm ² The fence in 450,000 pores / mm ² , from fence in 300,000 pores / mm ² The fence in 450,000 pores / mm ² , from fence in 350,000 pores / mm ² The fence in 400,000 pores / mm ² , from fence in 350,000 pores / mm ² The fence in 450,000 pores / mm ² , from fence in 350,000 pores / mm ² The fence in 450,000 pores / mm ² , from fence in 400,000 pores / mm ² The fence in 450,000 pores / mm ² and fence in
450,000 pores / mm ² to about 500,000 pores / mm ² .
[0068] In some embodiments, the outer coating layer additionally comprises the elements or ions of Ti, O, Ca and P.
[0069] In another aspect, the present invention provides a method
Petition 870190048981, of 05/24/2019, p. 31/47
27/33 all to produce the various modalities of the poly (aryl ether-ketone) (PAEK) or thermoplastic surgical implant material, such as polyethylene described above.
[0070] In an exemplary embodiment, the method comprises the steps of: (A) treating the outer substrate surface by one or more processes that comprise (i) plasma activation; (ii) electron beam irradiation; (iii) ultraviolet light; and (iv) low energy Ar + ion beam irradiation; to thereby produce an activated substrate surface layer; (B) applying a plurality of layers over the activated substrate surface layer in which at least one layer comprises a layer of valve metal applied at a thickness of about 1 nm to about 20 pm; and (C) converting a surface of the valve metal layer through an anodizing process to thereby form the porous valve metal oxide layer that is about 2 pm to about 10 pm thick.
[0071] In some modalities of the method for producing the poly (aryl ether-ketone) (PAEK) or thermoplastic surgical implant material, such as polyethylene, the valve metal layer is applied through a process selected independently of the group consisting of: cathodic arc deposition, physical vapor deposition by magnetron ion bombardment, pulsed laser deposition, electron beam physical vapor deposition, high intensity magnetron ion bombardment, filtered vapor arc deposition, deposition and ionic implantation of metal plasma immersion, vacuum arc implantation of metal vapor and plasma-assisted chemical vapor deposition. In other embodiments of the method for producing the poly (aryl ether ketone) (PAEK) or thermoplastic surgical implant material, such as polyethylene, the valve metal layer is applied by immersion coating or coating
Petition 870190048981, of 05/24/2019, p. 32/47
28/33 per rotation in a solution containing Ti compounds.
[0072] In one embodiment, the anodizing process corresponds to a spark anodizing process carried out in an alkaline bath containing Ca and P ions in a porous valve metal oxide layer in which the valve metal oxide layer porous contains amorphous calcium phosphate. In another embodiment, the anodizing process corresponds to a color anodizing process carried out in an acidic medium. Such a color anodizing process could create a colored surface.
[0073] In one embodiment, the plurality of layers is applied substantially to cover the activated substrate surface layer.
[0074] In some embodiments, the method for producing the poly (aryl ether-ketone) (PAEK) or thermoplastic surgical implant material, such as polyethylene, further comprises the step of applying a buffer layer over the surface layer of substrate activated before the application of the valve metal layer. In further embodiments, the step of applying the buffer layer comprises applying a plurality of alternating layers of a first layer of material and a second layer of material.
[0075] In some embodiments, the method for producing the poly (aryl-ether-ketone) (PAEK) or thermoplastic surgical implant material, such as polyethylene, further comprises the step of applying an adhesive layer between the surface layer of activated substrate and the buffer layer.
[0076] In some other embodiments, the method for producing the surgical poly (aryl ether-ketone) implant (PAEK) further comprises the step of further understanding applying a conductive stainless metal to thereby form a conductive layer below the metal layer valve before the anodizing process.
Petition 870190048981, of 05/24/2019, p. 33/47
29/33 [0077] In another embodiment of the method for producing the poly (aryl-ether-ketone) (PAEK) or thermoplastic surgical implant material, such as polyethylene, further comprises an additional step of applying a coating of a salt of silver in the metal oxide layer of the porous valve. AgNOa is an exemplary silver salt for use in the method.
[0078] In an exemplary embodiment of the method for producing poly (aryl-ether-ketone) (PAEK) or thermoplastic surgical implant material, such as polyethylene, PAEK is selected independently from a group consisting of polyether ketone (PEK ), polyether ether ketone (PEEK), polyether ether ketone (PEKK), polyether ether ketone ketone (PEEKK) and polyether ether ketone ketone (PEKEKK).
[0079] Reference will now be made to examples of the various modalities discussed above illustrated in the attached drawings of Figures 1 to 6. Whenever possible, the same numerical references will be used by all drawings to refer to the same or similar parts.
[0080] With reference to Figure 1, an illustration of a schematic section through an exemplary embodiment of the surgical implant according to the invention is shown. The illustrated exemplary surgical implant includes a substrate 1, the substrate having an outer surface of the substrate 14 and a plurality of layers arranged on the outer surface of the substrate 14. In one embodiment, the plurality of layers includes a substrate surface layer activated 2, the activated substrate surface layer 2 being disposed on at least a portion of the outer surface of the substrate 14. In one embodiment, the plurality of layers includes a valve metal layer 3 disposed on at least a portion of the activated substrate surface layer 2. In
Petition 870190048981, of 05/24/2019, p. 34/47
In another embodiment, the plurality of layers includes a porous valve metal oxide layer 4, wherein the valve metal layer 3 is disposed between the activated substrate surface layer 2 and the metal oxide layer of porous valve 4.
[0081] Figure 2 illustrates a schematic section through another exemplary embodiment of the surgical implant according to the invention. In the illustrated embodiment, the surgical implant includes a substrate 1, the substrate having an outer surface and a plurality of layers arranged on the outer surface of the substrate. In one embodiment, the plurality of layers includes a layer containing silicone and / or carbon 5. In another embodiment, the layer containing silicone and / or carbon 5 is disposed between the activated substrate surface layer 2 and the metal layer. valve 3. In an additional embodiment, the plurality of layers includes a porous valve metal oxide layer 4 disposed over the valve metal layer 3.
[0082] Figures 3A and 3B each illustrate a schematic section through another exemplary embodiment of the surgical implant according to the invention. In the illustrated embodiment, the surgical implant includes a substrate 1, the substrate having an outer surface and a plurality of layers arranged on the outer surface of the substrate, wherein the plurality of layers includes a buffer layer 6. In one embodiment, the buffer layer is disposed on at least a portion of the surface of the activated substrate surface layer 2. In another embodiment, the buffer layer 6 is disposed between the activated substrate surface layer 2 and the valve metal layer 3 .
[0083] Figure 3C is a more detailed illustration of the exemplary embodiment of buffer layer 6 illustrated in Figure 3B. As illustrated, the exemplary modality of the tam layer
Petition 870190048981, of 05/24/2019, p. 35/47
The bread 6 comprises a plurality of alternating layers of a first material 7 and a second material 8. In one embodiment, the first material 7 and the second material 8 can be the same or different. In one embodiment, the first material 7 comprises a metal material. In another embodiment, the second material 8 comprises a nitride of a metal material. In one embodiment, the first material 7 comprises a metal material and the second material, the second material 8, comprises a nitride of the metal material. In one embodiment, the first material 7 comprises Ti. In one embodiment, the first material 7 comprises Cr. In yet another embodiment, the first material 7 comprises Ti and Cr. In another embodiment, the second material comprises TiN. In another embodiment, the second material comprises CrN. In another embodiment, the second material comprises TiC. In another embodiment, the second material comprises CrC. In yet another embodiment, the second material comprises an item or a combination of items TiN, CrN, TiC and CrC.
[0084] In some embodiments, the buffer layer 6 comprises a plurality of alternating layers of a first material comprising an oxide of a first metal material; a second material comprising a nitride of a second metal material, the second metal material being the same or different from the first metal material; and a third metal material, for example, Ta2Os / AIN / Au.
[0085] Figure 3D illustrates a schematic section through another exemplary embodiment of the surgical implant according to the invention. In the illustrated embodiment, the surgical implant includes a substrate 1, the substrate having an outer surface and a plurality of layers arranged on the outer surface of the substrate, wherein the plurality of layers includes a conductive layer 15.
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32/33
In one embodiment, the conductive layer 15 is disposed between the buffer layer 6 and the valve metal layer 3. In another embodiment, the conductive layer comprises a non-oxidizable conductive metal. In a specific embodiment, the conductive layer comprises a conductive non-oxidizable metal selected independently from the group consisting of Au, Pt and Pd. In some embodiments, the conductive layer has a thickness that is not greater than 1,000 nm. In another embodiment, the conductive layer has a thickness that is not greater than 100 nm.
[0086] Figure 4 illustrates an exemplary bone anchor produced from a PEEK-like polymer with osseointegrating surface treatment. The illustrated bone anchor has a treated surface anchor body 10, anchor insertion head 9, suture opening 12 and screw recess 11.
[0087] Figure 5 illustrates a schematic surgical implant for use after removing an intervertebral disc from a human spine where the outer surface 20 and the inner surface 21 have been activated.
[0088] Figure 6 illustrates a surgical implant 30 for reconstructing a skullcap according to the modalities described here.
[0089] Figure 6 illustrates a surgical implant 30 in relation to a human skull 35 for reconstruction of a skullcap according to the modalities described here.
[0090] It will be appreciated by those skilled in the art that changes could be made to the exemplary modalities shown and described above without leaving the broad inventive concept of them. It is understood, therefore, that this invention is not limited to the exemplary modalities shown and described, but is intended to cover modifications within the spirit and scope of the present invention.
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33/33 tion as defined by the claims. For example, specific features of the exemplary embodiments may or may not be part of the claimed invention and features of the disclosed embodiments may be combined. Unless specifically described here, the terms one, one, o and a are not limited to one element, but should instead be read with the meaning of at least one.
[0091] It is understood that at least some of the Figures and descriptions of the invention have been simplified to focus on elements that are relevant to a clear understanding of the invention, while eliminating, for purposes of clarity, other elements that those skilled in the art will understand that they can also comprise a portion of the invention. However, due to the fact that such elements are well known in the art and because they do not necessarily facilitate a better understanding of the invention, a description of such elements is not provided here.
[0092] Additionally, to the extent that the method does not depend on the particular order of steps presented here, the particular order of steps should not be considered a limitation of the claims. Claims directed to the method of the present invention should not be limited to the performance of the steps in the written order and one skilled in the art can immediately understand that the steps can be varied and still remain in the spirit and scope of the present invention.

权利要求:
Claims (13)
[1]
1. Surgical implant, comprising:
a substrate having an outer surface and a plurality of layers arranged on the outer surface of the substrate, wherein the substrate comprises a polymeric material, and characterized by the fact that the plurality of layers comprises:
(i) an activated substrate surface layer;
(ii) a valve metal layer; and (iii) a porous valve metal oxide layer, wherein the valve metal layer is disposed between the activated substrate layer and the porous valve metal oxide layer, and a buffer layer, said layer of buffer disposed between the activated substrate surface layer and the valve metal layer.
[2]
2. Surgical implant, according to claim 1, characterized by the fact that the polymeric material of the substrate is a thermoplastic polymeric material, preferably in which the polymeric material is a material of poly (aryl-ether-ketone) (PAEK).
[3]
3. Surgical implant according to claim 1 or 2, characterized in that the porous valve metal oxide layer includes an amorphous calcium phosphate composition.
[4]
Surgical implant according to any one of claims 1 to 3, characterized in that the buffer layer comprises a plurality of alternating layers of a first material and a second material, preferably in which the first material comprises a material of metal and the second material comprises a nitride and / or a carbide of the metal material.
[5]
5. Surgical implant according to any one of claims 1 to 4, characterized by the fact that the layer of size
Petition 870190048981, of 05/24/2019, p. 39/47
2/4 bread comprises a plurality of alternating layers of a first material, a second material and a third material, preferably where the first material is Ta2Os, the second material is AIN and the third material is Au.
[6]
6. Surgical implant according to any one of claims 1 to 5, characterized by the fact that the substrate comprises a reinforced poly (aryl-ether-ketone) (PAEK).
[7]
Surgical implant according to any one of claims 1 to 6, characterized in that the plurality of layers further comprises a polysilane layer disposed between the activated substrate surface layer and the valve metal layer.
[8]
Surgical implant according to any one of claims 1 to 7, characterized in that the plurality of layers still comprises a conductive layer formed from a conductive non-oxidizable metal, preferably in which the conductive non-oxidizable metal is selected regardless of the group consisting of Au, Pt, Pd and combinations thereof.
[9]
10. Coating for a polymeric surgical implant, characterized in that it comprises a plurality of layers as defined in any one of claims 1 to 8, wherein an outer coating layer has pores with sizes in the range of about 0.1 pm at about 10 pm; and a pore density in the range: about 10,000 pores / mm ² to about 500,000 pores / mm ² and the outer coating layer additionally comprises the elements or ions of Ti, O, Ca and P, preferably in which the polymeric surgical implant is a surgical implant of poly (arylether ketone) (PAEK).
[10]
11. Method for producing a polymeric surgical implant as defined in any one of claims 1 to 9, characterized by
Petition 870190048981, of 05/24/2019, p. 40/47
3/4 due to the fact that it comprises the following steps:
A) treat the outer substrate surface through one or more processes, comprising:
(i) plasma activation;
(ii) electron beam irradiation;
(iii) ultraviolet light; and (iv) low energy Ar + ion beam irradiation;
to thereby produce an activated substrate surface layer;
B) apply a layer of buffer over the activated substrate surface layer;
C) applying a plurality of layers on the buffer layer, wherein at least one layer comprises a layer of valve metal applied at a thickness of about 1 nm to about 20 pm; and
D) converting a surface of the valve metal layer through an anodizing process to thereby form a porous valve metal oxide layer that is about 2 pm to about 10 pm thick.
11. Method, according to claim 10, characterized by the fact that the anodizing process is a spark anodizing process carried out in an alkaline bath containing Ca and P ions in a porous valve metal oxide layer, in which said porous valve metal oxide layer contains amorphous calcium phosphate.
[11]
Method according to claim 10 or 11, characterized in that applying the buffer layer comprises applying a plurality of alternating layers of a first layer of material and a second layer of material.
[12]
13. Method according to any one of the claims
Petition 870190048981, of 05/24/2019, p. 41/47
4/4 sections 10 to 12, characterized by the fact that it still comprises applying an adhesive layer between the activated substrate surface layer and the buffer layer.
[13]
Method according to any one of claims 10 to 13, characterized in that it further comprises applying a non-oxidizable conductive metal to form a conductive layer below the valve metal layer before the anodizing process.

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WO2012167063A1|2012-12-06|

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法律状态:
2018-04-03| B06F| Objections, documents and/or translations needed after an examination request according art. 34 industrial property law|

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2019-02-26| B07A| Technical examination (opinion): publication of technical examination (opinion)|

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2019-08-13| B09A| Decision: intention to grant|

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2019-10-22| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 01/06/2012, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

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申请号 | 申请日 | 专利标题

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US201161492985P| true| 2011-06-03|2011-06-03|

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PCT/US2012/040437|WO2012167063A1|2011-06-03|2012-06-01|Surgical implant|

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