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    SUMMARY PATENT OF INVENTION "magnesium alloy with adjustable degradation rate" the present invention relates to an alloy and an implant having a three-dimensional structure based on such an alloy. the alloy comprises a mgznca alloy containing nanoprecipitates which are less noble than the mg matrix alloy and have a zn content ranging from 0.1% by weight from zn to 2% by weight from zn and a calcium content that varies from 0.2% by weight to 0.5% by weight and which has one or more elements, with the remainder being mg. any second phase generated during the solidification process can be completely dissolved by heat treatment in solution. finely distributed nanoprecipitates can then be generated by a subsequent stage of thermal aging treatment. these precipitates are used to "fix" the grain boundaries and prevent the granular structure from thickening during further processing to obtain grain sizes below 5 µm.
    公开号:BR112015022632B1
    申请号:R112015022632-9
    申请日:2014-03-11
    公开日:2020-01-07
    发明作者:Thomas Imwinkelried；Stefan Beck；Peter Uggowitzer；Joerg Loeffler
    申请人:DePuy Synthes Products, Inc.；
    IPC主号:
    专利说明:

    Descriptive Report of the Invention Patent for COMPOSITION OF MAGNESIUM ALLOY, IMPLANT, AND METHOD OF PRODUCTION OF THE COMPOSITION.
    REMISSIVE REFERENCE TO RELATED DEPOSIT REQUESTS [001] This application claims priority to U.S. provisional application No. 61 / 783,554, filed on March 14, 2013; U.S. Provisional Application No. 61 / 909,100, filed on November 26, 2013; and U.S. Provisional Application No. 61 / 942,951, filed February 21, 2014; whose contents are hereby incorporated by way of reference, in their entirety.
    BACKGROUND OF THE INVENTION [002] Magnesium implants were used clinically in the treatment of bone fractures by several surgeons in the 1930s. For example, J. Verbrugge (1934) used implants of pure magnesium and Mg-8% Al alloy in 21 patients . However, after the Second World War, the use of magnesium as a resorbable implant material fell into oblivion. In recent years, researchers have revived their interest in resorbable magnesium implants. One of the main focuses of magnesium research is the development of alloys and coatings. The main objectives are to control the rate of degradation, to prevent the formation of gas bubbles during degradation and to avoid possible harmful elements in the formation of the alloy. Therefore, there is a need for magnesium alloys with homogeneous degradation behavior, whose degradation rate can be controlled and / or adjusted as desired.
    [003] Pure commercial grade magnesium (3N-Mg) has poor mechanical properties compared to alloys, such as AZ91 or WE43. The possibilities for hardening pure magnesium are quite limited. Hardening can be achieved by refining the microstructure of the grains, using plastic deformation to induce recrystallization.
    Petition 870170014739, of 03/07/2017, p. 5/14
    2/27 dynamic application (eg by extrusion). The fine-grained microstructure is not only necessary to obtain a better resistance level, but it is also necessary to avoid mechanical anisotropy (difference in strength between tension and compression). However, the microstructure may not be stable.
    [004] The modalities of the present invention overcome one or more of the challenges mentioned above.
    BRIEF SUMMARY OF THE INVENTION [005] The present disclosure provides several exemplary embodiments of the present invention, some of which are discussed below.
    [006] In one aspect, the present invention provides an MgZnCa alloy composition and an implant with a three-dimensional structure based on such an alloy composition.
    [007] In one embodiment, the alloy composition comprises an Mg matrix; and, optionally, nanoprecipitates; the composition having a Zn content ranging from 0.1% by weight from Zn to 2.0% by weight from Zn; a Ca content ranging from 0.2% by weight of Ca to 0.5% by weight of Ca; a content of one or more other elements; and the remaining Mg content; being that the nanoprecipitates are less noble or more noble than the matrix of Mg, or a mixture of them. In another embodiment, the MgZnCa alloy composition consists essentially of an Mg matrix; and, optionally, nanoprecipitates; the composition having a Zn content ranging from 0.1% by weight from Zn to 2.0% by weight from Zn; a Ca content ranging from 0.2% by weight of Ca to 0.5% by weight of Ca; a content of one or more other elements; and the remaining Mg content; being that the nanoprecipitates are less noble or more noble than the matrix of Mg, or a mixture of them. In another embodiment, the MgZnCa alloy composition consists of an Mg matrix; and, optional
    Petition 870160010078, of 03/22/2016, p. 5/52
    3/27 nanoprecipitates; the composition having a Zn content ranging from 0.1% by weight from Zn to 2.0% by weight from Zn; a Ca content ranging from 0.2% by weight of Ca to 0.5% by weight of Ca; a content of one or more other elements; and the remaining Mg content; being that the nanoprecipitates are less noble or more noble than the matrix of Mg, or a mixture of them.
    [008] In some of these modalities, the alloy composition is substantially free of microgalvanic elements. In other of these modalities, the alloy composition is monophasic. In other of these modalities, the total of other elements is less than about 0.1%, by weight, of the composition. In other of these modalities, the one or more other elements are located in a secondary phase. In other of these modalities, nanoprecipitates are less noble than the Mg matrix and comprise (Mg, Zn) 2 Ca. In other of these modalities, nanoprecipitates are more noble than the Mg matrix and comprise Mg6Zn 3 Ca 2 . In some of these modalities, the alloy comprises nanoprecipitates which are less noble than the Mg matrix and nanoprecipitates which are more noble than the Mg matrix.
    [009] In some embodiments of the alloy, according to the present invention, the alloy has a grain size of less than 10 pm; less than 5 pm; or less than 2 pm. In some embodiments of the alloys of the present invention, the alloy has an elastic limit of at least 180 MPa. In one embodiment, the alloy has a maximum tensile strength of at least 240 MPa. In another embodiment, the alloy has at least 10% elongation at break. In yet another embodiment, the alloy has an in vitro degradation rate of less than 0.5 mg / cm 2 / day, as measured in a simulated body fluid.
    [0010] In other modalities, the implant is an orthopedic implant. In such modalities, the orthopedic implant comprises one or
    Petition 870160010078, of 03/22/2016, p. 6/52
    4/27 more of the following: a nail, a screw, a clamp, a plate, a rod, a tack, a pin, a pin to lock an intermediate nail (IM), an anchor, a plug-in pin, a plug, a fastener, a sleeve, a mesh, a transconector, a nut, a shaped body, a spinal cage, a cable, a K cable, a fabric structure, claw, splint, frame, foam and honeycomb structure. In some other embodiments, the implant has a lower rate of degradation compared to magnesium alloy implants that contain microgalvanic impurities.
    [0011] In other modalities, the implant is a non-orthopedic implant. In such modalities, the non-orthopedic implant includes a cardiovascular stent, a neurological stent and a vertebroplasty stent.
    [0012] In yet another modality of the implant, each alloy has an in vitro degradation rate of less than 0.5 mg / cm 2 / day, as measured in a simulated body fluid.
    [0013] In one aspect, the present invention provides a method of producing an alloy according to the modalities described herein. In one embodiment, the method comprises: (a) melting an alloy containing (i) commercially pure magnesium, with a purity of at least 99.96% by weight; and (ii) from 0.1 to 2.0% by weight of zinc, with a purity of at least 99.9% by weight, and (iii) from 0.2 to 0.5% by weight , of calcium, with a purity of at least 99.9%, by weight, said casting being preferably carried out in an inert atmosphere and in an inert reaction vessel; (b) perform heat treatment in molten alloy solution at two different temperatures, the first temperature being lower than an eutectic temperature of Mg-Zn and a second temperature being higher than the eutectic temperature of the ternary Mg-Zn-Ca system for, thus forming an MgZnCa alloy containing from 0.1% by weight of Zn to 2% by weight of Zn and 0.2% by weight
    Petition 870160010078, of 03/22/2016, p. 7/52
    5/27 weight, from Ca to 0.5%, by weight, from Ca (c) perform heat treatment of aging between 100 ° C and 300 ° C; and (d) extruding the alloy in a desired shape.
    [0014] The impurity limits for magnesium are preferably: Fe <30 ppm, Cu <20 ppm, Ni <5 ppm, Mn <200 ppm, Si <200 ppm, whereas the total amount of these impurities must, preferably be less than 400 ppm.
    BRIEF DESCRIPTION OF THE DRAWINGS [0015] Figure 1 is a graphical representation of the average evolution of hydrogen as a function of time for certain Mg alloys.
    [0016] Figure 2 shows reconstructions of pCT (2D slices) of Mg pins implanted in the femur of Sprague-Dawley rats, 12 weeks after the operation.
    [0017] Figure 3 shows the surface topography of implant samples after immersion in simulated body fluid (in English, SBF).
    [0018] Figure 4, which comprises Figures 4A-4B, is a (A) graphical representation of an isothermal section of an MgZn-Ca system at 300 ° C and (B) an illustration of the constitution of an MgZn1Ca0 alloy, 3, in accordance with the present disclosure.
    [0019] Figure 5 is a graphical representation of the average evolution of hydrogen, during immersion in simulated body fluid buffered with TRIS, as a function of the time of certain Mg alloys that were subjected to certain heat treatments.
    [0020] Figure 6, which comprises Figures 6A-6B, is a bar graph showing the average evolution of hydrogen, during immersion in simulated body fluid buffered with TRIS, for certain Mg alloys that were subjected to certain heat treatments .
    [0021] Figure 7 is a bar graph showing the grain size for certain extruded Mg alloys that have undergone certain heat treatments.
    Petition 870160010078, of 03/22/2016, p. 8/52
    6/27
    DETAILED DESCRIPTION OF THE INVENTION [0022] Now, reference will be made in detail to the various modalities of the present disclosure. In one embodiment, the MgZnCa alloy composition comprises an Mg matrix; and, optionally, nanoprecipitates; the composition having a Zn content ranging from 0.1% by weight from Zn to 2.0% by weight from Zn; a Ca content ranging from 0.2% by weight of Ca to 0.5% by weight of Ca; a content of one or more other elements; and the remaining Mg content; being that the nanoprecipitates are less noble or more noble than the matrix of Mg, or a mixture of them. In another embodiment, the MgZnCa alloy composition consists essentially of an Mg matrix; and, optionally, nanoprecipitates; the composition having a Zn content ranging from 0.1% by weight from Zn to 2.0% by weight from Zn; a Ca content ranging from 0.2%, by weight, from Ca to 0.5%. by weight of Ca; a content of one or more other elements; and the remaining Mg content; being that the nanoprecipitates are less noble or more noble than the matrix of Mg, or a mixture of them. In another embodiment, the MgZnCa alloy composition consists of an Mg matrix; and, optionally, nanoprecipitates; the composition having a Zn content ranging from 0.1% by weight from Zn to 2.0% by weight from Zn; a Ca content ranging from 0.2%, by weight, from Ca to 0.5%. by weight of Ca; a content of one or more other elements; and the remaining Mg content; being that the nanoprecipitates are less noble or more noble than the Mg matrix, or a mixture of them.
    [0023] The terms composition, alloy composition, MgZnCa alloy and alloy are used interchangeably in the present invention. Unless otherwise specified and indicated, the amounts disclosed in the present invention are based on the weight of the alloy composition.
    [0024] As used here, the term Mg matrix refers to the por
    Petition 870160010078, of 03/22/2016, p. 9/52
    7/27 Mg content of the alloy composition volume in which the constituent parts of the alloy, for example, Zn, Ca and / or impurities (also referred to in the present invention as other elements), are dissolved. For example, the Mg matrix can comprise pure Mg or Mg in solid solution with Zn, Ca and / or impurities, or mixtures thereof. The Mg matrix does not include secondary phases, that is, undissolved components, including precipitates.
    [0025] The Mg matrix is also called the remainder of Mg, remaining Mg or the surrounding Mg phase. For example, for certain embodiments, the composition can be described as an MgZnCa alloy containing nanoprecipitates, with a Zn content ranging from 0.1% by weight, from Zn to 2.0%, by weight, Zn and a calcium content ranging from 0.2% by weight to 0.5% by weight, less than 0.04% by weight of one or more of the other elements, the other elements being optionally located in a secondary phase, and with the rest of the alloy being Mg, with nanoprecipitates being less noble than the remaining Mg.
    [0026] In some aspects of the present invention, the composition can be substantially free of microgalvanic elements. In other embodiments, the composition may be free of secondary phases, including precipitates. A composition free of secondary phases can be obtained when all components of the composition are dissolved, thus forming a single-phase composition.
    [0027] In other aspects of the invention, the composition comprises a plurality of nanoprecipitates, the precipitates being less noble than the Mg matrix. In some of these embodiments, nanoprecipitates that are less noble than the Mg matrix comprise (Mg, Zn) 2 Ca. In other embodiments, the composition comprises a plurality of nanoprecipitates that are more noble than the Mg matrix. In some of these modalities, nano
    Petition 870160010078, of 03/22/2016, p. 10/52
    8/27 precipitates that are more noble than the Mg matrix comprise Mg 6 Zn 3 Ca 2 . Nanoprecipitates are typically less than 1000 nanometers and more typically less than 500 nanometers. In some embodiments, nanoprecipitates range from about 1000 nanometers to about 100 nanometers, from about 500 nanometers to about 100 nanometers or from about 300 nanometers to about 200 nanometers.
    [0028] With regard to the implants of the present invention, the implant has a three-dimensional structure and comprises an MgZnCa alloy disclosed herein. For example, in one embodiment, the implant has a three-dimensional structure made of an MgZnCa alloy, which comprises an Mg matrix and a plurality of nanoprecipitates, the alloy having a Zn content that varies from 0.1%, in weight, from Zn to 2%, by weight, from Zn, a calcium content ranging from 0.2%, by weight, to 0.5%, by weight, with less than 0.10%, by weight, from one or more other elements, with the remainder being Mg and the plurality of nanoprecipitates being less noble than the Mg matrix. In another embodiment, the implant has a three-dimensional structure and comprises a composition consisting essentially of an MgZnCa alloy, which comprises an Mg matrix and a plurality of nanoprecipitates, the alloy having a Zn content ranging from 0, 1% by weight of Zn to 2% by weight of Zn, a calcium content ranging from 0.2% by weight to 0.5% by weight with less than 0.10%, by weight of one or more other elements, with the remainder being Mg and the plurality of nanoprecipitates being less noble than the Mg matrix. In another embodiment, the implant has a three-dimensional structure and comprises a composition that consists essentially of an MgZnCa alloy, comprising the Mg matrix and a plurality of nanoprecipitates, the alloy having a Zn content ranging from 0, 1% by weight of Zn to 2% by weight
    Petition 870160010078, of 03/22/2016, p. 11/52
    9/27 Zn, a calcium content ranging from 0.2% by weight to 0.5% by weight with less than 0.10% by weight of one or more other elements, with the remainder being Mg and the plurality of nanoprecipitates are less noble than the Mg matrix. In such modalities, the less noble nanoprecipitates comprise (Mg, Zn) 2 Ca. [0029] In general, the Zn content in the various modalities of the MgZnCa alloy and an implant based on the various modalities of the MgZnCa alloy, according with the present invention, it can have any suitable amount between 0.1% by weight to 2% by weight. In one embodiment, the MgZnCa alloy has a Zn content that can be selected independently from the ranges of 0.1% by weight to 2% by weight; 0.5% by weight to 2% by weight; 0.6% by weight to 0.8% by weight; 1% by weight to 2% by weight; 0.1% by weight to 0.5% by weight; 0.1% by weight to 1% by weight; and any subset of the tracks presented here.
    [0030] In general, the Ca content in the various modalities of the MgZnCa alloy and in an implant based on the various modalities of the MgZnCa alloy, according to the present invention, can be any suitable amount between 0.2%, in 0.5% by weight. In one embodiment, the MgZnCa alloy has a Ca content that can be selected independently from the ranges of 0.2% by weight to 0.5% by weight; 0.2% by weight to 0.3% by weight; 0.2% by weight to 0.4% by weight; 0.3% by weight to 0.4% by weight and 0.4% by weight to 0.5% by weight.
    [0031] In general, the alloy compositions of the present invention are based on a material free of secondary phases that would otherwise act as cathodic microgalvanic cells. Often, the presence of a single impurity can reduce the solubility of the other impurities. During the solidification process, impurities can accumulate in the alloy's interdendritic spaces and in
    Petition 870160010078, of 03/22/2016, p. 12/52
    10/27 lead to the formation of secondary phases. In order to obtain the necessary level of purity of the MgZnCa alloy of the modalities described herein, the acceptable amount of other elements within the alloy is limited.
    [0032] For example, the total amount of other elements within the alloy composition is typically less than 0.10% by weight based on the weight of the composition, typically less than 0.06% by weight based on the weight of the composition, and more typically less than 0.04% by weight, based on the weight of the composition. The other elements can be dissolved in the Mg matrix or they can be in a secondary phase, or both. Typically, the alloy comprises less than 0.04%, by weight, of other elements in a secondary phase.
    [0033] In one embodiment, the MgZnCa alloy, which has a plurality of nanoprecipitates that are less noble than the Mg matrix, contains less than 400 ppm (by weight) in total other elements. In another embodiment, the MgZnCa alloy, which has a plurality of nanoprecipitates that are less noble than the Mg matrix, contains less than 200 ppm in total other elements. In yet another embodiment, the MgZnCa alloy, which has a plurality of nanoprecipitates that are less noble than the Mg matrix, contains less than 100 ppm in total other elements. In yet another embodiment, the MgZnCa alloy, which has a plurality of nanoprecipitates that are less noble than the Mg matrix, contains less than 50 ppm in total other elements.
    [0034] In such modalities, the other elements may include one or more among Fe, Cu, Ni, Co, Si, Mn, Al, Zr and P.
    [0035] The impurity content is kept at low levels to control the corrosion rate when implant based on such alloys is placed in the body. It is necessary to control the corrosion rate so that the implant has sufficient strength over a period of time
    Petition 870160010078, of 03/22/2016, p. 13/52
    11/27 to allow healing and not to interfere with the healing process. Although the by-products of the degradation of the magnesium alloys of the present invention are non-toxic, as the metal is corroded the pH near the implant increases to a basic pH. Similarly, hydrogen gas produced during the corrosion process must be eliminated. In the case of endovascular implants, these concerns are insignificant, as the constant blood flow over the implant removes hydrogen gas and other by-products of degradation.
    [0036] In general, the content of rare earths in the various modalities of the MgZnCa alloy compositions used in an implant, according to the present invention, is limited. In such modalities, rare earth elements include Sc, Y, lanthanide elements, with atomic numbers in the range 57 to 71, and actinide elements, with atomic numbers in the range 89 to 103. In one mode, the rare earth is less than 10 ppm. In another modality, the content of rare earths is less than 5 ppm.
    [0037] In some embodiments, the alloy is substantially free of microgalvanic elements. For the purposes of this application microgalvanic element refers to a secondary phase, including a precipitate, with a potential greater than that of the magnesium matrix (ie, which is electronically more noble). For the purposes of this application, substantially exempt (a) refers to the number of microgalvanic elements that is small enough not to alter the overall degradation behavior of the alloy from a degradation, in general, homogeneous to an intermittent and localized degradation.
    [0038] The mechanical properties of commercially pure magnesium are enhanced by hardening the solid solution with high purity zinc, without affecting the homogeneous nature of the alloy. A fine-grained microstructure can be obtained by plastic deformation and
    Petition 870160010078, of 03/22/2016, p. 14/52
    12/27 tabilized with secondary phases, including precipitates, which are less noble than the magnesium matrix. For example, the less noble (Mg, Zn) 2 Ca phase can be obtained through small additions of high purity calcium and adequate heat treatment. If necessary, the rate of degradation can be accelerated, while maintaining a uniform corrosion profile, through modification of the composition and the thermal treatment of aging to form precipitates that are more noble than the magnesium matrix, as precipitates of Mg6Zn3Ca 2 fine.
    [0039] Implants are also revealed, as implantable medical devices, made from the compositions disclosed here. The revealed implants have advantageous physical properties, including high elastic limit, maximum high tensile strength and elongation at break. In some embodiments, the alloy has a maximum tensile strength of at least 180 MPa. In some embodiments, the alloy has a maximum tensile strength of at least 200 MPa. In other embodiments, the alloy has a maximum tensile strength of at least 220 MPa. In some embodiments, the alloy has a maximum tensile strength of at least 240 MPa. In other embodiments, the alloy has a maximum tensile strength of at least 260 MPa, at least 280 MPa, at least 300 MPa, at least 320 MPa, at least 340 MPa, at least 360 MPa or at least 380 MPa. In some embodiments, the alloy has at least 10% elongation at break. In other modalities, the alloy has elongation at break values of: at least 12%, at least 14%, at least 16%, at least 18%, at least 20% and at least 22%.
    [0040] Implants according to exemplary embodiments of the present invention also have advantageous chemical properties in vitro and in vivo. In some embodiments, the alloy has an in vitro degradation rate of less than 1.0 mg / cm 2 / day. In other modalities
    Petition 870160010078, of 03/22/2016, p. 15/52
    13/27 since the alloy has an in vitro degradation rate of less than 0.5 mg / cm 2 / day, as measured in a simulated body fluid. In other embodiments, the alloy has an in vitro degradation rate of less than 0.05 mg / cm 2 / day, less than 0.1 mg / cm 2 / day, less than 0.15 mg / cm 2 / day, less than 0.2 mg / cm 2 / day, less than 0.25 mg / cm 2 / day, less than 0.3 mg / cm 2 / day, less than 0.35 mg / cm 2 / day, less than 0.4 mg / cm 2 / day or less than 0.45 mg / cm 2 / day, as measured in a simulated body fluid.
    [0041] Implantable medical devices based on the compositions described here can be manufactured for a variety of medical / clinical applications, including replacing an absent biological structure, supporting a damaged biological structure or to enhance an existing biological structure. The composition of the implants and / or the surfaces of the implants that come into contact with the body / body tissues can be created depending on the specific application being considered. Surgical implants can be manufactured for medical / clinical applications in the field of orthopedics, neurosurgery, among others. Non-limiting examples of surgical implants include: neurosurgical implants, for example, shunts and components for hydrocephalus; intracranial aneurysm loops; 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; implants for maxillofacial surgery; and spinal and pelvic systems like the Universal Spine System, Harrington System and conventional systems. Consequently, surgical implants that can be manufactured based on the compositions described here can include a wide range of products that vary in composition,
    Petition 870160010078, of 03/22/2016, p. 16/52
    14/27 as described here, 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.
    [0042] In some modalities, the implant is an orthopedic implant. In such embodiments, the orthopedic implant comprises one or more of the following: a nail, a screw, a clamp, a plate, a nail, a tack, a pin, a pin to lock an IM nail, an anchor, a locking pin , a plug, a fastener, a sleeve, a mesh, a transconector, a nut, a shaped body, a spinal cage, a cable, a K cable, a fabric structure, claw, splint, frame, foam and honeycomb structure . In some other embodiments, the implant has a lower rate of degradation compared to magnesium alloy implants that contain microgalvanic elements.
    [0043] In other modalities, the implant is a non-orthopedic implant. In such modalities, the non-orthopedic implant includes a cardiovascular stent, a neurological stent and a vertebroplasty stent.
    [0044] In vitro degradation tests, in simulated body fluid (SBF) with Tris buffer, show that uniform degradation, with extremely low degradation rate, can be obtained using the MgZnCa alloys of the present disclosure (see, for example, Figure 3C). These alloys, however, would have poor mechanical properties compared to alloys like WE43, if specific measures were not taken. It has been found that such a limitation can be overcome by strictly controlling the grain size during all processing steps, including casting. The hardening of the alloy can be achieved by refining the granular microstructure,
    Petition 870160010078, of 03/22/2016, p. 17/52
    15/27 using plastic deformation (extrusion, forging, angular compression of identical channels, etc.). In addition to achieving a better resistance level, it was also discovered that the fine-grained microstructure avoids mechanical anisotropy (difference in strength between tension and compression).
    [0045] The present disclosure further provides methods for producing various modalities of the MgZnCa alloy described herein. In one embodiment, the method includes the steps of: (a) melting an alloy containing (i) commercially pure magnesium, with a purity of at least 99.96% by weight; and (ii) from 0.1 to 2.0% by weight of zinc, with a purity of at least 99.9% by weight, and (iii) from 0.2 to 0.5% by weight , of calcium, with a purity of at least 99.9%, by weight, said casting being preferably carried out in an inert atmosphere and in an inert reaction vessel; (b) perform heat treatment in molten alloy solution at two different temperatures, the first temperature being lower than an eutectic temperature of Mg-Zn and a second temperature being higher than the eutectic temperature of the ternary Mg-Zn-Ca system for, thus forming an MgZnCa alloy containing from 0.1% by weight of Zn to 2% by weight of Zn and 0.2% by weight of Ca to 0.5% by weight of Ca (c) perform thermal aging treatment between 100 ° C and 300 ° C; and (d) extruding the alloy in a desired shape. In some embodiments, the MgZnCa alloy is monophasic. In some embodiments, the method may also include the step of a second heat treatment of aging of the shaped alloy to improve the strength or ductility of the alloy. In other embodiments, the method includes heat treatment with low temperatures of the shaped alloy, for example, from about 150 ° C to about 250 ° C, to adjust the degradation profile of the alloy. As used above, the eutectic temperature of Mg-Zn refers to a pseudobinary system of Mg-Zn with 0.2 to 0.5%, by weight, of Ca, being
    Petition 870160010078, of 03/22/2016, p. 18/52
    16/27 that pseudobinary is the cut through the ternary phase diagram for a given calcium content.
    [0046] The impurity limits for magnesium are preferably: Fe <30 ppm, Cu <20 ppm, Ni <5 ppm, Mn <200 ppm, Si <200 ppm, whereas the total amount of these impurities should, preferably be less than 400 ppm. In certain embodiments, precipitates of (Mg, Zn) 2 Ca are formed and consist of one of the few phases that are electronically less noble than pure magnesium.
    [0047] In certain embodiments, the first temperature is in the range of about 200 ° C to about 400 ° C, from about 300 ° C to about 400 ° C or from about 330 ° C to about 370 ° C. Typically, the molten alloy is heated at the first temperature for about 6 to about 24 hours. The second temperature is typically in the range of about 400 ° C to about 600 ° C, about 400 ° C to about 500 ° C or about 400 ° C to about 460 ° C. The second temperature is preferably higher than the solvus temperature of any possible precipitates, to ensure that all the elements of the alloy are in solid solution. Typically, the molten alloy is heated to the second temperature for about 6 to about 16 hours. Heat treatment for aging is typically between 100 ° C and 300 ° C, and, in certain embodiments, between about 150 ° C and about 250 ° C. Typically, the aging heat treatment is done for about 0.5 hours to about 6 hours. Such aging treatment produces fine and homogeneously distributed nanoprecipitates, before the extrusion process.
    [0048] Phase calculations of the MgZnCa alloy system demonstrated that there is a compositional window for low levels of Zn and Ca, in which complete dissolution of the elements that form the alloy is possible and there is no second residual phase of the casting process , after heat treatment in solution (see, for example, Figure
    Petition 870160010078, of 03/22/2016, p. 19/52
    17/27
    4B). Without sticking to the theory, it was believed that advantageous properties could result from a stable fine grain microstructure within the alloy and that such a microstructure could be obtained if the grain boundaries were fixed by the presence of fine precipitates. An aging heat treatment before extrusion has been found to result in the formation of nanoprecipitates that are not visible under an optical microscope, but are large enough to prevent thickening of the grains due to static recrystallization. These precipitates do not affect the dynamic recrystallization behavior during the extrusion process. Grain refining, therefore, remains possible, while thickening is prevented or, at least, delayed. Furthermore, as the precipitates are less noble than the magnesium matrix and do not have three-dimensional connectivity to each other, the precipitates do not negatively affect the degradation performance of the alloy. Without the desire to link to the theory, it is believed that the magnesium matrix does not have three-dimensional connectivity, because precipitates are not formed during solidification, but, instead, after the complete dissolution of the elements and subsequent heat treatment. The MgZnCa alloy system, which has the less noble fine precipitates, exhibits fine grain sizes less than 5 pm after the extrusion of the casting billet, including less than 2 pm and less than 1 pm.
    [0049] For example, with the addition of 0.1% by weight to 2.0% by weight of Zn and 0.2% by weight to 0.5% by weight of Ca to Mg, such finely dispersed precipitates can be created by a heat treatment of aging, after the initial heat treatment of the solution. The weight percentage of calcium and zinc can be adjusted to control the rate of degradation of the alloy. If the rate of degradation of the alloy is too slow and needs to be accelerated, precipitates of Mg 6 Zn 3 Ca 2 can be formed through a small change in
    Petition 870160010078, of 03/22/2016, p. 20/52
    18/27 alloy composition. As an example, for an Mg alloy with 1% by weight of Zn and 0.35% by weight of Ca, mainly nanoparticles of (Mg, Zn) 2 Ca are precipitated by a heat treatment of aging at 200 ° C, whereas for an Mg alloy with 1.5% by weight of Zn and 0.25% by weight of Ca, mainly nanoparticles of Mg6Zn 3 Ca 2 precipitate at the same temperature.
    [0050] In an alternative modality, the heat treatment stage of aging can be replaced by a heat treatment done during the extrusion stage, for example, during preheating and extrusion. Preheating for extrusion is typically done at the extrusion temperature in a separate oven, until the billet has reached a uniform temperature. The preheated billet is then transferred to a preheated extrusion chamber and extruded. If precipitates form during this preheating step, it is considered an aging treatment.
    [0051] After the alloy is formed, a low temperature heat treatment, such as an annealing step, can be performed. In some embodiments, the low temperature annealing step is performed after the extrusion step.
    [0052] For example, low temperature annealing is a heat treatment, typically of the shaped alloy, at a temperature and for a time sufficient to affect the formation of precipitates and, consequently, the degradation properties. In particular, it has been found that annealing at low temperature can lead to the growth of more noble precipitates, such as Mg6Zn3Ca2 precipitates, which generally accelerate the degradation of the alloy. In addition, a low temperature annealing process can also affect the microstructure of the alloy, with a longer annealing process that produces larger grains.
    Petition 870160010078, of 03/22/2016, p. 21/52
    19/27 [0053] In some embodiments, low temperature annealing is carried out in a range of about 100 ° C to about 300 ° C or from about 150 ° C to about 250 ° C. For example, in some embodiments, low temperature annealing is carried out at 200 ° C. Typically, low temperature annealing is carried out for about 1 to about 100 hours.
    [0054] Magnesium alloys, in the exemplary modalities described above, have properties specifically favorable for processing and for the purpose for which they are intended in comparison with traditional magnesium alloys: the ductility of magnesium alloys is quite high. For the purposes of the present disclosure, the term ductility (or tenacity, deformation capacity) refers to the ability of a metallic material to undergo permanent deformation under sufficiently high mechanical loads, before breaking. This capacity is of great importance for several construction pieces, since only a ductile material is capable of dissipating local peaks of mechanical stress, through its permanent deformation, without breaking, and with simultaneous cold solidification. This aspect, in particular, makes it particularly advantageous to use the magnesium alloys of the invention as material, for example, for biodegradable implants, in particular, biodegradable implants for bone fixation. With a given material, the ductility depends on the temperature, the stress rate, the multi-axis character of the state of mechanical stress in action and the environment. Characteristic ductility values include, for example, elongation at break and overweight, resistance to impact impact and resistance to fracture, as described elsewhere in the present disclosure.
    EXAMPLES [0055] For the purpose of additional disclosure, certain alloys (MgZn5Ca0.25) that contain a high content of Zn, called ZX50, have been
    Petition 870160010078, of 03/22/2016, p. 22/52
    20/27 prepared, together with alloys with less Zn content, as described here, such as MgZn1Ca0.3, called ZX10, The alloys were also prepared with different degrees of purity: Conventional purity (CP), high purity (HP) and ultra high purity vacuum distilled (XHP). Reference can also be made to the ASTM B92 / B92M-11 standard designations. For the specific CP ZX50 sample described here, an Mg bar with a purity of 99.8% by weight was used. The purity of the HP and XHP samples is mentioned below.
    PREPARATION OF Mg ALLOYS [0056] For the production of HP ZX50, high purity Mg (99.98%), Ca (99.0%) and Zn (99.99%) were used. For the XHP, ZX50 and ZX10 alloys, high purity Mg (99.999%), Ca (99.99%) and Zn (99.999%) alloys were synthesized in a graphite crucible, under a protective gas mixture at 750 ° C . Subsequently, the molten product was poured into a conical graphite mold (average diameter of 55 mm, height approximately 150 mm), which was cooled with water at the bottom to force directional solidification, in order to avoid shrinkage cavities. Subsequently, the billets were homogenized, that is, treated with solution (alloys ZX50: 350 ° C / 12 h; alloy ZX10: 350 ° C / 12 h plus 450 ° C / 8 h), followed by cooling with pressurized air. The chemical compositions of certain samples were determined by luminescent discharge mass spectrometry (shown in Table 1).
    EXTRUSION PROCEDURE [0057] The homogenized alloys were machined for billets with a diameter of 50 mm and a length of 120 mm. For XHP ZX10, the billet was aged at 250 ° C for 30 min to create fine (precipitated) intermetallic particles and homogeneously distributed, before the extrusion process. Subsequently, the billet was heated to
    Petition 870160010078, of 03/22/2016, p. 23/52
    21/27
    300 ° C and indirect extrusion was performed at a speed and ram of 0.15 mm / s for a rod profile with a diameter of 10 mm, corresponding to an extrusion rate of 25: 1. Pressurized air cooling was applied to the outlet side of the extrusion press. For ZX50 alloys, extrusion to a diameter of 10 mm was performed by direct extrusion at 325 ° C. Indirect extrusion has been found to result in higher rates of dynamic recrystallization.
    [0058] To check the influence of trace elements on the degradation profile, ZX50 alloys were prepared using high purity Mg (HP) and ultra high purity Mg distilled under vacuum (XHP) (see WO2013 / 107644 on Mg vacuum distillation high purity, hereby incorporated by reference). The chemical composition, including reference to harmful elements, is provided in Table 1. The use of Mg XHP and Zn and Ca ultrapure in the synthesis of XHP ZX50 results in a reduction in the content of trace elements by a factor of about 100.
    TABLE 1. Chemical composition of ZX50 with conventional purity (CP), high purity (HP) and ultra-high purity (XHP).
    turns on Zn[% by weight] Ca [% by weight] Mn[pm] Si [pm] Fe [pm] Cu [pm] Ni[pm] Co [pm] CPZX50 5.24 0.27 1630 440 42 9 8 8 HPZX50 5.21 0.29 160 430 31 8 7 5 XHP 5.26 0.31 0.8 2.9 0.5 0.09 0.05 < ZX50 0.05
    IMMERSION TESTS [0059] The degradation of the alloys was measured by the hydrogen evolution method, as described in G. Song, A. Atrens, D.H. St John, Magnesium Technology Conference at TMS. New Orleans, LA, USA, (2001) 255 (hereby incorporated by reference) and evaluated using a test setup enhanced by our center, as
    Petition 870160010078, of 03/22/2016, p. 24/52
    22/27 described in M. Schinhammer, J. Hofstetter, C. Wegmann, F. Moszner, JF Loffler, PJ Uggowitzer, On the immersion testing of degradable implant materials in simulated body fluid: Active pH regulation using CO 2 Adv. Eng. Mater. 15 (20 13) 434-441 (incorporated herein by reference). The device exhibits a high gas volume resolution and has been specially designed for slow-degrading materials; it also takes into account daily fluctuations in atmospheric pressure and gas dissolution. Sample sizes were used with surface areas ranging from 259 ± 1 mm 2 to 626 ± 6.7 mm 2 . Three samples were tested per batch and their average hydrogen evolution was evaluated in ml / cm 2 . All data points were corrected for atmospheric pressure and gas dissolution. The ionic concentration of the SBF used for the immersion tests is described in AC Hanzi, I. Gerber, M. Schinhammer, JF Loffler, PJ Uggowitzer, On the in vitro and in vivo degradation performance and biological response of new biodegradable Mg-Y- Zn alloys Acta Biomater. 6 (2010) 18241833 (incorporated herein by reference); CO 2 (99.90% by volume) or Tris was used as a buffer. During the degradation test, the pH was maintained at 7.45 ± 0.017 with a temperature of 36.91 ± 0.30 ° C for two weeks. The samples were ground on abrasive SiC paper, 4000 granularity. Immediately before immersion, they were polished with a 1 pm polishing cloth, washed in an ultrasonic bath using isopropanol and dried with hot air.
    [0060] Figure 1, which shows the average evolution of hydrogen as a function of time for ZX50 alloys, of conventional purity y (CP), high purity (HP) and ultra-high purity (XHP), immersed in simulated body fluid ( SBF) buffering with CO 2 , with pH from 7.45 to 37 ° C (note the different scales on the x-axis; typical data dispersion is illustrated by error bars), illustrates the importance of the impurity content. The amounts of hydrogen increase steadily at the beginning,
    Petition 870160010078, of 03/22/2016, p. 25/52
    23/27 with a small reduction in the rate of degradation over time. The XHP ZX50 alloy evolves significantly less hydrogen than the CP and HP alloys within the same time interval. The significant improvement (after 2 weeks in more than an order of magnitude from CP to HP and a factor of approximately 3 from HP to XHP) can be attributed to the reduced content of trace elements and the related impediment of cathodic sites that cause degradation.
    [0061] The replacement of a CO 2 buffer by the organic compound Tris results in a higher rate of degradation and is followed by a change in the character of the corrosion morphology. For alloys in CO2-buffered SBF, a very homogeneous degradation is observed (Figure 3A), while in Tris-SBF there is a distinctive localized corrosion attack and the local attack is more pronounced in ZX50 alloys with rapid degradation (Figure 3B). However, such a change in the degradation morphology does not occur in Mg not incorporated into the alloy. Furthermore, there is only a very light localized attack on the XHP ZX10 (Figure 3C). These findings indicate an important influence of the composition of the alloy on the susceptibility to degradation in specific environments.
    [0062] Figure 3 illustrates the surface topography of samples after immersion in SBF, as follows: (a) XHP ZX50 does not show local corrosive attack after two weeks of immersion in SBF buffering with CO2 and (b) evident corrosive attack in buffered SBF with Tris after just 3 days; (c) there is no visible indication of local corrosive attack for XHP ZX10 after 2 weeks of immersion in Tris-buffered SBF.
    [0063] Figure 4A illustrates the constitution of Mg-Zn-Ca alloys at 300 ° C, that is, the temperature used for extrusion in the production of the ZX10 alloy (hot forming temperature). As used in Figures 4A and B, HCP means hexagonal-closed packaging and
    Petition 870160010078, of 03/22/2016, p. 26/52
    24/27 refers to the structure of the Mg matrix crystals. In order to avoid the formation of the ternary phase of Mg6Zn3Ca 2 , it is observed that the Zn content should be less than approximately 1.0% by weight, but to also use a certain degree of hardening of solid solution, 1%, by weight, it was chosen for the ZX10 alloy and the Ca content was evaluated together with the grain refining effect of the Mg2Ca particles. To produce a very fine particle size, a solution treatment was carried out, followed by an aging procedure below or at the hot formation temperature (see the extrusion method above). Figure 4B shows (a) the amplitude of the AT ST window (Zn and Ca are completely dissolved in Mg and the solidus temperature has not yet been reached) of the solution treatment, in a Zn content of 1%, by weight, and (b) the influence of the Ca content on the amplitude of the solution treatment window. In this case, 0.3% by weight of Ca was chosen. The constitution of the MgZn1Ca0.3 (ZX10) alloy with low zinc content is shown in Figure 4A. At 300 ° C, only the Mg 2 Ca phase is present. Mg 2 Ca and (Mg, Zn) 2 Ca are equivalent; Mg 2 Ca can contain a certain amount of Zn, without changing its nature. According to its Zener drag effect, the resulting grain size remains at low levels, ie approximately 2 pm (see the extrusion parameters above). The corresponding mechanical properties of the ZX10 alloy are as follows. Under tension: elastic limit (TYS) = 240 MPa, maximum tensile strength (UTS) = 255 MPa, elongation at break = 27%; under compression: elastic compression limit (CYS) = 205 MPa, maximum compressive strength (UCS) = 245 MPa, elongation at break = 13%. The stress and compression conditions are determined by ASTM or ISO standards (for example, DIN 50106 compression and DIN EN 10002-1 tension). The ZX10 alloy presents not only high strength and good ductility, but also low mechanical anisotropy.
    Petition 870160010078, of 03/22/2016, p. 27/52
    25/27 [0064] As shown in Figure 2, the good mechanical properties of the XHP ZX10 alloy are accompanied by excellent biocorrosion behavior. Figure 2 illustrates the in vivo degradation performance of the XHP ZX10 alloy (Figure 2B) compared to the CP ZX50 alloy (Figure 2A) after 12 weeks of implantation time. The fast-corroding CP ZX50 alloy has been completely degraded and severe bone irritation is observed, while the XHP ZX10 alloy exhibits a desired slow and homogeneous degradation. In this case, no hydrogen bubbles were observed clinically and the living organism was able to absorb the small amount of hydrogen generated, a fact that is highly significant from a medical perspective.
    LOW TEMPERATURE RECOVERY [0065] CP ZX10 alloy (which has the following impurities, as measured by optical emission spectroscopy (OES): Al: 229 ppm; Cu: 11 ppm; Fe: 32 ppm; Mn: 309 ppm; Ni : 10 ppm; Si: 323 ppm; and Zn: 47 ppm) and the XHP ZX10 alloy were prepared as described above for ZX10 alloys (i.e., MgZn1Ca0.3). After the extrusion procedure, the CP ZX10 and XHP ZX10 alloys were subjected to low temperature annealing at 200 ° C for 10 hours (h) and 100 hours (h) and immersion tests were performed, as described above, in buffered SBF with Tris. As shown in Figure 5, the rate of degradation of the alloys increases as the time of the low temperature annealing step increases. For example, alloys subjected to low temperature annealing for 100 h degrade at a faster rate than those subjected to low temperature annealing for 10 h. In addition, alloys that are subjected to low temperature annealing exhibit a higher rate of degradation compared to alloys that are not subjected to the low temperature annealing step (compare in the condition after extrusion with 10 h and 100 h). Additionally, Figure 5 shows that CP alloys degrade the
    Petition 870160010078, of 03/22/2016, p. 28/52
    26/27 a faster rate compared to XHP alloys, as a result of the low temperature annealing step. The results of low temperature annealing are further exemplified in Figures 6A and 6B, which show that alloys subjected to a low temperature annealing of 100 h degrade faster than alloys subjected to a low temperature annealing of 10 h after two weeks in Tris-buffered SBF, and both alloys degrade faster than alloys not subjected to low temperature annealing (in the condition after extrusion <10 h <100 h).
    [0066] As shown in Figure 7, low temperature annealing increases the grain size of the CP ZX10 and XHP ZX10 alloys. For example, CP ZX10 alloys in the post-extrusion condition exhibit a grain size of about 2 pm (data not shown), a grain size of about 3.0 pm after low temperature annealing for 10 h and a size of grain of about 3.4 pm after annealing at low temperature for 100 h. Similarly, XHP ZX10 alloys in the post-extrusion condition exhibit a grain size of about 2 pm (data not shown), a grain size of about 4.3 pm after low temperature annealing for 10 h and a size of about 4.5 pm after annealing at low temperature for 100 h. Therefore, in terms of grain size, after extrusion <10 h <100 h. In addition, after low temperature annealing, the grain size of XHP ZX10 alloys is larger than the grain size of CP ZX10 alloys. The error bars represent the standard deviation in Figures 5, 6 and 7.
    [0067] 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 intends
    Petition 870160010078, of 03/22/2016, p. 29/52
    27/27 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. 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.
    [0068] It should be understood that at least some of the descriptions of the invention have been simplified to focus on elements that are relevant to a clear understanding of the invention, while, for the sake of clarity, other elements have been eliminated, elements that skilled in the art will understand that they may 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.
    [0069] 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 (30)
    [1]
    1. MgZnCa alloy, characterized by the fact that it contains:
    nanoprecipitates and having a Zn content ranging from 0.1% by weight from Zn to 2.0% by weight from Zn; a Ca content ranging from 0.2% by weight of Ca to 0.5% by weight of Ca; less than 0.1%, by weight, of one or more other elements; and with the rest of the alloy being Mg;
    the nanoprecipitates being less noble than the remaining Mg.
    [2]
    2. MgZnCa alloy, according to claim 1, characterized by the fact that a portion of the one or more other elements are located in a secondary phase.
    [3]
    3. MgZnCa alloy according to claim 2, characterized by the fact that the one or more other elements located in a secondary phase represent less than 0.04%, by weight, of the composition.
    [4]
    MgZnCa alloy according to any one of claims 1 to 3, characterized in that the alloy composition contains less than 400 ppm in total other elements.
    [5]
    MgZnCa alloy according to any one of claims 1 to 4, characterized by the fact that the other elements comprise one or more of Fe, Cu, Ni, Co, Si, Mn, Al, Zr and P.
    [6]
    MgZnCa alloy according to any one of claims 1 to 5, characterized in that the alloy is substantially free of microgalvanic elements.
    [7]
    MgZnCa alloy according to any one of claims 1 to 6, characterized in that the precipitates comprise (Mg, Zn) 2Ca.
    [8]
    8. MgZnCa alloy, according to any of the
    Petition 870190065761, of 12/07/2019, p. 9/16
    2/5 claims 1 to 7, characterized by the fact that it further comprises precipitates that are more noble than the remaining Mg in which the precipitates comprise Mg6Zn3Ca2.
    [9]
    MgZnCa alloy according to any one of claims 1 to 8, characterized in that the alloy has a grain size of less than 5 pm.
    [10]
    MgZnCa alloy according to any one of claims 1 to 9, characterized by the fact that the alloy has an elastic limit of at least 180 MPa.
    [11]
    MgZnCa alloy according to any one of claims 1 to 10, characterized by the fact that the alloy has a maximum tensile strength of at least 240 MPa.
    [12]
    MgZnCa alloy according to any one of claims 1 to 11, characterized in that the alloy has at least 10% elongation at break.
    [13]
    13. Implant, characterized by the fact that it comprises the alloy as defined in any one of claims 1 to 12.
    [14]
    14. Implant, according to claim 13, characterized by the fact that the implant has an in vitro degradation rate of less than 0.5 mg / cm 2 per day, as measured in a simulated body fluid.
    [15]
    15. Implant, according to claim 13 or 14, characterized by the fact that the implant is an orthopedic implant.
    [16]
    16. Implant according to claim 15, characterized by the fact that the orthopedic implant comprises one or more of the following: a nail, a screw, a clamp, a plate, a nail, a tack, a pin, a pin for lock and an IM nail, an anchor, a pin, a plug, a fastener, a sleeve, a mesh, a transconector, a nut, a shaped body, a spinal cage, a cable, a K cable, a structure
    Petition 870190065761, of 12/07/2019, p. 10/16
    3/5 of fabric, a claw, a splint, a frame, a foam, and a honeycomb structure.
    [17]
    17. Implant, according to claim 13 or 14, characterized by the fact that the implant is a non-orthopedic implant.
    [18]
    18. Implant, according to claim 17, characterized by the fact that the non-orthopedic implant comprises a cardiovascular stent, a neurological stent, and a vertebroplasty stent.
    [19]
    19. Implant according to any of claims 13 to 18, characterized by the fact that the implant has a lower rate of degradation compared to implants made of magnesium alloy which contain microgalvanic elements.
    [20]
    20. An alloy production method as defined in any of claims 1 to 12, characterized by the fact that it comprises the steps of:
    (a) melting a mixture containing (i) magnesium with a purity of at least 99.96% by weight, (ii) from 0.1% by weight to 2.0% by weight of zinc, with a purity of at least 99.9% by weight; and (iii) from 0.2%, by weight, to 0.5%, by weight, of calcium, with a purity of at least 99.9%, by weight, to form a molten alloy;
    (b) perform heat treatment in molten alloy solution at two different temperatures, in which the first temperature is lower than a eutectic temperature of Mg-Zn and a second temperature is higher than a eutectic temperature of the ternary Mg-ZnCa system, thus , form an MgZnCa alloy containing 0.1% by weight of Zn to 2% by weight of Zn and a calcium content in the range of 0.2% by weight of Ca to 0.5 % by weight of Ca and having less than 0.1% by weight of one or more other elements, with the remainder being Mg,
    Petition 870190065761, of 12/07/2019, p. 11/16
    4/5 (c) perform thermal aging treatment between 100 ° C and 300 ° C to create dispersed nanoprecipitates; and (d) extruding the alloy in a desired shape to form a shaped alloy.
    [21]
    21. Method according to claim 20, characterized by the fact that the first temperature is 330 ° C to 370 ° C.
    [22]
    22. Method according to claim 20 or 21, characterized in that the second temperature is from 400 ° C to 460 ° C.
    [23]
    23. Method according to any of claims 20 to 22, characterized in that at least some of the one or more other elements are located in a secondary phase.
    [24]
    24. Method according to claim 23, characterized in that the one or more other elements located in a secondary phase represent less than 0.04%, by weight, of the composition.
    [25]
    25. Method according to any one of claims 20 to 24, characterized in that the alloy composition contains less than 400 ppm in total other elements.
    [26]
    26. Method according to any one of claims 20 to 25, characterized in that the other elements comprise one or more of Fe, Cu, Ni, Co, Si, Mn, Al, Zr, and P.
    [27]
    27. Method according to any one of claims 20 to 26, characterized in that it further comprises the step of carrying out a second heat treatment of aging of the shaped alloy to improve its strength or ductility.
    Petition 870190065761, of 12/07/2019, p. 12/16
    5/5
    [28]
    28. Method according to any one of claims 20 to 27, characterized in that it further comprises the low temperature annealing step of the alloy formed at 150 ° C to 250 ° C.
    [29]
    29. Method according to claim 28, characterized by the fact that low temperature annealing is carried out at 200 ° C.
    [30]
    30. Method according to claim 28 or 29, characterized in that the annealing at low temperature is carried out for 1 hour to 100 hours.
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    同族专利:
    公开号 | 公开日
    KR102253200B1|2021-05-21|
    US20160022876A1|2016-01-28|
    CA2906419A1|2014-10-02|
    CN105143483B|2017-11-10|
    KR20150130488A|2015-11-23|
    JP2019081957A|2019-05-30|
    JP6840716B2|2021-03-10|
    EP2971206A1|2016-01-20|
    WO2014159328A1|2014-10-02|
    JP6502315B2|2019-04-17|
    BR112015022632A2|2017-07-18|
    US10478529B2|2019-11-19|
    CN105143483A|2015-12-09|
    JP2016519209A|2016-06-30|
    CA2906419C|2021-07-06|
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    法律状态:
    2018-11-13| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2019-05-14| B07A| Technical examination (opinion): publication of technical examination (opinion) [chapter 7.1 patent gazette]|
    2019-11-12| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2020-01-07| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 11/03/2014, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    US201361783554P| true| 2013-03-14|2013-03-14|
    US61/783,554|2013-03-14|
    US201361909100P| true| 2013-11-26|2013-11-26|
    US61/909,100|2013-11-26|
    US201461942951P| true| 2014-02-21|2014-02-21|
    US61/942,951|2014-02-21|
    PCT/US2014/023047|WO2014159328A1|2013-03-14|2014-03-11|Magnesium alloy with adjustable degradation rate|
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