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WO2017084363A1 - Matériau médical dégradable d'alliage zn-cu-cx et procédé pour le préparer - Google Patents

Matériau médical dégradable d'alliage zn-cu-cx et procédé pour le préparer Download PDF

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Publication number
WO2017084363A1
WO2017084363A1 PCT/CN2016/089733 CN2016089733W WO2017084363A1 WO 2017084363 A1 WO2017084363 A1 WO 2017084363A1 CN 2016089733 W CN2016089733 W CN 2016089733W WO 2017084363 A1 WO2017084363 A1 WO 2017084363A1
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alloy
degradable
alloy material
medically
raw material
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Chinese (zh)
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黄华
袁广银
丁文江
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Shanghai Jiao Tong University
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Shanghai Jiao Tong University
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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
    • A61L31/02—Inorganic materials
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C18/00—Alloys based on zinc
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C18/00—Alloys based on zinc
    • C22C18/02—Alloys based on zinc with copper as the next major constituent

Definitions

  • the invention relates to a Zn-based alloy material in the field of biomedical materials which can be completely degraded in vivo, and in particular relates to a medical degradable Zn-Cu-X alloy material and a preparation method thereof.
  • biodegradable absorbent materials have become an important direction for the development of biomaterials.
  • biodegradable absorbent materials for clinical applications are mainly polymers and certain ceramic materials, such as polylactic acid, calcium phosphate and the like.
  • ceramic materials such as polylactic acid, calcium phosphate and the like.
  • degradable metal-based medical biomaterials have received special attention.
  • the introduction of such new metal-based degradable medical biomaterials has changed the traditional concept of metal-based implant materials, that is, using bioactive materials as metals.
  • Implant material At present, there are three main types of degradable metal-based biomaterials: iron-based, magnesium-based, and zinc-based alloys. They skillfully utilize the corrosion-prone properties of these alloys in the human environment to achieve the degradation of metal implanted devices in the body until The medical purpose of the disappearance eventually disappeared. At the same time, because they are metal-based materials, their strength, plasticity, stiffness, and processing properties are far superior to those of polylactic acid and other degradable polymer materials that have been used in clinical medicine. More suitable for clinical applications in orthopedic and cardiovascular interventional stents.
  • the degradation rate of iron-based biomaterials is relatively slow; while the degradation rate of magnesium-based biomaterials is relatively fast, so magnesium-based biomaterials often need to be surface modified to reduce their degradation.
  • Velocity; the degradation rate of zinc-based biomaterials is between the above two types of biomaterials, and its corrosion rate is the easiest to meet clinical needs.
  • zinc is one of the essential trace elements in the human body. The zinc content in adults is 1.4-2.3 g, and the dietary allowance for zinc in healthy adults is 15-40 mg per day. Therefore, zinc has good biocompatibility.
  • the mechanical properties of pure zinc are poor, strength And plasticity can not meet the requirements of implantation.
  • the present invention provides a medical biodegradable zinc alloy and a method of preparing the same.
  • the zinc alloy is alloyed by selecting an alloying element which is harmless or poisonous to the human body, and then the alloyed zinc alloy is subjected to heat treatment and plastic deformation processing to obtain a degradable zinc alloy medical biomaterial which meets clinical needs.
  • the invention provides a medically degradable Zn-Cu-X alloy material, the alloy material comprising the following weight percentage elements: 1 ⁇ Cu ⁇ 10%, 0 ⁇ X ⁇ 4%, the balance being zinc;
  • the element X is a mixture of one or more of Mg, Ca, Sr, Si, Fe, Mn, Ag, Y, Nd, Gd, Er, Ho or Dy.
  • the X is Mg, Fe, Ag, Nd, Gd.
  • the excessive Cu content leads to a decrease in the comprehensive mechanical properties of the alloy material, and at the same time, the corrosion degradation rate of the alloy is greatly increased; when the Cu content is too low (the Cu content is less than 1%) alloy The lower elongation results in the difficulty in processing the alloy during the preparation of the medical implant device, and the alloy content is too low, so that the antibacterial effect of the alloy is not obvious.
  • the invention also provides a preparation method of a medical degradable Zn-Cu-X alloy material, comprising the following steps:
  • Step S1 The alloying element ratio according to claim 1 is used to weigh each raw material
  • Step S2 sequentially heating and melting the pure zinc, the Cu-containing raw material, and the X-containing raw material, and uniformly stirring to form an alloy melt;
  • Step S3 The alloy melt is refined, allowed to stand, and cooled after casting to obtain a medically degradable Zn-Cu-X alloy material.
  • the Cu-containing raw material is a pure Cu or Cu-Zn intermediate alloy; and the X-containing raw material is one or more of pure X, Zn-X intermediate alloy or Cu-X intermediate alloy.
  • the Cu-containing raw material is a Cu-Zn intermediate alloy; and the X-containing raw material is a Zn-X intermediate alloy.
  • step S2 the pure zinc, the Cu-containing raw material, and the X-containing raw material are sequentially heated and melted.
  • the body is: first, the pure zinc is added to the melt, and when the temperature of the melt rises to 530-550 ° C, the raw material containing Cu is added, and after the raw material containing Cu is completely melted, the raw material containing X is further added.
  • the X-containing raw material is added at 480 to 510 °C.
  • refining is performed using hexachloroethane, and the refining temperature is 500 ⁇ 20 °C.
  • the amount of hexachloroethane is from 0.2 to 0.3% by weight based on the total weight of the alloy melt.
  • the standing temperature is 500 ⁇ 20° C. and the standing time is 10-15 min.
  • the process of homogenizing the alloy material obtained in the step S3, and hot-rolling or rolling deformation is further included.
  • the homogenization treatment temperature is 350 to 380 ° C, the treatment time is 6 to 10 h; the hot extrusion temperature is 300 to 320 ° C, and the extrusion ratio is 9 to 30:1.
  • the invention can greatly improve the mechanical properties of the alloy by adding a certain amount of Cu element having antibacterial effect to the base Zn, and at the same time, the alloy has antibacterial and other biological effects in the living environment environment; and another component is added at the same time.
  • X which can improve the mechanical properties and corrosion degradation properties of Zn-Cu-based alloys by utilizing the biological effects of promoting bio-tissue repair, anti-inflammatory, or regulating alloy structure to further improve the mechanical properties and corrosion degradation properties of Zn-Cu-based alloys.
  • the invention relates to a multi-degradable Zn-based alloy material composed of fully bio-safe human nutrient elements Zn, Cu and X elements, which has good biocompatibility, excellent mechanical properties and controllable corrosion rate. It has important application potential in the field of medical degradable implant materials and has a good application prospect.
  • the present invention has the following beneficial effects:
  • Zinc-based alloy is selected as the degradable medical metal material. It is well known that zinc is the most essential trace element in the human body. Among them, zinc can promote cell renewal, enhance the body's immunity, and maintain the growth and development of the body. Zinc is a component of many proteins and nucleic acid synthetases and is the active center of hundreds of enzymes. Zinc is an insulin component and is a key factor in maintaining normal life. Therefore, zinc-based alloys have good biocompatibility. At the same time, the corrosion degradation rate of zinc alloy is between iron-based alloy and magnesium-based alloy, and its corrosion rate is most suitable for clinical application.
  • Copper alloy is selected as the main alloying element. Copper accounts for one-millionth of the body's weight, and each person contains about 100-150mg. Adults must consume 3 to 5 mg of copper per day to maintain a metabolic balance.
  • the physiological functions of copper mainly include the following aspects: 1) Maintaining normal hematopoietic function, which is manifested in the following two aspects: 1 promote the absorption and transportation of iron; 2 ceruloplasmin can promote the synthesis of heme and hemoglobin. 2) Maintain normal bones, blood vessels and skin. The copper enzyme lysyl oxidase promotes the crosslinking of collagen, elastin in bone, blood vessels and skin. 3) Maintain the health of the central nervous system.
  • Copper ions can induce endothelial growth factor, promote the proliferation of endothelial cells, accelerate the process of angiogenesis, but prevent the excessive proliferation of smooth muscle cells; and inhibit the effects of thrombosis, which can effectively reduce restenosis caused by vascular stents and the like. Rate (reference: GfHu. Copper enhances proliferation of human endothelial cells under culture [J]. Journal of Cellular Biochemistry. 1998, 69(3): 326-335.). 6) Copper ions can promote the formation and growth of bone tissue by promoting the deposition of collagen, which promotes osteogenesis (Reference: C. opposition, L.-J. Bordeleau, J. Barralet, CJ Doillon.
  • Copper ions have a bactericidal effect, which is of great value for implanting instruments, which can prevent infection after the device is implanted, thereby alleviating the pain and trouble of the patient.
  • Others Copper also affects many physiological, biochemical and pathophysiological processes such as cholesterol metabolism, myocardial oxidative metabolism, body defense function, and hormone secretion. Therefore, the copper element is selected as the main alloying element of the zinc-based alloy. On the one hand, the strength and plasticity of zinc increase the role of strengthening and toughening materials. On the other hand, during the degradation process, the release of trace copper ions is It has the above-mentioned beneficial biological functions for the human body.
  • the zinc alloy of the present invention is added with a beneficial alloying component X (X is one or more of Mg, Ca, Sr, Si, Fe, Mn, Ag, Y, Nd, Gd, Er, Ho and Dy).
  • X is one or more of Mg, Ca, Sr, Si, Fe, Mn, Ag, Y, Nd, Gd, Er, Ho and Dy.
  • the mixing of the species can further optimize the microstructure of the alloy by adjusting its content, thereby improving the mechanical properties and biocompatibility of the alloy, and appropriately controlling the corrosion degradation rate of the alloy.
  • the obtained tensile strength is 230-500 MPa
  • the yield strength is 180 MPa to 430 MPa
  • the elongation is 3 to 55% of the plate, the bar or the wire
  • the corrosion degradation rate is in the range of 0.02 to 1.0 mm/year.
  • the alloy belongs to the deformed zinc alloy, the plasticity is superior to the magnesium-based biomaterial, so it is very easy to process into an implanted device, and in particular, it can be conveniently processed into a stent for cardiovascular interventional therapy.
  • This embodiment designs a degradable medical Zn-Cu-X alloy material comprising the following alloy components by weight: Cu is 3%, Mg is 0.5%, and the balance is Zn.
  • the embodiment further relates to a method for preparing the foregoing degradable medical Zn-Cu-X alloy material, and the preparation method comprises the following steps:
  • the ratio of alloy raw materials is used.
  • pure Zn purity greater than 99.994%
  • H62 brass is added.
  • pure Mg pure Mg (purity greater than 99.99%) at 500 ° C, then moderately stir the alloy melt and refine it with hexachloroethane, and let stand Casting is carried out after 10 to 15 minutes. After the temperature was lowered to 200 ° C or lower, the mold was opened, and the sample was taken out and water-cooled to obtain an ingot blank.
  • the blank was homogenized at 350 ° C for 8 hours, and then turned into a cylindrical ingot having a diameter of 60 mm, and then extruded at 280 ° C to a ratio of 9:1 and water-cooled to obtain a Zn-Cu-Mg alloy rod.
  • the alloy yield strength was 425 MPa
  • the breaking strength was 430 MPa
  • the elongation was about 3%
  • the corrosion degradation rate in the simulated body fluid hanks' at 37 ° C was 0.03 mm/year.
  • the alloy has high strength and relatively low elongation, and contains Mg and Cu elements to promote bone proliferation and healing, and is suitable for making some orthopedic degradable implantable instruments.
  • This embodiment designs a degradable medical Zn-Cu-X alloy material comprising the following alloy components by weight: Cu is 6%, Gd is 0.1%, and the balance is Zn.
  • the embodiment further relates to a method for preparing the foregoing degradable medical Zn-Cu-X alloy material, and the preparation method comprises the following steps:
  • the ratio of alloy raw materials is used.
  • pure Zn purity greater than 99.994%
  • H62 brass is added.
  • Zn-30% Gd master alloy After the intermediate alloy is completely melted, the alloy melt is moderately stirred and hexachloroethane is used. Refining, and letting it sit for 10 to 15 minutes. After the temperature is lowered to below 200 ° C, open The mold was taken out and the sample was taken out and water-cooled to obtain an ingot blank.
  • the blank was homogenized at 360 ° C for 8 hours, and then turned into a cylindrical ingot having a diameter of 60 mm, and then extruded at 300 ° C to a ratio of 20:1 and water-cooled to obtain a Zn-Cu-Gd alloy rod.
  • the alloy yield strength is 290 MPa
  • the breaking strength is 320 MPa
  • the elongation is about 45%
  • the corrosion degradation rate in the simulated body fluid hanks' at 37 ° C is 0.3 mm/year.
  • the alloy has excellent plasticity and better. Strength, easy to process into degradable implantable instruments of different sizes and shapes.
  • This embodiment designs a degradable medical Zn-Cu-X alloy material comprising the following alloy components by weight: 2% Cu, 0.6% Mg, 0.03% Gd, and the balance Zn.
  • the embodiment further relates to a method for preparing the foregoing degradable medical Zn-Cu-X alloy material, and the preparation method comprises the following steps:
  • the ratio of alloy raw materials is used.
  • pure Zn (purity greater than 99.994%) is heated and melted in the crucible.
  • H62 yellow is added in sequence.
  • pure Mg (purity greater than 99.99%) is added at 500 ° C, followed by melting of the alloy.
  • the body was moderately stirred and refined with hexachloroethane and allowed to stand for 10 to 15 minutes before pouring.
  • the mold was opened, and the sample was taken out and water-cooled to obtain an ingot blank.
  • the blank was homogenized at 370 ° C for 8 hours, it was turned into a cylindrical ingot with a diameter of 60 mm, and then extruded at 300 ° C for 9:1 extrusion and water cooling to obtain a Zn-Cu-Mg-Gd alloy rod. material.
  • the alloy yield strength is 390 MPa
  • the breaking strength is 410 MPa
  • the elongation is about 23%
  • the corrosion degradation rate in the simulated body fluid hanks' at 37 ° C is 0.08 mm/year.
  • the alloy has moderate plasticity and good strength value. It is suitable for the preparation of medical implantable devices with certain requirements for plasticity and strength.
  • This embodiment designs a degradable medical Zn-Cu-X alloy material comprising the following alloy components by weight: 2% Cu, 0.1% Ag, and the balance Zn.
  • the embodiment further relates to a method for preparing the foregoing degradable medical Zn-Cu-X alloy material, and the preparation method comprises the following steps:
  • the ratio of alloy raw materials is used.
  • pure Zn purity greater than 99.994%
  • H62 yellow is added in sequence.
  • Copper (Cu-38wt.%Zn master alloy), after the intermediate alloy is completely melted, then add Zn-40wt.%Ag (impurity content less than 0.01%) at 500 ° C, after it is completely melted, the alloy melt Stirring was carried out, and refining was carried out with hexachloroethane, and then allowed to stand for 10 to 15 minutes, followed by pouring.
  • the mold was opened, and the sample was taken out and water-cooled to obtain an ingot blank.
  • the blank was homogenized at 370 ° C for 8 hours, and then turned into a cylindrical ingot having a diameter of 60 mm, and then extruded at 310 ° C to a ratio of 9:1 and water-cooled to obtain a Zn-Cu-Ag alloy rod.
  • the alloy yield strength was 360 MPa
  • the breaking strength was 395 MPa
  • the elongation was about 17%
  • the corrosion degradation rate in the simulated body fluid hanks' at 37 ° C was 0.6 mm/year.
  • the alloy has high strength and good elongation, and has good antibacterial effect due to the inclusion of Ag and Cu elements, and is suitable for producing some special degradable implantable instruments which have high requirements on antibacterial performance.
  • This comparative example designs a Zn-X alloy material comprising the following alloy components by weight: 1% Mg and the balance Zn.
  • the present comparative example also relates to a method for preparing the aforementioned degradable medical Zn-X alloy material, and the preparation method comprises the following steps:
  • the ratio of the alloy raw materials is used.
  • pure Zn purity greater than 99.994%
  • pure Mg purity greater than 99.996%
  • the alloy melt was moderately stirred and refined with hexachloroethane and allowed to stand for 10 to 15 minutes before pouring. After the temperature was lowered to 200 ° C or lower, the mold was opened, and the sample was taken out and water-cooled to obtain an ingot blank.
  • the blank was homogenized at 350 ° C for 8 hours, and then turned into a cylindrical ingot having a diameter of 60 mm, and then extruded at 280 ° C to a ratio of 9:1 and water-cooled to obtain a Zn-Mg alloy rod.
  • the alloy yield strength was 387 MPa
  • the breaking strength was 402 MPa
  • the elongation was about 2%
  • the corrosion degradation rate in the simulated body fluid hanks' at 37 ° C was 0.13 mm/year.
  • the alloy has high strength and very low elongation, which makes the alloy material inconvenient to be plastically processed into a desired product, and does not contain Cu element, so that the antibacterial effect of the material is not obvious.
  • the comprehensive performance of Zn-1%Mg alloy is inferior to that of Zn-4%Cu-1%Mg, especially the plasticity and antibacterial properties of the material lead to unsatisfactory implementation.
  • This comparative example designs a degradable medical Zn-Cu-X alloy material comprising the following alloy components by weight: 4% Cu, 5% Mg, and the balance Zn.
  • the present comparative example also relates to a method for preparing the aforementioned degradable medical Zn-Cu-X alloy material, and the preparation method comprises the following steps:
  • the ratio of alloy raw materials is used.
  • pure Zn purity greater than 99.994%
  • H62 brass is added.
  • pure Mg pure Mg (purity greater than 99.99%) at 500 ° C, then moderately stir the alloy melt and refine with hexachloroethane, and quiet Casting is carried out after 10 to 15 minutes.
  • the mold was opened, and the sample was taken out and water-cooled to obtain an ingot blank.
  • the blank was homogenized at 350 ° C for 8 hours, and then turned into a cylindrical ingot having a diameter of 60 mm, and then extruded at 280 ° C to a ratio of 9:1 and water-cooled to obtain a Zn-Cu-Mg alloy rod.
  • the alloy yield strength was 460 MPa
  • the breaking strength was 480 MPa
  • the elongation was about 1%
  • the corrosion degradation rate in the simulated body fluid hanks' at 37 ° C was 0.73 mm/year.
  • the alloy has high strength and very low elongation, is difficult to process into a desired medical device implant product, and is prone to brittle fracture, and the implementation effect is not satisfactory.
  • This comparative example designs a degradable medical Zn-Cu-X alloy material comprising the following alloy components by weight: 15% Cu, 0.1% Gd, and the balance Zn.
  • the present comparative example also relates to a method for preparing the aforementioned degradable medical Zn-Cu-X alloy material, and the preparation method comprises the following steps:
  • the ratio of alloy raw materials is used.
  • pure Zn purity greater than 99.994%
  • H62 brass is added.
  • Zn-30% Gd master alloy After the intermediate alloy is completely melted, the alloy melt is moderately stirred and hexachloroethane is used. Refining, and letting it sit for 10 to 15 minutes. After the temperature was lowered to 200 ° C or lower, the mold was opened, and the sample was taken out and water-cooled to obtain an ingot blank.
  • the blank is homogenized at 360 ° C for 8 hours, it is turned into a cylindrical ingot with a diameter of 60 mm, and then extruded at 300 ° C for 20:1 extrusion. Water-cooled to obtain a Zn-Cu-Gd alloy rod.
  • the alloy yield strength is 260MPa
  • the breaking strength is 310MPa
  • the elongation is about 28%
  • the corrosion degradation rate in the simulated body fluid hanks' at 37 °C is 0.27mm/year.
  • the alloy still has excellent plasticity and better.
  • Strength but the mechanical properties of the alloy are reduced compared to the Zn-6Cu-0.1Gd (wt.%) alloy in Example 2, and the alloy cost is also improved due to the large addition of Cu.
  • the performance of the implementation is higher, but the performance of the resulting material is reduced. Therefore, the content of the main alloying element Cu should preferably be 1 ⁇ Cu ⁇ 10%.

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Abstract

L'invention concerne un matériau médical dégradable d'alliage Zn-Cu-X et un procédé pour le préparer. Le matériau d'alliage comprend, en pourcentage en poids, Cu : 1 ≤ Cu ≤ 10 %, X : 0 ≤ X ≤ 4 % et le complément en Zn, X représentant un ou plusieurs éléments parmi Mg, Ca, Sr, Si, Fe, Mn, Ag, Y, Nd, Gd, Er, Ho ou Dy. L'invention concerne également la préparation du matériau d'alliage. Le matériau d'alliage à base de Zn dégradable multiélément composé de Zn, de Cu et de X qui sont des éléments nutriments pour l'homme biologiquement sans danger, présente une bonne biocompatibilité, d'excellentes propriétés mécaniques et une vitesse de corrosion ajustable, et une bonne perspective d'application dans le domaine des matériaux médicaux implantés biodégradables.
PCT/CN2016/089733 2015-11-16 2016-07-12 Matériau médical dégradable d'alliage zn-cu-cx et procédé pour le préparer Ceased WO2017084363A1 (fr)

Applications Claiming Priority (2)

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CN201510785360.1A CN106702212A (zh) 2015-11-16 2015-11-16 医用可降解Zn-Cu-X合金材料及其制备方法
CN201510785360.1 2015-11-16

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