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    • 专利摘要:
    summary patent of invention "coating for a substrate of titanium alloy". the present invention relates, at least in part, to a surgical implant and a method for manufacturing the surgical implant. in one embodiment, the surgical implant comprises a metallic substrate; a tantalum interlayer disposed adjacent to the metallic substrate and comprising? -tantalum and amorphous tantalum; at least one layer of ctd disposed adjacent to the tantalum interlayer; the amorphous tantalum having a phase gradient that increases from the side of the metallic substrate to the side of ctd; the ctd layer having a hardness value and an elastic modulus value; and the hardness value has a gradient that increases in the opposite direction to the tantalum side; and the elastic modulus value has a gradient from the tantalum side.
    公开号:BR112015021860B1
    申请号:R112015021860
    申请日:2014-02-27
    公开日:2020-06-09
    发明作者:Thorwarth Götz；Thorwarth Kerstin；Hauert Roland
    申请人:Depuy Synthes Products Inc；
    IPC主号:
    专利说明:

    Descriptive Report of the Invention Patent for SURGICAL IMPLANT AND ITS MANUFACTURING METHOD.
    BACKGROUND OF THE INVENTION
    [001] Due to its unique combination of hardness, wear resistance, low deposition temperature (below 150 ° C), biocompatibility and friction characteristics (friction coefficient less than 0.1), the CTD is ideally suited for applications in a variety of fields, including tribology, corrosion protection and medical devices. However, in CTD applications such as hard coatings, the high residual stresses associated with their deposition give rise to poor adhesion strength, fragility fracture and delamination under high local loading. With reference to Figure 1A, for example, a secondary electron microscopy (MES) image of a cross-section of the unclassified CTD 106 coating deposited on a titanium-aluminum-niobium substrate (Ti6Al7Nb) 102 is shown. As shown in Figure 1, the unclassified CTD coating 106 showed a low tolerance for deformations under it (eggshell effect), and due to its fragility and low elongation at breakage it developed cracks 108. Layer 107 is a platinum coating used to improve the conductivity around the unclassified CTD coating 106 deposited on an aluminum-niobium titanium substrate (Ti6Al7Nb) 102. Figure 1B illustrates a contrast-adjusted MES image shown in Figure 1A, which better shows the cracks in the CTD coating . Cracks 108 compromise the integrity of the CTD coating 106 and lead to failure of the Ti6Al7Nb substrate coated with CTD 102 (for example, delaminated prosthesis) through the generation of debris caused by intense wear. Consequently, there is a need for coated and more robust metal-based prostheses that are capable of exi
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    2/32 bir high tolerance for elastic and plastic deformations and, therefore, prevent the development of cracks that compromise the integrity of the coating and the coated prosthesis.
    BRIEF SUMMARY OF THE INVENTION
    [002] In one aspect, the present invention provides a surgical implant. In one embodiment, the surgical implant comprises a metallic substrate. In one embodiment, there is a tantalum interlayer disposed in a position adjacent to the metallic substrate. In one embodiment, the tantalum interlayer comprises α-tantalum and amorphous tantalum. In one embodiment, the surgical implant includes at least one layer of CTD disposed adjacent to the tantalum interlayer. In one embodiment, the tantalum interlayer has a phase gradient between the side of the metallic substrate and the side of the CTD. In one embodiment, the tantalum interlayer has a phase gradient from β-tantalum to α-tantalum between the side of the metallic substrate and the side of the CTD. In one embodiment, the amorphous tantalum of the tantalum interlayer has a gradient of crystallinity increasing from the side of the metallic substrate to the side of the CTD. In one embodiment, the CTD layer has a hardness value and an elastic modulus value. In one embodiment, the hardness value of the CTD layer has a gradient increasing in the opposite direction from the tantalum side. In one embodiment, the elastic modulus value of the CTD layer has a gradient that increases in the opposite direction from the tantalum side.
    [003] In some embodiments, the metallic substrate of the surgical implant independently includes titanium, a titanium-based alloy, a cobalt-based alloy or steel. In some embodiments, the tantalum interlayer of the surgical implant has a thickness in the range of 1 nm to 2 pm.
    [004] In some embodiments, the tantalum interlayer additionally comprises, independently, an element or with
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    3/32 rank, with the element or compound promoting the growth of α-tantalum. In some of these modalities, the element independently includes titanium, niobium, tungsten and combinations thereof. In other of these modalities, the compound independently includes titanium compound, niobium compound, tungsten compound or combinations thereof.
    [005] In some embodiments, the tantalum interlayer of the surgical implant additionally comprises nanoparticles of tantalum compound. In some embodiments, the tantalum interlayer of the surgical implant is a tantalum-carbide and tantalum nanocomposite. In some embodiments, the surgical implant has a layer of CTD with a gradient of hardness value that increases from 12 GPa to 22 GPa. In some embodiments, the surgical implant has a layer of CTD with a gradient of elastic modulus value that increases from 120 GPa to 220 GPa. In some embodiments, the surgical implant has at least one layer of CTD that comprises a plurality of alternating sublayers. In one embodiment, the plurality of alternating sublayers comprises a CTD sublayer and a doped CTD sublayer. In one embodiment, the doped CTD sublayer is doped with a metal. In one embodiment, the metal doped CTD sublayer is titanium doped.
    [006] In another aspect, the present invention provides a method for making an exemplary surgical implant according to the present invention. In one embodiment, the method comprises inserting a metallic substrate into a vacuum system. In one embodiment, the method includes cleaning the metal substrate by bombarding with Ar + to an RF autopolarization in the range of about -200 volts to about -2,000 volts. In one embodiment, the metal substrate is cleaned by bombardment with Ar + at an RF autopolarization of -600 volts.
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    [007] In one embodiment, the method includes depositing a tantalum interlayer while applying an electrical polarization to the substrate. In one embodiment, the polarization is an RF self-polarization. In one embodiment, the applied RF autopolarization is in the range of -50 volts to -600 volts. In one embodiment, the applied RF self-polarization is changed in predetermined increments. In one embodiment, the applied RF autopolarization is changed in gradual increments in the range of an increase of 5 volts to an increase of 50 volts.
    [008] In one embodiment, the method includes depositing a layer of CTD. In one embodiment, the CTD layer is deposited by introducing a hydrocarbon in a second RF autopolarization specified to the substrate. In one embodiment, the CTD layer is deposited by introducing a hydrocarbon into the second RF autopolarization which is changed from -50 volts to - 600 volts in a gradual increase. In one embodiment, the second applied RF autopolarization is changed by a gradual increase in the range from a 5 volts increase to a 50 volts increase. In one embodiment, the CTD layer is deposited by introducing a hydrocarbon that has a molecular weight in the range of 92 g / mol to 120 g / mol. In one embodiment, the CTD layer is deposited by the introduction of a hydrocarbon independently selected from the group consisting of toluene, xylene, trimethyl benzene, and combinations thereof.
    [009] In some embodiments, the method for making a surgical implant according to the present invention includes the step of introducing an acetylene atmosphere in a third RF autopolarization to the substrate. In one embodiment, the third applied RF autopolarization is changed from -50 volts to - 600 volts in a second gradual increment. In one modality, the second incre
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    5/32 gradual growth is in the range of a 5 volts increase to a 50 volts increase.
    [0010] In another embodiment, a method for making a surgical implant, in accordance with the present invention, includes the steps of:
    (a) inserting a metallic substrate into a vacuum system; (b) clean the metallic substrate by bombarding it with Ar - to an RF autopolarization to the substrate in the range of about -200 volts to about -2,000 volts, preferably to an RF autopolarization of -600 volts; (c) depositing a tantalum interlayer by applying an electrical polarization, including an RF autopolarization, to the substrate during tantalum deposition, said RF autopolarization in the range of -50 volts to -600 volts; (d) depositing a layer of CTD by introducing an acetylene atmosphere to an RF autopolarization, with the RF autopolarization being changed from -50 volts to - 600 volts in a gradual increment for a first period of time; (e) after the first period of time, introduce a source of organotitanium into the acetylene atmosphere for a second period of time; and (f) repeat steps (d) and (e) up to 100 repetitions. In one mode, the gradual increase is in the range of an increase of 5 volts to an increase of 50 volts.
    BRIEF DESCRIPTION OF THE VARIOUS VIEWS OF THE DRAWINGS
    [0011] The previous summary, as well as the following detailed description of the modalities of the surgical implant and the method of its manufacture, will be better understood when read together with the attached drawings of an exemplary modality. It should be understood, however, that the invention is not limited to the precise provisions and instrumentalities shown.
    [0012] In the drawings:
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    [0013] Figure 1A is a scanning electron microscopy (MES) image of a lubricant coating of CTD and unclassified tantalum deposited on TiAl6Nb7;
    [0014] Figure 1B is a scanning electron microscopy (MES) image of a lubricant coating of CTD and unclassified tantalum deposited on TiAl6Nb7;
    [0015] figure 2 is a schematic cross-sectional view of a surgical implant coated in accordance with an exemplary embodiment of the present invention;
    [0016] figure 3 is a schematic cross-sectional view of a classified CTD lubricant coating deposited on a surgical implant according to an exemplary embodiment of the present invention;
    [0017] figure 4 is a schematic cross-sectional view of a surgical implant that has a coating comprising alternating layers of CTD and metal doped CTD;
    [0018] figure 5 is a schematic cross-sectional view of a surgical implant according to an exemplary embodiment of the present invention having the tantalum interlayer comprising nanocomposite tantalum carbide and tantalum dispersed in tantalum;
    [0019] figure 6A is an image showing a top perspective view of a CTD cervical disc prosthesis coated according to an exemplary embodiment of the present invention;
    [0020] figure 6B is another image showing a top perspective view of a cervical disc prosthesis shown in figure 6A.
    DETAILED DESCRIPTION OF THE INVENTION
    [0021] Referring to the drawings in detail, in which similar reference numbers indicate similar elements throughout the
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    7/32 document, a schematic cross-sectional view of a coated surgical implant generally designated with reference number 100 is shown in figures 2 to 6, according to the exemplary embodiments of the present invention.
    [0022] The present invention relates, in general, to prosthetic orthopedic implants, particularly to articular components such as those for use with replacements of knees, hips, shoulders, elbows, toes, fingers, wrists, ankles and vertebral disc. More specifically, the present invention relates to a method for making a non-modular prosthetic hinge component having a metallic substrate, a tantalum interlayer and a CTD layer.
    [0023] In one aspect, the present invention provides a surgical implant that has a metallic substrate coated with at least one layer comprising CTD. As shown in figure 2, in one embodiment, the surgical implant 100 comprises a metallic substrate 102 that has a coating that includes a tantalum interlayer 104 disposed adjacent to the metallic substrate 102. In one embodiment, the surgical implant 100 includes the substrate metallic 100 and the tantalum interlayer 104 comprising α-tantalum. In one embodiment, surgical implant 100 includes metallic substrate 102 and tantalum interlayer 104 comprising amorphous tantalum. In one embodiment, surgical implant 100 includes metallic substrate 102 and tantalum interlayer 104 comprising α-tantalum and amorphous tantalum. In one embodiment, the surgical implant 100 includes the metallic substrate 102 and at least one layer of CTD 106 disposed adjacent to the tantalum interlayer 104. In one embodiment, the tantalum interlayer has a phase gradient between the side of the metallic substrate and the CTD side. In one embodiment, surgical implant 100 includes metal substrate 102 and tantalum interlayer 104 comprising tantalum
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    Amorphous 8/32 having a crystallinity gradient. In one embodiment, the surgical implant 100 includes the metallic substrate 102 and the tantalum interlayer 104 comprising amorphous tantalum having a crystallinity gradient that increases from the side of the metallic substrate 102 to the side of the CTD layer 106. In one embodiment, the implant Surgical 100 includes tantalum interlayer 104 having a phase gradient from βtantal to α-tantalum.
    [0024] In one embodiment, the surgical implant 100 includes the metallic substrate 102, the tantalum interlayer 104 and the CTD layer 106 having a hardness value and an elastic modulus value. In one embodiment, the surgical implant 100 includes the metallic substrate 102, the tantalum interlayer 104 and the CTD layer 106 having a hardness value and an elastic modulus value, the hardness value having a gradient that increases in the direction contrary to the side of the tantalum interlayer 104. In one embodiment, the surgical implant 100 includes the metallic substrate 102, the tantalum interlayer 104 and the CTD layer 106 having a hardness value and an elastic modulus value, the value being elastic modulus has a gradient that increases in the opposite direction from the side of the tantalum interlayer 104.
    [0025] In one embodiment, surgical implant 100 includes metallic substrate 102; the tantalum interlayer 104 disposed adjacent to the metal substrate 100 and comprising α-tantalum and amorphous tantalum; at least one layer of CTD 106 disposed adjacent to the tantalum interlayer 104. In one embodiment, surgical implant 100 includes metallic substrate 102; the tantalum interlayer 104 disposed adjacent to the metal substrate 102 and comprising α-tantalum and amorphous tantalum; and at least one layer of CTD 106 disposed adjacent to the tantalum interlayer 104, the amorphous tantalum having a concentration gradient that increases from
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    9/32 side of metallic substrate 100 to side of CTD layer 106. In one embodiment, surgical implant 100 includes metallic substrate 102; the tantalum interlayer 104 disposed adjacent to the metal substrate 102 and comprising α-tantalum and amorphous tantalum; and at least one layer of CTD 106 disposed adjacent to the tantalum interlayer 104, the layer of CTD 106 having a hardness value and an elastic modulus value; and the hardness value has a gradient that increases in the opposite direction from the side of the tantalum interlayer 104. In one embodiment, the surgical implant 100 includes the metallic substrate 102; the tantalum interlayer 104 disposed adjacent to the metal substrate 102 and comprising α-tantalum and amorphous tantalum; and at least one layer of CTD 106 disposed adjacent to the tantalum interlayer 104, the elastic modulus value having a gradient that increases in the opposite direction from the side of the tantalum interlayer 104.
    [0026] The metallic substrate 102 of surgical implant 100 according to the exemplary embodiments of the present invention can comprise any suitable metal, metallic alloy or a combination of both. In general, the metal substrate 102 can include any metals and metal alloys that have any advantageous combinations of properties, thermal and mechanical characteristics, including little heating and high levels of strength resistance during repetitions of alternating loads. In one embodiment, the metal substrate 102 comprises a titanium based alloy. In one embodiment, the metallic substrate 102 comprises a titanium-based alloy selected from the group consisting of TiAl6V4, T iAl6Nb7 and a combination thereof. In one embodiment, the metal substrate 102 comprises a cobalt-chromium alloy (CoCrMo). In one embodiment, the metal substrate 102 comprises steel. In one embodiment, the metallic substrate 102 comprises at least
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    10/32 minus one element selected from the group consisting of titanium, nickel, iron, cobalt, niobium, zinc, tungsten, molybdenum and tantalum. In one embodiment, the metal substrate 102 comprises a metal alloy in which at least one of the elements is selected from the group consisting of titanium, nickel, iron, cobalt, niobium, zinc, tungsten, molybdenum and tantalum. In one embodiment, the metallic substrate 102 comprises titanium and / or a titanium alloy selected from the group consisting of commercially unalloyed pure titanium (CP), TiAl6V4, TiAl6Nb7 or nickel-titanium (superelastic NiTi or NiTi with shape memory).
    [0027] In some exemplary embodiments, the metallic substrate 102 of the surgical implant 100 according to the present invention preferably comprises a titanium alloy. The benefits of using titanium alloys as prosthetic materials include high capacity to withstand mechanical load, high resistance to fatigue, elasticity, high chemical stability, enhanced compatibility with magnetic resonance imaging (MRI) and computed tomography (CT) and superior biocompatibility . In addition, many different types of surgical implants, including bone plates, pins, artificial knee and hip joints, and intervertebral disc prostheses can be advantageously manufactured from titanium-based alloys. However, titanium-based alloys exhibit inappropriate wear behavior at the joint in addition to difficult finishing capabilities, requiring a wear-resistant coating.
    [0028] With respect to figures 2 and 3, the tantalum interlayer
    104 according to an exemplary embodiment of the present invention is preferably disposed adjacent to the metallic substrate 102. In one embodiment, the tantalum interlayer 104 comprises crystalline tantalum. In one embodiment, the interlayer of
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    11/32 tantalum 104 comprises crystalline tantalum and amorphous tantalum. In one embodiment, the tantalum interlayer 104 comprises α-tantalum. In one embodiment, the tantalum interlayer 104 comprises β-tantalum and α-tantalum. In one embodiment, the tantalum interlayer 104 comprises β-tantalum and amorphous tantalum. In one embodiment, the tantalum interlayer 104 comprises β-tantalum, α-tantalum and amorphous tantalum.
    [0029] With reference to figure 3, in one embodiment, the tantalum interlayer 104 comprises nanocomposite tantalum with a tantalum compound, such as a carbide, such as an sublayer 104B. In one embodiment, sublayer 104B comprises an element or compound to promote the growth of α-tantalum. In this modality, the element independently includes titanium, niobium or tungsten. In another embodiment, the compound independently includes a titanium compound, a niobium compound or a tungsten compound. In one embodiment, the tantalum interlayer 104 comprises tantalum as a sublayer 104A and nanocomposite tantalum and a tantalum compound, for example, tantalum carbide, as a sublayer 104. As shown in figure 5, in one embodiment, the tantalum interlayer 104 is entirely composed of nanocomposite tantalum and a tantalum compound (see 104C in figure 5). In one embodiment, the tantalum interlayer 104 comprises an α-tantalum nanocomposite and a tantalum compound. In one embodiment, the tantalum interlayer 104 comprises at least one layer of tantalum, β-tantalum, α-tantalum and mixtures thereof, and at least one layer of nanocomposite tantalum and tantalum compound.
    [0030] With respect to figures 3 and 5, in one embodiment, the tantalum interlayer 104 comprises nanoparticles of tantalum compound, such as tantalum carbide. In one embodiment, the inter-bed
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    12/32 of tantalum 104 comprises nanoparticles of tantalum and tantalum compound, such as β-tantalum, α-tantalum and mixtures thereof. In one embodiment, the tantalum interlayer 104 comprises β-tantalum, amorphous tantalum and nanoparticles of tantalum compound. In one embodiment, the tantalum interlayer 104 comprises α-tantalum, amorphous tantalum and tantalum compound nanoparticles. In one embodiment, the tantalum interlayer 104 comprises β-tantalum, amorphous tantalum and nanoparticles of tantalum compound dispersed in the tantalum interlayer 104. In one embodiment, the tantalum interlayer 104 comprises α-tantalum, amorphous tantalum and nanoparticles of compound tantalum dispersed in the tantalum interlayer 104. In one embodiment, the tantalum interlayer 104 comprises β-tantalum, α-tantalum, amorphous tantalum and nanoparticles of tantalum compound dispersed in the tantalum interlayer 104.
    [0031] With respect to figures 2 to 5, in one embodiment, the tantalum interlayer 104 comprises about 50 to about 100 in atomic percentage (or at.%) Of α-tantalum. In one embodiment, the tantalum interlayer 104 comprises about 50 to about 100 percent atomic (or at.%) Amorphous tantalum. In one embodiment, the tantalum interlayer 104 comprises from about 70 to about 99 in atomic percentage (or at.%) Nanoparticles of tantalum compound. In one embodiment, the tantalum interlayer 104 comprises from about 10 to about 30 in atomic percentage (or at.%) Of α-tantalum; from about 10 to about 30 in atomic percentage (or at.%) of amorphous tantalum; and from about 50 to about 99 in atomic percentage (or at.%) of tantalum compound nanoparticles.
    [0032] In some embodiments, the tantalum interlayer 104 comprises nanocomposite tantalum including a tantalum carbide composition. In one embodiment, the tantalum interlayer
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    13/32
    104 comprises nanocomposite tantalum having from about 5 to about 50 in atomic percentage (or at.%) Of tantalum and from about 50 to about 99 in atomic percentage (or at.%) Of tantalum carbide.
    [0033] With respect to figures 2 to 5, in some embodiments, the tantalum interlayer 104 comprises a phase gradient that extends at least partially through it. In one embodiment, the tantalum interlayer 104 comprises a tantalum phase gradient. In one embodiment, the tantalum interlayer 104 comprises a phase gradient that includes α-tantalum. In one embodiment, the tantalum interlayer 104 comprises a phase gradient that includes amorphous tantalum. In some embodiments, the tantalum interlayer 104 comprises a phase gradient that includes α tantalum, the phase gradient extending from the side of the metallic substrate 102 of the surgical implant 100 to the side of the CTD layer 106 of the surgical implant 100 In some embodiments, the tantalum interlayer 104 comprises a phase gradient that includes amorphous tantalum, the phase gradient extending from the side of the metallic substrate 102 of the surgical implant 100 to the side of the CTD layer 106 of the surgical implant. 100. In some embodiments, the tantalum interlayer 104 comprises a gradient of crystallinity that extends at least partially through it. In one embodiment, the tantalum interlayer 104 comprises a gradient of tantalum crystallinity. In one embodiment, the tantalum interlayer 104 comprises a gradient of crystallinity that includes α-tantalum. In one embodiment, the tantalum interlayer 104 comprises a crystallinity gradient from β-tantalum to α-tantalum. In some embodiments, the tantalum interlayer 104 comprises a crystallinity gradient that includes α-tantalum, the crystallinity gradient extending from the side of the
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    14/32 metallic substrate 102 from surgical implant 100 to the side of CTD layer 106 of surgical implant 100.
    [0034] With respect to figures 2 to 5, in some embodiments, the tantalum interlayer 104 has a thickness in the range of about 1 nm to about 2 pm (or 2000 nm). In one embodiment, the tantalum interlayer 104 has a thickness that has a value in a range selected from the group consisting of from about 1 nm to about 10 nm, from about 1 nm to about 20 nm; from about 1 nm to about 40 nm, from about 1 nm to about 60 nm; from about 1 nm to about 100 nm; from about 10 nm to about 100 nm, from about 10 nm to about 300 nm, from about 10 nm to about 500 nm, from about 10 nm to about 700 nm, from about 10 nm to about 1000 nm, from about 10 nm to about 1200 nm, from about 10 nm to about 1400 nm, from about 10 nm to about 1600 nm, from about 10 nm to about 1800 nm, from about 10 nm to about 2000 nm; from about 20 nm to about 100 nm, from about 20 nm to about 300 nm, from about 20 nm to about 500 nm, from about 20 nm to about 700 nm, from about 20 nm to about 1000 nm, from about 20 nm to about 1200 nm, from about 20 nm to about 1400 nm, from about 20 nm to about 1600 nm, from about 20 nm to about 1800 nm, from about 20 nm to about 2000 nm; from about 50 nm to about 100 nm, from about 50 nm to about 300 nm, from about 50 nm to about 500 nm, from about 50 nm to about 700 nm, from about 50 nm to about 1000 nm, about 50 nm to about 1200 nm, about 50 nm to about 1400 nm, about 50 nm to about 1600 nm, about 50 nm to about 1800 nm, from about 50 nm to about 2000 nm; from about 100 nm to about 200 nm, from about 100 nm to about 300 nm, from about 100 nm to about 400 nm, from about 100 nm to about 500 nm, from about 100 nm to about 600 nm, about 100 nm to about 700 nm, about 100
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    15/32 nm to about 800 nm, from about 100 nm to about 900 nm, from about 100 nm to about 1000 nm, from about 100 nm to about 1100 nm, from about 100 nm to about 1200 nm, from about 100 nm to about 1300 nm, from about 100 nm to about 1400 nm, from about 100 nm to about 1500 nm, from about 100 nm to about 1600 nm, about from 100 nm to about 1700 nm, from about 100 nm to about 1800 nm, from about 100 nm to about 1900 nm, from about 200 nm to about 300 nm, from about 300 nm to about 400 nm, from about 400 nm to about 500 nm, from about 500 nm to about 600 nm, from about 200 nm to about 400 nm, from about 300 nm to about 500 nm, from about 400 nm to about 600 nm, from about 500 nm to about 700 nm, from about 200 nm to about 500 nm, from about 300 nm to about 600 nm, from about 400 nm to about 700 nm, from about 500 nm to about 800 nm, from about 200 nm to about 600 nm, from about 300 nm to about 700 nm, from 400 nm to about 800 nm, from about 500 nm to about 900 nm, from about 200 nm to about 700 nm, from about 300 nm to about 800 nm, from about 400 nm to about 900 nm, from about 500 nm to about 1000 nm, from about 200 nm to about 800 nm, from about 300 nm to about 900 nm, from about 400 nm to about 1000 nm, from about 500 nm to about 1100 nm, from about 200 nm to about 900 nm, from about 300 nm to about 1000 nm, from about 400 nm to about 1100 nm, from about 500 nm to about 1200 nm , from about 200 nm to about 1000 nm, from about 300 nm to about 1100 nm, from about 400 nm to about 1200 nm, from about 500 nm to about 1300 nm, from about 200 nm at about 1100 nm, from about 300 nm to about 1200 nm, from about 400 nm to about 1300 nm, from about 500 nm to about 1400 nm, from about 200 nm to about 1200 nm, from about 300 nm to about 1300 nm, from about 400 nm to about 1400 nm, from about 500
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    16/32 nm to about 1500 nm, from about 200 nm to about 1300 nm, from about 300 nm to about 1400 nm, from about 400 nm to about 1500 nm, from about 500 nm to about 1600 nm, from about 200 nm to about 1400 nm, from about 300 nm to about 1500 nm, from about 400 nm to about 1600 nm, from about 500 nm to about
    1700 nm, from about 200 nm to about 1500 nm, from about 300 nm to about 1600 nm, from about 400 nm to about 1700 nm, from about 500 nm to about 1800 nm, from about 200 nm the fence
    1600 nm, from about 300 nm to about 1700 nm, from about 400 nm to about 1800 nm, from about 500 nm to about 1900 nm, from about 200 nm to about 1700 nm, from about 300 nm the fence
    1800 nm, from about 400 nm to about 1900 nm, from about 500 nm to about 2000 nm, from about 200 nm to about 1800 nm, from about 300 nm to about 1900 nm, from about 400 nm the fence
    2000 nm, from about 200 nm to about 1900 nm, from about 300 nm to about 2000 nm, from about 200 nm to about 2000 nm, from about 600 nm to about 700 nm, from about 600 nm the fence
    800 nm, from about 700 nm to about 800 nm, from about 600 nm to about 900 nm, from about 700 nm to about 900 nm, from about 800 nm to about 900 nm, from about 600 nm to about 1000 nm, from about 700 nm to about 1000 nm, from about 800 nm to about 1000 nm, from about 900 nm to about 1000 nm, from about 1000 nm to about 1100 nm, from about 1100 nm to about 1200 nm, from about 600 nm to about 1100 nm, from about 700 nm to about 1100 nm, from about 800 nm to about 1100 nm, from about 900 nm to about 1100 nm, from about 1000 nm to about 1200 nm, from about 1100 nm to about 1300 nm, from about 600 nm to about 1200 nm, from about 700 nm to about 1200 nm , from about 800 nm to about 1200 nm, from about 900 nm to about 1200 nm, from about 1000 nm to about 1300 nm, from about 1100
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    17/32 nm at about 1400 nm, from about 600 nm to about 1300 nm, from about 700 nm to about 1300 nm, from about 800 nm to about 1300 nm, from about 900 nm to about from 1300 nm, from about 1000 nm to about 1400 nm, from about 1100 nm to about 1500 nm, from about 600 nm to about 1400 nm, from about 700 nm to about 1400 nm, from about from 800 nm to about 1400 nm, from about 900 nm to about 1400 nm, from about 1000 nm to about 1500 nm, from about 1100 nm to about 1600 nm, from about 600 nm to about 1500 nm, from about 700 nm to about 1500 nm, from about 800 nm to about 1500 nm, from about 900 nm to about 1500 nm, from about 1000 nm to about 1600 nm, from about 1100 nm to about 1700 nm, from about 600 nm to about 1600 nm, from about 700 nm to about 1600 nm, from about 800 nm to about 1600 nm, from about 900 nm to about 1600 nm, from about 1000 nm to about
    1700 nm, from about 1100 nm to about 1800 nm, from about 600 nm to about 1700 nm, from about 700 nm to about 1700 nm, from about 800 nm to about 1700 nm, from about 900 nm surrounding
    1700 nm, from about 1000 nm to about 1800 nm, from about 1100 nm to about 1900 nm, from about 600 nm to about 1800 nm, from about 700 nm to about 1800 nm, from about 800 nm to about 1800 nm, from about 900 nm to about 1800 nm, from about 1000 nm to about 1900 nm, from about 1100 nm to about 2000 nm, from about 600 nm to about 1900 nm, from about 700 nm to about 1900 nm, from about 800 nm to about 1900 nm, from about 900 nm to about 1900 nm, from about 1000 nm to about 2000 nm, from about nm at about nm, from about 600 nm to about 2000 nm, from about 700 nm to about 2000 nm, from about 800 nm to about 2000 nm, and from about 900 nm to about 2000 nm.
    [0035] Elemental carbon exists in numerous short fibers called allotropes. The most common carbon allotrope is graphite
    Petition 870190085134, of 30/08/2019, p. 22/45
    18/32 (α-graphite). Diamond is the second allotrope of carbon, but it is much less common than graphite. Most graphite is α-graphite and has a layered structure in which each carbon atom is directly linked to three other carbon atoms. The bond between the carbon atoms in each layered structure is described as being coordinated three times with planar trigonal coordination geometry reflecting sp 2 hybridization of atomic orbitals. In contrast, the diamond has a structure in which each carbon is coordinated four times with tetrahedral symmetry, reflecting sp 3 hybridization of atomic orbitals. CTD is amorphous carbon with a high fraction of diamond-like bonds (sp 3 ) between carbon atoms. Supposedly, CTD films comprise a combination of sp 3 sites coordinated four times, as in diamond, and sp 2 sites coordinated three times, as in graphite.
    [0036] With respect to figures 2 to 5, in one embodiment, the surgical implant 100 includes at least one layer of CTD 106 disposed adjacent to the tantalum interlayer 104. In one embodiment, the layer of CTD 106 can be synthesized by any suitable techniques including reactive sputtering with magnetron, by physical vapor deposition (PVD), chemical vapor deposition (CVD), plasma chemical vapor deposition (PCVD), plasma intensified chemical vapor deposition (PECVD), arc of filtered cathodic vacuum, laser ablation, plasma beam source and dense plasma focusing (DPF). In one embodiment, different deposition methods are used to manufacture the CTD 106 layer with preferred tribological properties. In one embodiment, the CTD layer 106 comprises amorphous carbon or amorphous diamond (i-C, amorphous tetrahedral carbon ta-C). In one embodiment, the CTD layer 106 comprises hydrogenated amorphous carbon (a-C: H). In one embodiment, the CTD layer 106 additionally includes a material comprising
    Petition 870190085134, of 30/08/2019, p. 23/45
    19/32 an element in addition to carbon. In one embodiment, the CTD layer 106 additionally includes a material comprising an element selected from the group consisting of silicon (Si), nitrogen (N), metal (Me), fluorine (F). Typically, a CTD film doped with Si, N, metal atoms and F would be designated a-Si-C: H, a-C: H-N, a-Me-C: H and a-C: H-F, respectively.
    [0037] In some embodiments, the CTD layer 106 has a hardness value and an elastic modulus value. With respect to figures 2, 3 and 5, in one embodiment, the CTD layer 106 has a hardness value that has a gradient that extends at least partially through the CTD layer 106. In one embodiment, the CTD layer 106 has a hardness value that has a gradient that increases in the opposite direction from the side of the tantalum interlayer 104. In one embodiment, the CTD layer 106 has an elastic modulus value that has a gradient that increases in the opposite direction from the side of the interlayer tantalum 104. In one embodiment, the CTD layer 106 has a hardness value gradient that increases from about 12 GPa to about 22 GPa. In one embodiment, the CTD layer 106 has an elastic modulus value gradient. which increases: from about 120 GPa to about 220 GPa; from about 100 GPa to about 200 GPa; from about 50 GPa to about 100 GPa.
    [0038] With reference to figure 4, in some embodiments, at least one layer of CTD 106 comprises a plurality of alternating sublayers comprising a sublayer of CTD
    106A and a metal doped CTD sublayer 106B. In one embodiment, the CTD layer 106 comprises a plurality of alternating sublayers comprising a CTD sublayer
    106A and a metal doped CTD sublayer 106B, with the metal doped CTD sublayer 106B being doped with titanium. In one embodiment, at least one layer of CTD 106 has two
    Petition 870190085134, of 30/08/2019, p. 24/45
    20/32 graduated graduated through at least a portion of it. In one embodiment, at least one layer of CTD 106 has tantalum with graduated hardness on the side of interlayer 104 (see 106C in figure 4).
    [0039] Any specific examples of surgical implants described herein should not be considered as limiting the scope of the surgical implants of the present invention, but instead, as an example of their preferred modalities. Surgical implants that are contemplated in the present invention include prostheses that are designed to replace damaged or missing body parts. In some embodiments, surgical implant 100 is placed permanently or is removed from the patient's body when it is no longer needed. In some modalities, surgical implant 100 is selected from the group consisting of hip implants, accesses for chemotherapy and screws. In one embodiment, surgical implant 100 is an articulated bone prosthesis. In one embodiment, surgical implant 100 is selected from the group consisting of a total hip joint prosthesis and a total knee joint prosthesis. In one embodiment, surgical implant 100 is a metal-metal joint prosthesis.
    [0040] Surgical implant 100 advantageously reduces wear debris and the toxicity of wear products on articulated joint prostheses, including metal-metal-type (MOM) joint prostheses, in which both articulated surfaces are made of metal. The CTD and tantalum interlayer coatings of surgical implant 100 beneficially improve the performance of metal-on-metal (MOM) joint prostheses by providing coated joint surfaces that are rigid (wear resistant), chemically inert (biologically compatible) ) and have low friction coefficients. One of these coating substances
    Petition 870190085134, of 30/08/2019, p. 25/45
    21/32 is CTD. The CTD and tantalum interlayer coatings of surgical implant 100 beneficially improve the chemical and mechanical wear resistance of coated joint implants. The CTD and tantalum coatings of the surgical implant 100 beneficially improves the adhesion between the coatings and the metallic substrate 102 of the surgical implant 100 to prevent or delay the delamination of the coatings from the metallic substrate 102. The compositional gradients of the CTD layer 106 and / or tantalum interlayer 104 beneficially improve the adhesion between CTD layer 106 and / or tantalum interlayer 104 and metallic substrate 102 and reduce or avoid stresses that would have otherwise developed in the unclassified CTD layer 106 and / or unclassified tantalum interlayer 104 due to non-compatibility of the lattice (intrinsic stresses) or the difference in thermal coefficients of unclassified CTD layer 106 and / or unclassified tantalum interlayer 104 and the metallic substrate 102 (thermal stresses). Intrinsic stresses and thermal stresses in combination with stresses that arise during the joint are known to cause delamination of coated surgical implants.
    [0041] In another aspect, the present invention provides a method for the manufacture of surgical implants in accordance with the exemplary embodiments of the present invention. In an exemplary embodiment, the method for manufacturing surgical implant 100 comprises: (a) inserting the metallic substrate 102 into a vacuum system; (b) cleaning the metal substrate 102; (c) depositing the tantalum interlayer 104 on the metal substrate 102; and (d) depositing the CTD layer 106 on the tantalum interlayer 104.
    [0042] In one embodiment, cleaning of metal substrate 102 is done by bombarding ions of metal substrate 102 from
    Petition 870190085134, of 30/08/2019, p. 26/45
    22/32 a gaseous plasma. In an ion bombardment mode, the ion bombardment energy and ion flow (density) are preferably controlled by radio frequency (RF) energy. However, in other embodiments, any other sources of energy with which a varied or static electric field (DC) can be established can be used. In one embodiment, the ion bombardment is preferably done in a vacuum so that a stable RF plasma can be generated. In one embodiment, RF energy is used to control the ion and gas plasma bombardment process. In one embodiment, the increase in RF energy increases the potential of gaseous plasma and the equivalent polarization of direct current (DC). In one embodiment, increasing the RF energy increases the ion density of the plasma gas. In one embodiment, the reduction of RF energy reduces the potential of gaseous plasma and the polarization of DC (ion bombardment energy). In one embodiment, the reduction of RF energy reduces the ion density of the plasma gas. In one embodiment, the working pressure of the gases in the vacuum chamber into which the metal substrate 102 is inserted is used to control the process of bombardment of ions and gas plasma.
    [0043] In one embodiment, the cleaning of the metal substrate 102 comprises the application of bombardment with argon ion (Ar + ) to the metal substrate 102 in a vacuum. In one embodiment, the Ar + bombardment of the metallic substrate 102 in a vacuum is carried out in an RF autopolarization of -600 volts. In one embodiment, the Ar + bombardment of the metallic substrate 102 in a vacuum is done with an RF autopolarization in the range of about -100 volts to about -2,000 volts. In this mode, the RF autopolarization is changed in gradual increments in the range of an increase from 5 volts to an increase of 50 volts.
    Petition 870190085134, of 30/08/2019, p. 27/45
    23/32
    [0044] In one embodiment, the deposition of the tantalum interlayer
    104 on the metal substrate 102 comprises applying an electrical polarization to the substrate during tantalum deposition from a tantalum source. In one embodiment, the electrical polarization is an RF self-polarization. In one embodiment, the deposition of the tantalum interlayer 104 onto the metal substrate 102 comprises applying an RF autopolarization to the substrate during a sputter discharge with tantalum magnetron, with the RF autopolarization being in the range of -50 volts at - 2000 volts, preferably -100 volts to -400 volts. In one embodiment, the deposition of the tantalum interlayer 104 onto the metal substrate 102 comprises applying an RF autopolarization to a substrate during a sputter discharge with tantalum magnetron, the RF autopolarization being gradually changed. In one embodiment, the deposition of the tantalum interlayer 104 onto the metal substrate 102 comprises applying an RF autopolarization to a substrate during a sputter discharge with tantalum magnetron, the RF autopolarization being changed in predetermined increments. In one embodiment, the predetermined increments are in the range of an increase of 5 volts to an increase of 50 volts. In one embodiment, the deposition of the tantalum interlayer 104 onto the metal substrate 102 comprises applying an RF autopolarization to a substrate during a sputter discharge with tantalum magnetron, the RF autopolarization being gradually and gradually changing. predetermined increases. In one embodiment, the predetermined increments are in the range of an increase of 5 volts to an increase of 50 volts. In one embodiment, the deposition of the tantalum interlayer 104 onto the metal substrate 102 comprises applying an RF autopolarization to a substrate during a sputter discharge with tantalum magnetron, the
    Petition 870190085134, of 30/08/2019, p. 28/45
    24/32 RF autopolarization is changed in increments in the range of an increase from 5 volts to an increase of 50 volts.
    [0045] In one embodiment, the deposition of the CTD layer 106 comprises introducing a hydrocarbon that has a molecular weight in the range of 92 g / mol to 120 g / mol at a second RF autopolarization. In one embodiment, the deposition of the CTD layer 106 comprises introducing the hydrocarbon that has a molecular weight in the range of 92 g / mol to 120 g / mol, in the second RF autopolarization, the second RF autopolarization being changed from - 50 volts at - 600 volts in a gradual increment. In one embodiment, the deposition of the CTD layer 106 comprises introducing the hydrocarbon that has a molecular weight in the range of 92 g / mol to 120 g / mol, in the second RF autopolarization, the second RF autopolarization being changed from - 50 volts at - 600 volts in a gradual increase and the gradual increase is in the range of an increase of 5 volts to an increase of 50 volts. In one embodiment, the deposition of the CTD layer 106 comprises introducing the hydrocarbon which has a molecular weight in the range of 92 g / mol to 120 g / mol, in the second RF autopolarization, the hydrocarbon being independently selected from the group consisting of in: toluene, xylene, trimethyl benzene, and combinations thereof.
    [0046] In one embodiment, the method for manufacturing surgical implants according to the present invention further includes the step of introducing an acetylene atmosphere into a third RF autopolarization. In one embodiment, the third RF autopolarization is changed from -50 volts to - 600 volts in a second gradual increment. In one mode, the second gradual increase is in the range of a 5-volt increase to a 50-volt increase. [0047] In another embodiment, the method for the manufacture of surgical implants, according to the present invention, comprises the
    Petition 870190085134, of 30/08/2019, p. 29/45
    Next 25/32: (a) inserting a metallic substrate 102 into a vacuum system;
    (b) cleaning the metal substrate 102 by bombardment with Ar + in a predetermined RF autopolarization; (c) depositing the tantalum interlayer 104 on the metal substrate 102 by applying a predetermined RF autopolarization or range of RF auto polarizations during tantalum deposition from a sputter discharge with tantalum magnetron; (d) depositing the CTD layer 106 by introducing an acetylene atmosphere to a predetermined RF autopolarization or range of RF autopolarizations for a first period of time; (e) after the first period of time, introduce a source of organotitanium into the acetylene atmosphere for a second period of time; and (f) repeat steps (d) and (e) up to 100 repetitions, 50 repetitions or 10 repetitions.
    [0048] In such a modality, the method for the manufacture of surgical implants comprises inserting the metallic substrate 102 in a vacuum system and cleaning the metallic substrate 102 by bombardment with Ar + at an RF autopolarization of -600 volts. In one embodiment, the method for manufacturing surgical implants involves inserting the metal substrate 102 into a vacuum system and cleaning the metal substrate 102 by bombarding it with Ar + to an RF autopolarization in the range of about -200 to about - 2000.
    [0049] In another embodiment, the deposition of the tantalum interlayer 104 comprises applying an RF autopolarization to the substrate being coated by a tantalum magnetron discharge, with the RF autopolarization being in the range of -50 volts to -600 volts , preferably, -100 volts to -400 volts. In one embodiment, the deposition of the tantalum interlayer 104 comprises applying an RF autopolarization to the substrate being coated by a tantalum magnetron discharge, with the RF autopolarization being changed gradually. In one embodiment, the deposition of
    Petition 870190085134, of 30/08/2019, p. 30/45
    26/32 tantalum interlayer 104 comprises applying an RF autopolarization to the substrate being coated by a discharge with tantalum magnetron, the RF autopolarization being changed in predetermined increments. In one embodiment, the deposition of the tantalum interlayer 104 comprises applying an RF autopolarization to the substrate being coated by a tantalum magnetron discharge, with the RF autopolarization being changed in increments of 50 volts.
    [0050] In another modality, the deposition of the CTD layer
    106 comprises introducing an acetylene atmosphere to an RF autopolarization, the RF autopolarization being changed from -50 volts to - 600 volts. In one embodiment, the deposition of the CTD layer 106 comprises introducing an acetylene atmosphere to an RF autopolarization, the RF autopolarization being changed from 50 volts to - 600 volts in a gradual increase over a first period of time. In one embodiment, the deposition of the CTD layer 106 comprises introducing an acetylene atmosphere to an RF autopolarization, the RF autopolarization being changed from 50 volts to - 600 volts in a gradual increase over a first period of time, being that the gradual increase is in the range of an increase of 5 volts to an increase of 50 volts. In one embodiment, the method for manufacturing surgical implants comprises repeating the steps for depositing the CTD layer 106 a predetermined number of times. In one embodiment, the method for manufacturing surgical implants involves repeating the steps for depositing the CTD layer 106 up to ten repetitions. In one embodiment, the deposition of the CTD layer 106 further comprises introducing an organotitanium source into the acetylene atmosphere after the first period of time for a second period of time.
    Petition 870190085134, of 30/08/2019, p. 31/45
    27/32
    Examples
    Example 1: Lining of a spinal disc prosthesis
    [0051] This example illustrates the lining of a spinal disc prosthesis according to an embodiment of the present invention. The spinal disc prosthesis is produced from TiAl6Nb7 alloy, which features a ball-in-socket design. The coating process employed an organic vapor-activated metal-hybrid plasma deposition / physical vapor deposition (PA-MOCVD / PVD).
    [0052] The supplies used in this example included a vertebral disc prosthesis made from TiAl6Nb7 alloy, which features a ball-in-socket design; a 5 cm (2 inch) DC magnetron sputtering system (Advanced Energy, Fort Collins, USA); an EMAG Emmi-Sonic 60 HC ultrasonic cleaning bath (Naenikon, Switzerland); and a cleaning solution comprising a 1: 1 ethanol / acetone solvent mixture.
    [0053] The procedure for coating the spinal disc prosthesis used in the present example included the following steps.
    [0054] Step (a): The spinal disc prosthesis was placed in the ultrasonic cleaning bath in a cleaning solvent comprising a 1: 1 ethanol / acetone mixture. The vertebral disc prosthesis was sonicated in the solvent at a frequency of 45 kHz for 10 minutes.
    [0055] Step (b): The clean spinal disc prosthesis from step (a) was inserted into a 5 centimeter (2 inch) DC magnetron vacuum chamber. The 5 cm (2 inch) DC magnetron was equipped with DC Ta and Ti magnetron cathodes, RF substrate polarization, and a mass flow controller for gaseous and vaporized media (MKS Instruments, Norristown, USA), and pumps (Pfeiffer Vacuum GmbH, Asslar, Germany). THE
    Petition 870190085134, of 30/08/2019, p. 32/45
    28/32 vacuum chamber was pumped (subjected to vacuum) to a pressure less than 1x10-5 Pa.
    [0056] Step (c): The magnetron target was cleaned by sputtering by operating the magnetron DC with an argon atmosphere at 0.5 Pa and DC sputtering energy of 200 W for 5 minutes.
    [0057] Step (d): The surfaces of the spinal disc prosthesis were cleaned by sputtering by operating an RF power supply with an RF energy of 13.56 MHz, an argon atmosphere of 2.4 Pa, and RF self-polarization regulated at 600 V for 60 minutes.
    [0058] Step (e): The tantalum (Ta) interlayer was deposited on the spinal disk prosthesis cleaned by sputtering by igniting the Ta magnetron at an RF autopolarization of -300 V, Ta magnetron energy 200 W, and deposition rate of 400 nm of Ta in 60 minutes.
    [0059] Step (f): The magnetron discharge has been turned off.
    [0060] Step (g): The deposition of CTD from a 1.0 Pa toluene atmosphere, and -300 V operating RF energy, was applied to the spinal disc prosthesis with a gradual transition to acetylene ( operating pressure of 2.5 Pa; RF autopolarization of -600 V; and total layer thickness of 3 micrometers).
    [0061] The coated spinal disc prosthesis, according to the procedure described in this example, had a CTD coating that showed mechanical (high hardness), optical (high optical band span), electrical (high electrical resistivity), chemical properties (inert) and tribological (low friction and wear coefficient) exceptional. In one embodiment, the coated spinal disc prosthesis had a CTD coating with a gradient of hardness and elastic modulus beginning
    Petition 870190085134, of 30/08/2019, p. 33/45
    29/32 at 12 GPa and 120 GPa, respectively, at the Ta / CTD interface, and ending with 23 GPa and 230 GPa, respectively, on the surface.
    Example 2: Lining of a hip joint prosthesis
    [0062] This example illustrates the lining of a hip joint prosthesis according to an embodiment of the present invention. The hip joint prosthesis is produced from the TiAl6Nb7 alloy, which features a ball-in-socket design. The coating process employed a deposition of activated chemical vapors-hybrid plasma / physical vapor deposition (PA-CVD / PVD).
    [0063] The supplies used in this example included a hip joint prosthesis made from TiAl6Nb7 alloy, which features a ball-in-socket design; a 5 cm (2 inch) DC magnetron sputtering system (Advanced Energy, Fort Collins, USA); an EMAG Emmi-Sonic 60 HC ultrasonic cleaning bath (Naenikon, Switzerland); and a cleaning solution comprising a 1: 1 ethanol / acetone solvent mixture.
    [0064] The procedure for covering the hip joint prosthesis used in the present example included the following steps.
    [0065] Step (a): The hip joint prosthesis produced from the TiAl6Nb7 alloy was placed in the ultrasonic cleaning bath in a cleaning solvent comprising a 1: 1 ethanol / acetone mixture. The hip joint prosthesis was sonicated at a frequency of 45 kHz for 10 minutes.
    [0066] Step (b): The clean hip joint prosthesis from step (a) was inserted into a 5 centimeter (2 inch) DC magnetron vacuum chamber. The 5 cm (2 inch) DC magnetron was equipped with DC Ta and Ti magnetron cathodes, RF substrate polarization, and a mass flow controller for gaseous and vaporized media (MKS Instruments, Norristown, USA), and pumps (Pfeiffer Vacuum GmbH, Asslar, Germany). THE
    Petition 870190085134, of 30/08/2019, p. 34/45
    30/32 vacuum chamber was pumped (subjected to vacuum) to a pressure less than 1x10-5 Pa.
    [0067] Step (c): The hip joint prosthesis was cleaned by sputtering by operating the DC magnetron with an argon atmosphere at 0.5 Pa and 200 W energy for 5 minutes.
    [0068] Step (d): The surfaces of the hip joint prosthesis cleaned by sputtering were cleaned by sputtering by operating an RF power supply with an RF energy of 13.56 MHz, an argon atmosphere of 2 , 4 Pa, and regulated RF autopolarization of -600 V for 90 minutes.
    [0069] Step (e): The interlayer was deposited on the clean hip joint prosthesis by sputtering by igniting the Ta magnetron at an RF autopolarization of -300 V, 200 W Ta magnetron energy, and deposition rate of 400 nm of Ta in 45 minutes.
    [0070] Step (f): The magnetron discharge has been turned off.
    [0071] Step (g): CTD deposition was applied to the hip joint prosthesis coated with the Ta interlayer from step (e) from a 2.5 Pa acetylene atmosphere, -600 V RF autopolarization for 1 minute.
    [0072] Step (h): An argon / titanium tetraisopropoxide (TTIP) carrier gas stream was introduced into the acetylene discharge at an air flow rate of 10 standard cubic centimeters per minute (ccpm) through the bubbler. TTIP heated to 80 ° C for a duration of 1 minute.
    [0073] Step (i): Steps (g) and (h) were repeated 10 times and then the coated hip joint prosthesis was removed from the vacuum chamber.
    [0074] The coated spinal disc prosthesis, according to the procedure described in this example, had a CTD coating
    Petition 870190085134, of 30/08/2019, p. 35/45
    31/32 which showed exceptional mechanical (high hardness), optical (high optical range), electrical (high electrical resistivity), chemical (inert) and tribological (low friction and wear coefficient) properties. In one embodiment, the procedure followed in this experiment produced a hip joint prosthesis with a multilayer coating of CTD / CTD doped with Ti oxide, which has superior flexibility in view of having thinner sublayers compared to a prosthesis that has only one layer monolithic CTD.
    [0075] 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 embodiments shown and described, but is intended to cover modifications within the spirit and scope of the present invention 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. The words side, right, left, bottom and top designate directions in the drawings to which reference is made. The words inward and outward refer to directions in the opposite direction to, respectively, the geometric center of the surgical implant 102. Unless specifically described here, the terms one, one, o, and are not limited to one element, but, instead, they must be read with the meaning of at least one.
    [0076] 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 also can understandPetition 870190085134, of 08/30/2019, p. 36/45
    32/32 gives 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. [0077] 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 additionally remain in the spirit and scope of the present invention.
    权利要求:
    Claims (21)
    [1]
    1. Surgical implant, characterized by the fact that it comprises:
    a metallic substrate;
    a tantalum interlayer disposed adjacent to the metallic substrate and comprising α-tantalum and β-tantalum;
    at least one layer of diamond-like carbon (CTD) disposed adjacent to the tantalum interlayer;
    wherein the tantalum interlayer has a phase gradient from β-tantalum to α-tantalum between one side of the metallic substrate and one side of the CTD;
    the CTD layer having a hardness value and an elastic modulus value; and the hardness value has a gradient that increases in the opposite direction to the tantalum side; and the elastic modulus value has a gradient that increases in the opposite direction to the tantalum side.
    [2]
    2. Surgical implant, according to claim 1, characterized by the fact that the metallic substrate is titanium or a titanium-based alloy.
    [3]
    3. Surgical implant, according to claim 1, characterized by the fact that the metallic substrate is a cobalt-based alloy.
    [4]
    4. Surgical implant, according to claim 1, characterized by the fact that the metallic substrate is steel.
    [5]
    5. Surgical implant, according to claim 1, characterized by the fact that the tantalum interlayer has a thickness in the range of 1 nm to 2 pm.
    [6]
    6. Surgical implant, according to claim 5, characterized by the fact that the amorphous tantalum has a gradient of
    Petition 870190085134, of 30/08/2019, p. 38/45
    2/4 phase that increases from the metallic substrate side to the CTD side.
    [7]
    7. Surgical implant, according to claim 1, characterized by the fact that the tantalum interlayer additionally comprises a compound or element to promote the growth of alpha tantalum.
    [8]
    8. Surgical implant, according to claim 7, characterized by the fact that the compound is independently selected from the group consisting of: a titanium compound, a niobium compound, a tungsten compound and combinations thereof; and the element is independently selected from the group consisting of: titanium, niobium, tungsten and combinations thereof.
    [9]
    9. Surgical implant, according to claim 5, characterized by the fact that the tantalum interlayer additionally comprises nanoparticles of tantalum compound.
    [10]
    10. Surgical implant, according to claim 9, characterized by the fact that the tantalum interlayer is a tantalum and tantalum carbide nanocomposite.
    [11]
    11. Surgical implant, according to claim 1, characterized by the fact that the gradient of the hardness value increases from 12 GPa to 22 GPa.
    [12]
    12. Surgical implant, according to claim 11, characterized by the fact that the gradient of the elastic modulus value increases from 120 GPa to 220 GPa.
    [13]
    13. Surgical implant according to claim 1, characterized in that the at least one CTD comprises a plurality of alternating sublayers comprising a CTD sublayer and a metal doped CTD sublayer.
    Petition 870190085134, of 30/08/2019, p. 39/45
    3/4
    [14]
    14. Surgical implant, according to claim 13, characterized by the fact that the metal doped CTD sublayer is titanium doped.
    [15]
    15. Method for manufacturing a surgical implant, as defined in claim 1, characterized by the fact that it comprises:
    inserting a metallic substrate into a vacuum system;
    clean the metallic substrate by bombardment with Ar + to an RF autopolarization in the range of about -200 volts to about 2000 volts;
    depositing a tantalum interlayer by applying an RF autopolarization to the substrate during tantalum deposition from a tantalum source, said RF autopolarization in the range of -50 volts to -600 volts;
    deposit a layer of CTD by introducing a hydrocarbon that has a molecular weight in the range of 92 g / mol to 120 g / mol, in the second RF autopolarization, the second RF autopolarization being changed from -50 volts to - 600 volts in a gradual increment.
    [16]
    16. Method for making a surgical implant, according to claim 15, characterized by the fact that the gradual increase is in the range of an increase of 5 volts to an increase of 50 volts.
    [17]
    17. Method for making a surgical implant, according to claim 16, characterized by the fact that the hydrocarbon is independently selected from the group consisting of: toluene, xylene, trimethyl benzene and combinations thereof.
    [18]
    18. Method for manufacturing a surgical implant, according to claim 15, characterized by the fact that it additionally comprises the step of:
    Petition 870190085134, of 30/08/2019, p. 40/45
    4/4 introducing an acetylene atmosphere in a third RF autopolarization, with the third RF autopolarization being changed from -50 volts to - 600 volts in a second gradual increment.
    [19]
    19. Method for manufacturing a surgical implant, according to claim 18, characterized by the fact that the second gradual increment is in the range of an increase from 5 volts to an increase of 50 volts.
    [20]
    20. Method for making a surgical implant, characterized by the fact that it comprises the following steps:
    (a) inserting a metallic substrate into a vacuum system;
    (b) clean the metallic substrate by bombarding with Ar + to an RF autopolarization in the range of about -200 volts to about -2000 volts, preferably to an RF autopolarization of -600 volts;
    (c) depositing a tantalum interlayer by applying an RF autopolarization to a substrate during tantalum deposition, said RF autopolarization in the range of -50 volts to -600 volts;
    (d) depositing a layer of CTD by introducing an acetylene atmosphere to an RF autopolarization, the RF autopolarization being changed from -50 volts to - 600 volts in a gradual increase over a first period of time;
    (e) after the first period of time, introduce a source of organotitanium into the acetylene atmosphere for a second period of time; and (f) repeat steps (d) and (e) for up to ten repetitions.
    [21]
    21. Method for making a surgical implant, according to claim 20, characterized by the fact that the gradual increase is in the range of an increase from 5 volts to an increase of 50 volts.
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    同族专利:
    公开号 | 公开日
    CN105073149B|2017-10-10|
    JP2016518153A|2016-06-23|
    CA2903775C|2021-09-07|
    KR20150128910A|2015-11-18|
    US20140257494A1|2014-09-11|
    WO2014163919A1|2014-10-09|
    US9308090B2|2016-04-12|
    EP2996732A1|2016-03-23|
    EP2996732B1|2020-01-01|
    JP6242999B2|2017-12-06|
    KR102191113B1|2020-12-16|
    CN105073149A|2015-11-18|
    CA2903775A1|2014-10-09|
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    法律状态:
    2018-02-27| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2019-07-23| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2020-04-07| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2020-06-09| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 27/02/2014, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    US13/793,470|US9308090B2|2013-03-11|2013-03-11|Coating for a titanium alloy substrate|
    PCT/US2014/018890|WO2014163919A1|2013-03-11|2014-02-27|Coating for a titanium alloy substrate|
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