Zinc suture button

By using degradable zinc alloy materials and microarc oxidation treatment technology, loop zinc plates were prepared, which solved the problem of permanent metallic loop plates in the prior art requiring a second surgical removal, and achieved efficient bone healing and Soft tissue fixation reduces medical costs and patient recurrence rates.

WO2024251261A1PCT designated stage expired Publication Date: 2024-12-12BEIJING SHINING BIOMATERIALS CO LTD

Patent Information

Application Number
PCT/CN2024/098090
Authority / Receiving Office
WO · WO
Patent Type
Applications
Current Assignee / Owner
Priority Date
2023-06-09
Filing Date
2024-06-07
Publication Date
2024-12-12

AI Technical Summary

Technical Problem

The existing permanent medical metal belt loop plate needs to be removed for a second surgical procedure after the injured tissue heals, resulting in increased medical costs and patient incidence, and is not degradable, affecting the recovery of soft tissues such as knee ligaments.

Method used

A loop zinc plate made of a degradable zinc alloy material contains Zn and other elements such as Mn, Mg, Li, Ti, Cu, Ca, Sr, Fe, Ag, Co, Cr, Ce, Zr, Ge and Sn, through microarc oxidation treatment and chemical conversion coating techniques, make the first surface degradation rate greater than the second surface, release substances that contribute to bone healing, improve the healing speed in the bone tract and maintain the fixation effect.

Benefits of technology

The loop zinc plate releases substances that help bone tissue heal during the degradation process, speeding up the healing speed, while avoiding the overall degradation rate being too fast affecting the soft tissue fixation effect, reducing medical costs and patient recurrence rates.

✦ Generated by Eureka AI based on patent content.

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Abstract

The present application relates to a zinc suture button. The material of the zinc suture button comprises at least one of Mn, Mg, Li, Ti, Cu, Ca, Sr, Fe, Ag, Co, Cr, Ce, Zr, Ge and Sn, and, on the basis of weight percentages, comprises 0.01wt.%-10wt.% of Mn, 0.01wt.%-8.5wt.% of Mg, 0.1wt.%-1.5wt.% of Li, 0.01wt.%-5wt.% of Ti, 0.1wt.%-2.75wt.% of Cu, 0.01wt.%-5wt.% of Ca, 0.01wt.%-5wt.% of Sr, 0.01wt.%-5wt.% of Fe, 0.01wt.%-10wt.% of Ag, 0.01wt.%-5wt.% of Co, 0.01wt.%-5wt.% of Cr, 0.01wt.%-10wt.% of Ce, 0.01wt.%-5wt.% of Zr, 0.01wt.%-5wt.% of Ge and 0.01wt.%-5wt.% of Sn, with the balance being Zn. The material of the zinc suture button has an elongation rate of greater than or equal to 20%, a yield strength of greater than or equal to 250 MPa, and a tensile strength of greater than or equal to 300 MPa. The zinc suture button is made of a medical degradable zinc alloy material. The zinc suture button comprises a first surface and a second surface, the first surface being used for being attached to a bone surface, and the degradation rate of the first surface being greater than that of the second surface.
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Description

Zinc plate with loop Technical Field

[0001] The present application relates to the technical field of medical devices, and in particular to a zinc plate with a loop. Background Art

[0002] Long-term, high-speed, and intense exercise, as well as car accidents, falls, and sprains, can all lead to anterior cruciate ligament (ACL) damage or rupture. This damage disrupts the connection between the tibia and femur, creating instability in the knee joint. This damage can also damage the meniscus and cartilage in the knee joint. Furthermore, this can lead to loss of knee mobility and the potential for serious soft tissue diseases such as knee ligament damage.

[0003] Existing implants with loops, made of permanent medical metals like stainless steel and titanium alloys, are corrosion-resistant and mechanically stable, but they are not biodegradable. Therefore, a second surgery is required to remove the implant after the injured tissue has healed, which increases medical costs and patient morbidity.

[0004] Therefore, it is necessary to provide a new technical solution to at least one of the above technical problems.

[0005] Summary of the Invention

[0006] One purpose of this application is to provide a new technical solution for zinc plate with loops.

[0007] According to a first aspect of the present application, a zinc plate with a tab is provided. The material of the zinc plate includes, in addition to Zn, at least one of Mn, Mg, Li, Ti, Cu, Ca, Sr, Fe, Ag, Co, Cr, Ce, Zr, Ge, and Sn. Calculated by weight percentage, the Mn is 0.01wt.% to 10wt.%, the Mg is 0.01wt.% to 8.5wt.%, the Li is 0.1wt.% to 1.5wt.%, the Ti is 0.01wt.% to 5wt.%, the Cu is 0.1wt.% to 2.75wt.%, the Ca is 0.01wt.% to 5wt.%, the Sr is 0.01wt.% to 5wt.%, the Fe is 0.01wt.% to 5wt.%, the Ag is 0.01wt.% to 10wt.%, the Co is 0.01wt.% to 5wt.%, and the Cr is 0.01wt.% to 5wt.%. , the Ce is 0.01wt.%~10wt.%, the Zr is 0.01wt.%~5wt.%, the Ge is 0.01wt.%~5wt.%, the Sn is 0.01wt.%~5wt.%, and Zn is the balance; the elongation of the material of the zinc plate with loops is greater than or equal to 20%, the yield strength is greater than or equal to 250MPa, and the tensile strength is greater than or equal to 300MPa; the zinc plate with loops is made of medical degradable zinc alloy, and the zinc plate with loops includes a first surface and a second surface, the first surface and the second surface are arranged back to back, the first surface is used to be close to the bone surface, and the degradation rate of the first surface is greater than the degradation rate of the second surface.

[0008] Optionally, the material of the zinc plate with loop (1) includes, in addition to Zn, the following:

[0009] Mn, Cu and Ag are configured to improve the ductility of the zinc-tab plate;

[0010] Mg, Li, Cu, Ca and Fe, configured to increase the strength of the zinc ring plate; or

[0011] Mg, Ca and Sr, formulated to enhance osteogenic properties.

[0012] Optionally, Mn, Mg, Li, Ti, Cu, Ca, Sr, Fe, Ag, Co, Cr and Ce elements all undergo eutectic reaction within the above element range to form nanoscale densely distributed MnZn13 phase, Mg2Zn11 phase, LiZn4 phase, TiZn16 phase, Cu5Zn8 phase, CaZn13 phase, SrZn13 phase, FeZn13 phase, Ag5Zn8 phase, CoZn13 phase, CrZn19 phase and CeZn3 phase;

[0013] Sn, Si, Se, and Ge elements do not react with the Zn matrix to form intermetallic compounds, and a uniform alloy is obtained through eutectic reaction.

[0014] The manner of making the degradation rate of the first surface (11) greater than the degradation rate of the second surface (12) includes at least one of the following manners.

[0015] Optionally, the first surface has a plurality of micro protrusions distributed in an array. Preferably, when the first surface (11) has a plurality of micro protrusions distributed in an array, the substance released by the first surface is Zn 2+ Mg 2+ 、Mn 2+ , Ca 2+ 、Sr 2+ or Li + .

[0016] Optionally, the first surface is a frosted surface.

[0017] Optionally, a coating for accelerating degradation of the first surface is formed on the first surface.

[0018] Optionally, the coating is a chemical conversion coating formed by immersing the first surface in a saturated NaHCO 3 solution.

[0019] Optionally, the first surface is a surface treated with micro-arc oxidation.

[0020] Optionally, the electrolyte for micro-arc oxidation treatment includes KOH, NaHCO3 and NaF; wherein the concentration of KOH is 0.5g / L to 3g / L, the concentration of NaHCO3 is 10g / L to 60g / L, and the concentration of NaF is 0g / L to 60g / L.

[0021] Optionally, the electrolyte for the micro-arc oxidation treatment includes NaOH and hydrated calcium glycerophosphate; wherein the concentration of the NaOH is 0.5 g / L to 3 g / L, and the concentration of the hydrated calcium glycerophosphate is 1 g / L to 10 g / L.

[0022] Optionally, the electrolyte for micro-arc oxidation treatment includes Na2SiO3 and NaOH; wherein the concentration of Na2SiO3 is 10g / L to 60g / L, and the concentration of NaOH is 0.5g / L to 3g / L.

[0023] Optionally, the zinc plate with a loop (1) is in the shape of a plate, and the cross section of the zinc plate with a loop (1) is a rounded rectangle;

[0024] Optionally, the length of the zinc plate with a loop is 8 mm to 15 mm, and the thickness of the zinc plate with a loop is 1 mm to 3 mm.

[0025] Optionally, a lead-in hole and a wire loop hole are provided on the zinc plate with a loop, and a diameter of the lead-in hole is smaller than a diameter of the wire loop hole.

[0026] Optionally, the diameter of the lead hole is 1.4 mm to 1.6 mm, and the diameter of the wire loop hole is 1.8 mm to 2.0 mm.

[0027] Optionally, the lead-in holes and the wire loop holes are distributed along the length direction of the zinc plate with loops.

[0028] Optionally, a plurality of the lead holes and a plurality of the wire loop holes are provided on the zinc plate with loops.

[0029] Optionally, two lead holes and two wire loop holes are provided on the zinc plate with loops, and the two wire loop holes are located between the two lead holes.

[0030] Optionally, the surface of the zinc plate with loops, the lead holes and the wire loop holes are all chamfered.

[0031] According to a second aspect of the present application, a method for preparing a zinc alloy is provided. The zinc alloy is used to manufacture the above-mentioned zinc plate with a loop. The preparation method comprises:

[0032] The raw materials are placed into the crucible of the vacuum induction melting furnace according to the set weight percentage;

[0033] The vacuum induction melting furnace is evacuated to a vacuum degree of 5 Pa to 20 Pa;

[0034] A protective gas is introduced into the vacuum induction melting furnace, and a set vacuum degree is maintained in the vacuum induction melting furnace, wherein the protective gas is argon or nitrogen, and the set vacuum degree is 0.03 MPa-0.6 MPa;

[0035] The raw materials are heated in a crucible to form a metal melt, and the metal melt is brought into a clear state. During the heating process, the metal melt is electromagnetically stirred and refined and kept warm. The heating temperature is 400°C to 900°C, the holding temperature is 300°C to 600°C, and the holding time is 0.5 hours to 24 hours.

[0036] The molten metal is poured to form an ingot to be cast.

[0037] Optionally, the raw material used for smelting the zinc alloy has a purity of 99.9 wt.%;

[0038] The Zn and Cu raw materials are placed in a crucible of a vacuum induction melting furnace.

[0039] Optionally, the raw material used for smelting the zinc alloy has a purity of 99.9 wt.%;

[0040] The two raw materials, Zn and Fe, are placed in a crucible of a vacuum induction melting furnace.

[0041] Optionally, the raw material used for smelting the zinc alloy has a purity of 99.9 wt.%;

[0042] The three raw materials of Zn, Cu and Mg are placed in a crucible of a vacuum induction melting furnace.

[0043] In an embodiment of the present application, a bone tunnel is opened in the bone joint so that the first surface of the zinc plate with loops fits the bone surface, thereby fixing soft tissues such as ligaments. The first surface of the zinc plate with loops is treated so that the degradation rate of the first surface is greater than the degradation rate of the second surface. By increasing the degradation rate of the first surface, not only does the first surface of the zinc plate with loops release substances that contribute to bone tissue healing during the degradation process, thereby accelerating the healing rate of bone tissue in the bone tunnel. In addition, by utilizing the characteristic that the degradation rate of the second surface of the zinc plate with loops is slower than that of the first surface, the tissue is kept fixed by the zinc plate with loops in a state of accelerated healing, thereby avoiding the overall degradation rate of the zinc plate with loops being too fast, which affects the fixation effect of the soft tissue during the recovery process.

[0044] Other features and advantages of the present application will become apparent from the following detailed description of exemplary embodiments of the present application with reference to the accompanying drawings. BRIEF DESCRIPTION OF THE DRAWINGS

[0045] The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate embodiments of the present application and, together with the description, serve to explain the principles of the present application.

[0046] FIG1 is a perspective view of a zinc plate with a loop according to an embodiment of the present application;

[0047] FIG2 is a front view of a zinc plate with a loop according to an embodiment of the present application;

[0048] FIG3 is a top view of a zinc plate with a loop according to an embodiment of the present application.

[0049] Description of Reference Numerals

[0050] 1. Zinc plate with loop; 11. First surface; 12. Second surface; 13. Lead hole; 14. Wire loop hole. DETAILED DESCRIPTION

[0051] Various exemplary embodiments of the present application will now be described in detail with reference to the accompanying drawings. It should be noted that unless otherwise specifically stated, the relative arrangements of components and steps, numerical expressions and numerical values ​​set forth in these embodiments do not limit the scope of the present application.

[0052] The following description of at least one exemplary embodiment is merely illustrative in nature and is in no way intended to limit the present disclosure, its application, or uses.

[0053] Techniques and equipment known to ordinary technicians in the relevant art may not be discussed in detail, but where appropriate, the techniques and equipment should be considered part of the specification.

[0054] In all examples shown and discussed herein, any specific values ​​should be interpreted as merely exemplary and not limiting. Therefore, other examples of the exemplary embodiments may have different values.

[0055] It should be noted that like reference numerals and letters refer to like items in the following figures, and therefore, once an item is defined in one figure, it need not be further discussed in subsequent figures.

[0056] According to one embodiment of the present application, a zinc plate with a tab 1 is provided. The material of the zinc plate with a tab 1 includes at least one of Mn, Mg, Li, Ti, Cu, Ca, Sr, Fe, Ag, Co, Cr, Ce, Zr, Ge and Sn. Calculated by weight percentage, the Mn is 0.01wt.% to 10wt.%, the Mg is 0.01wt.% to 8.5wt.%, the Li is 0.1wt.% to 1.5wt.%, the Ti is 0.01wt.% to 5wt.%, the Cu is 0.1wt.% to 2.75wt.%, the Ca is 0.01wt.% to 5wt.%, the Sr is 0.01wt.% to 5wt.%, and the Fe is 0.01wt.% to 5wt.%, Ag is 0.01wt.% to 10wt.%, Co is 0.01wt.% to 5wt.%, Cr is 0.01wt.% to 5wt.%, Ce is 0.01wt.% to 10wt.%, Zr is 0.01wt.% to 5wt.%, Ge is 0.01wt.% to 5wt.%, Sn is 0.01wt.% to 5wt.%, and Zn is the balance. The material of the zinc-tab plate 1 has an elongation greater than or equal to 20%, a yield strength greater than or equal to 250MPa, and a tensile strength greater than or equal to 300MPa. The zinc plate with loops 1 is made of medical degradable zinc alloy. The zinc plate with loops 1 includes a first surface 11 and a second surface 12. The first surface 11 and the second surface 12 are arranged opposite to each other. The first surface 11 is used to be close to the bone surface. The degradation rate of the first surface 11 is greater than the degradation rate of the second surface 12.

[0057] In an embodiment of the present application, the zinc plate with a loop 1 is made of a medical degradable zinc alloy material. The medical degradable zinc alloy material includes Zn and at least one of Mn, Mg, Li, Ti, Cu, Ca, Sr, Fe, Ag, Co, Cr, Ce, Zr, Ge and Sn. Calculated in percentage by weight, Mn is 0.01wt.% to 10wt.%, Mg is 0.01wt.% to 8.5wt.%, Li is 0.1wt.% to 1.5wt.%, Ti is 0.01wt.% to 5wt.%, Cu is 0.1wt.% to 2.75wt.%, Ca is 0.01wt.% to 5wt.%, Sr is 0.01wt.% to 5wt.%, Fe is 0.01wt.% to 5wt.%, Ag is 0.01wt.% to 10wt.%, Co is 0.01wt.% to 5wt.%, Cr is 0.01wt.% to 5wt.%, Ce is 0.01wt.% to 10wt.%, Zr is 0.01wt.% to 5wt.%, Ge is 0.01wt.% to 5wt.%, and Sn is 0.01wt.% to 5wt.%.

[0058] Adding Mn, Cu, and Ag can improve the ductility of the zinc plate with loops 1. Adding Mg, Li, Cu, Ca, and Fe can improve the strength of the zinc plate with loops 1. Adding Ti, Zr, and Ge can improve the degradation uniformity of the zinc plate with loops 1. Adding Mg, Ca, and Sr can improve the osteogenic properties.

[0059] In the alloy of the present invention, the elements Mn, Mg, Li, Ti, Cu, Ca, Sr, Fe, Ag, Co, Cr, and Ce all undergo eutectic reactions within the aforementioned element ranges, forming densely distributed nanoscale MnZn13 phases, Mg2Zn11 phases, LiZn4 phases, TiZn16 phases, Cu5Zn8 phases, CaZn13 phases, SrZn13 phases, FeZn13 phases, Ag5Zn8 phases, CoZn13 phases, CrZn19 phases, and CeZn3 phases. These phases significantly enhance grain refinement. While elements such as Sn, Si, Se, and Ge do not react with the Zn matrix to form intermetallic compounds, the eutectic reaction still yields a uniformly structured alloy, thereby enhancing the strength of the zinc alloy.

[0060] In the embodiment of the present application, the method for preparing the zinc alloy includes:

[0061] The raw materials are placed into the crucible of the vacuum induction melting furnace according to the set weight percentage.

[0062] The vacuum induction melting furnace is evacuated to a vacuum degree of, for example, 5Pa-20Pa.

[0063] A shielding gas is introduced into the vacuum induction melting furnace to maintain a set vacuum level. The shielding gas may be argon or nitrogen. After the shielding gas is introduced, the vacuum level of the vacuum induction melting furnace is maintained at 0.03 MPa to 0.6 MPa.

[0064] The raw materials are heated in a crucible to form a metal melt. The metal melt is then brought to a clear state. During the heating process, the metal melt is electromagnetically stirred and refined and held. For example, the heating temperature is 400°C to 900°C, the holding temperature is 300°C to 600°C, and the holding time is 0.5 to 24 hours.

[0065] The molten metal is poured to form an ingot to be cast.

[0066] In one example, the zinc alloy 1 is prepared as follows:

[0067] The purity of the raw materials used for smelting zinc alloy is 99.9wt.%. A vacuum induction melting furnace is used to put the two raw materials, Zn and Cu, into the crucible of the melting furnace. Calculated by weight percentage, Cu is 1.33wt.%, and Zn is the balance. After closing the lid, start vacuuming. When the air pressure drops to about 10Pa, introduce protective gas and stop vacuuming. When argon gas is introduced into the furnace and the pressure reaches 0.04MPa, start power heating. When the temperature reaches 650℃, the metal melt reaches a clear state. While the metal melt reaches a clear state, electromagnetic stirring, refining and heat preservation are carried out. The heat preservation time is 1 hour, and pouring is carried out. The mold is made of high-purity graphite, and the cooling method is air cooling. After the ingot cools to room temperature, take it out and store it.

[0068] In one example, the preparation method of zinc alloy 2 is:

[0069] The purity of the raw materials used for smelting zinc alloy is 99.9wt.%. A vacuum induction melting furnace is used to put the two raw materials, Zn and Fe, into the crucible of the melting furnace. Calculated by weight percentage, Fe is 2.5wt.%, and Zn is the balance. After closing the lid, start vacuuming. When the air pressure drops to about 10Pa, introduce protective gas and stop vacuuming. When argon gas is introduced into the furnace and the pressure reaches 0.04MPa, start power heating. When the temperature reaches 700℃, the metal melt reaches a clear state. While the metal melt reaches a clear state, electromagnetic stirring, refining and heat preservation are carried out. The heat preservation time is 1.5 hours, and pouring is carried out. The mold is made of high-purity graphite, and the cooling method is air cooling. After the ingot cools to room temperature, take it out and store it.

[0070] In one example, the preparation method of zinc alloy 3 is:

[0071] The purity of the raw materials used for smelting zinc alloy is 99.9wt.%. A vacuum induction melting furnace is used to put the three raw materials Zn, Cu and Mg into the crucible of the melting furnace. Calculated by weight percentage, Cu is 1.33wt.%, Mg is 4.25wt.%, and Zn is the balance. After closing the lid, start vacuuming. When the air pressure drops to about 10Pa, introduce protective gas and stop vacuuming. When argon gas is introduced into the furnace and the pressure reaches 0.04MPa, start power heating. When the temperature reaches 500℃, the metal melt reaches a clear state. While the metal melt reaches a clear state, electromagnetic stirring, refining and heat preservation are carried out. The heat preservation time is 2 hours, and pouring is carried out. The mold is high-purity graphite and the cooling method is air cooling. After the ingot cools to room temperature, take it out and store it.

[0072] Of course, the preparation method of the zinc alloy is not limited to the above embodiment, and those skilled in the art can select the amount of various raw materials and the heating temperature according to actual needs.

[0073] As shown in Figure 1, the zinc plate with loops 1 in the embodiment of the present application is used to fix soft tissues of the knee joint, such as anterior cruciate ligament, meniscus injury, and cartilage injury. The zinc plate with loops 1 has a first surface 11 that fits with the bone surface, and a second surface 12 that is arranged opposite to the first surface 11. A bone channel is opened on the bone joint, and the zinc plate with loops 1 is fitted with the bone joint by adjusting the coil length, thereby fixing soft tissues such as ligaments. The first surface 11 of the zinc plate with loops 1 is fitted with the bone surface after processing. The degradation rate of the treated first surface 11 is greater than the degradation rate of the second surface 12. By accelerating the degradation rate of the first surface 11 of the zinc plate with loops 1, the substances released after degradation accelerate the healing of bone tissue. The degradation rate of the second surface 12 of the zinc plate with loops 1 is lower than the degradation rate of the first surface 11, which helps the zinc plate with loops 1 to continue to be fixed to the bone surface when the soft tissue is not completely healed, and prevents the overall degradation rate of the zinc plate with loops 1 from being too fast, affecting the fixation of unhealed ligaments and other soft tissues, and causing secondary damage to the patient.

[0074] In the embodiment of the present application, the first surface 11 of the zinc plate with loops 1 is bonded to the bone surface. The first surface 11 of the zinc plate with loops 1 is treated to degrade at a rate greater than that of the second surface 12. By increasing the degradation rate of the first surface 11, not only does the first surface 11 of the zinc plate with loops 1 release substances that aid bone healing during degradation, thereby accelerating bone healing, but the slower degradation rate of the second surface 12 of the zinc plate with loops 1 relative to the first surface 11 also allows the zinc plate with loops 1 to maintain bone tissue in a state of accelerated healing, preventing the zinc plate with loops 1 from degrading too quickly as a whole and affecting the fixation of soft tissues such as ligaments during recovery.

[0075] In one example, the first surface 11 has a plurality of micro protrusions distributed in an array.

[0076] By arranging multiple micro-protrusions on the first surface 11 of the zinc plate with loops 1 to increase the contact area between the first surface 11 and the bone surface, the bone surface can fully receive the substances released by the first surface 11 in the process of accelerating the degradation of the first surface 11, thereby improving the healing speed of bone tissue.

[0077] Of course, in the embodiment of the present application, the first surface 11 is not limited to the above structure, and those skilled in the art can configure it according to actual needs. For example, the first surface 11 is formed with a concave structure.

[0078] During the preparation process of the zinc plate with loop 1, different alloys are used to prepare the first surface 11 so that the substances released are different. The substances released from the first surface 11 can be Zn 2+ Mg 2+ 、Mn 2+ , Ca 2+ 、Sr 2+ or Li + wait.

[0079] For example, the substances released from the first surface 11 include Zn 2+ .Zn 2+ It can promote the differentiation of osteoblasts and inhibit bone resorption by osteoclasts by promoting bone marker genes such as alkaline phosphatase, type I collagen, osteocalcin, and osteopontin, which is beneficial to promoting bone formation and mineralization.

[0080] For example, the substances released from the first surface 11 include Mg 2+ Mg 2+ By participating in the activation of multiple enzymes in the human body, it can inhibit the nervous system, participate in protein synthesis, etc., which is beneficial to promote bone healing.

[0081] For example, the substances released from the first surface 11 include Mn 2+ .Mn 2+ It plays an important role in promoting human growth and development, regulating the endocrine system, participating in human bone hematopoiesis and human sugar and fat metabolism, accelerating protein synthesis, improving immune function, etc., which is beneficial to promoting bone healing.

[0082] For example, the substances released from the first surface 11 include Ca 2+ .Ca 2+ It is closely related to the body's bone growth, the stress response of the nervous system, and the body's normal coagulation function, and is beneficial to bone formation.

[0083] For example, the substances released from the first surface 11 include Sr 2+ . Sr 2+ It is an important component of the human skeleton, promoting new bone formation and facilitating bone defect repair.

[0084] For example, the substances released from the first surface 11 include Li + . Li + It promotes the osteogenic differentiation of bone marrow mesenchymal stem cells, thereby promoting bone repair.

[0085] Of course, in the embodiment of the present application, the first surface 11 is not limited to the substances released above, and those skilled in the art can select suitable raw materials to prepare the zinc plate with loop 1 according to actual needs.

[0086] Optionally, the first surface is a frosted surface.

[0087] Setting the first surface 11 as a frosted surface is beneficial to increasing the contact area between the first surface and the bone surface. In the process of accelerating the degradation of the first surface 11, the bone surface can fully receive the substances released by the first surface 11, thereby improving the healing speed of bone tissue.

[0088] In one example, a coating for accelerating degradation of the first surface 11 is formed on the first surface 11 .

[0089] By processing the first surface 11 of the zinc plate with a tab, a coating is formed on the first surface 11 to accelerate the degradation of the first surface 11 of the zinc plate with a tab, so that the degradation rate of the first surface 11 of the zinc plate with a tab is greater than the degradation rate of the second surface 12.

[0090] Of course, in the embodiment of the present application, the first surface 11 is not limited to the above structure, and those skilled in the art can configure it according to actual needs. For example, a substance that helps accelerate the degradation of the first surface 11 can be coated on the first surface 11 of the zinc plate with a loop.

[0091] In one example, the coating is a chemical conversion coating formed by immersing the first surface 11 in a saturated NaHCO 3 solution.

[0092] The zinc plate with tabs 1 is plate-shaped, with a rounded rectangular cross-section. It includes a first surface 11 and a second surface 12. The first surface 11 is in contact with the bone surface, and the second surface 12 is disposed opposite the first surface 11. The first surface 11 of the zinc plate 1, which is in contact with the bone surface, is immersed in a saturated NaHCO3 solution to form a chemical conversion coating on the first surface 11.

[0093] The degradation rate of the first surface 11, immersed in a supersaturated NaHCO solution, is greater than that of the second surface 12. During use, the first surface 11, which is in contact with the bone surface, releases substances that aid bone tissue healing during degradation, thereby accelerating bone tissue healing within the bone canal. Furthermore, by utilizing the slower degradation rate of the second surface 12 than the first surface 11, the slowly degrading portion of the zinc plate with loops 1 maintains the fixation effect on soft tissues such as ligaments while the first surface 11 degrades and accelerates bone tissue healing, preventing the zinc plate with loops 1 from degrading too quickly as a whole and affecting the fixation of soft tissues such as ligaments.

[0094] In one example, the first surface 11 is a surface that has been subjected to micro-arc oxidation treatment.

[0095] Micro-arc oxidation (MAO), also known as plasma electrolytic oxidation (PEO), is developed based on anodizing technology, and the coating formed is superior to anodizing.

[0096] After the first surface 11 of the zinc plate with a loop 1 is treated by micro-arc oxidation, the degradation rate of the first surface 11 is greater than the degradation rate of the second surface 12 .

[0097] In one example, the electrolyte for the micro-arc oxidation treatment includes KOH, Na2SiO3 and NaF; wherein the concentration of the KOH is 0.5g / L to 3g / L, the concentration of the NaHCO3 is 10g / L to 60g / L, and the concentration of the NaF is 0g / L to 60g / L.

[0098] In the embodiment of the present application, the first surface 11 of the zinc plate with a loop 1 is subjected to a micro-arc oxidation treatment, so that the degradation rate of the first surface 11 is greater than the degradation rate of the second surface 12 .

[0099] In this embodiment, the electrolyte for micro-arc oxidation treatment is KOH+Na2SiO3+NaF.

[0100] The concentration of KOH is 0.5 g / L to 3 g / L, the concentration of NaHCO3 is 10 g / L to 60 g / L, and the concentration of NaF is 0 g / L to 60 g / L. Micro-arc oxidation is performed in this electrolyte to form a coating on the first surface 11 of the zinc-tabbed plate 1, thereby accelerating the degradation rate of the first surface 11 of the zinc-tabbed plate 1 that is in contact with the bone.

[0101] In one example, the electrolyte for the micro-arc oxidation treatment includes NaOH and hydrated calcium glycerophosphate; wherein the concentration of the NaOH is 0.5 g / L to 3 g / L, and the concentration of the hydrated calcium glycerophosphate is 1 g / L to 10 g / L.

[0102] In the embodiment of the present application, the first surface 11 of the zinc plate with a loop 1 is subjected to a micro-arc oxidation treatment, so that the degradation rate of the first surface 11 is greater than the degradation rate of the second surface 12 .

[0103] In this embodiment, the electrolyte for micro-arc oxidation treatment is NaOH+hydrated calcium glycerophosphate.

[0104] The concentration of NaOH is 0.5 g / L to 3 g / L, and the concentration of hydrated calcium glycerophosphate is 1 g / L to 10 g / L. Micro-arc oxidation is performed in the electrolyte to form a coating on the first surface 11 of the zinc-tabbed plate 1, thereby accelerating the degradation rate of the first surface 11 of the zinc-tabbed plate 1 that is in contact with the bone.

[0105] In one example, the electrolyte for the micro-arc oxidation treatment includes Na2SiO3 and NaOH; wherein the concentration of the Na2SiO3 is 10g / L to 60g / L, and the concentration of the NaOH is 0.5g / L to 3g / L.

[0106] In the embodiment of the present application, the first surface 11 of the zinc plate with a loop 1 is subjected to a micro-arc oxidation treatment, so that the degradation rate of the first surface 11 is greater than the degradation rate of the second surface 12 .

[0107] In this embodiment, the electrolyte for micro-arc oxidation treatment is Na2SiO3+NaOH.

[0108] The concentration of Na2SiO3 is 10g / L to 60g / L, and the concentration of NaOH is 0.5g / L to 3g / L. Micro-arc oxidation is performed in the electrolyte to form a coating on the first surface 11 of the zinc-tabbed plate 1, thereby accelerating the degradation rate of the first surface 11 of the zinc-tabbed plate 1 that is in contact with the bone.

[0109] Of course, the electrolyte in the embodiments of the present application is not limited to the above components, and those skilled in the art can set it according to actual needs.

[0110] In one example, the length of the zinc plate with a loop 1 is 8 mm to 15 mm, and the thickness of the zinc plate with a loop 1 is 1 mm to 3 mm.

[0111] As shown in Figures 1 to 3, the zinc-tabbed sheet 1 is plate-shaped, with a rounded rectangular cross-section. The length of the zinc-tabbed sheet 1 ranges from 8 mm to 15 mm, preferably 12 mm. The thickness of the zinc-tabbed sheet 1 ranges from 1 mm to 3 mm, preferably 1.5 mm.

[0112] Of course, in the embodiment of the present application, the zinc plate with a loop 1 is not limited to the above dimensions, and those skilled in the art can set them according to actual needs.

[0113] In one example, a lead hole 13 and a wire loop hole 14 are formed on the zinc plate with loop 1 , and the diameter of the lead hole 13 is smaller than the diameter of the wire loop hole 14 .

[0114] In the embodiment of the present application, the zinc plate with loop 1 is connected to the ligament graft through the coil of the loop hole 14. Adjusting the coil size is beneficial to pulling and positioning the ligament graft in the bone canal. The zinc plate with loop 1 is fixed to the outside of the bone.

[0115] As shown in Figures 1 and 2, the zinc plate with loops 1 is provided with a lead-in hole 13 and a loop hole 14. A traction wire is passed through the lead-in hole 13 to form a coil, and the position of the zinc plate with loops 1 is adjusted by adjusting the coil size. The loop hole 14 allows the zinc plate with loops 1 to form a contact with the bone joint and connect with the ligament at the injured site.

[0116] The end of the traction wire is passed through the wire loop hole 14, so that the zinc plate with loop 1 is closely attached to the bone joint to form a support. In this embodiment, the zinc plate with loop 1 not only helps the ligaments at the injured area to form a connection and fix it, but also releases substances that promote bone healing through degradation of the zinc plate with loop 1, thereby promoting the healing of the bone joint.

[0117] In one example, the diameter of the lead hole 13 is 1.4 mm to 1.6 mm, and the diameter of the wire loop hole 14 is 1.8 mm to 2.0 mm.

[0118] As shown in Figures 1 and 2, the diameter of the lead hole 13 is smaller than the diameter of the wire loop hole 14. The diameter of the lead hole 13 is 1.4mm to 1.6mm, and the diameter of the lead hole 13 is preferably 1.5mm. The diameter of the wire loop hole 14 is 1.8mm to 2.0mm, and the diameter of the wire loop hole 14 is preferably 1.9mm.

[0119] Of course, in the embodiment of the present application, the diameters of the lead hole 13 and the wire loop hole 14 are not limited to the above dimensions, and those skilled in the art can set them according to actual needs.

[0120] In one example, the wire lead holes 13 and the wire loop holes 14 are distributed along the length direction of the zinc plate with loop 1 .

[0121] As shown in Figure 2, the zinc plate with tabs 1 is plate-shaped, with a rounded rectangular cross-section. Both the lead hole 13 and the tab hole are circular through-holes. The direction from the center of the lead hole 13 to the center of the tab hole 14 is the same as the length of the zinc plate with tabs 1.

[0122] The lead-in holes 13 and the wire loop holes 14 are arranged along the length direction of the zinc plate with loops 1, which helps to fix the zinc plate with loops 1 at a specified position through the pulling wire.

[0123] In one example, the zinc plate with loops 1 is provided with a plurality of wire lead holes 13 and a plurality of wire loop holes 14 .

[0124] The zinc plate with loops 1 is provided with a plurality of lead holes 13, which are conducive to adjusting the position of the zinc plate with loops 1 by means of a traction line. By adjusting the direction of the zinc plate with loops 1 by means of the traction line, the contact position between the first surface 11 of the zinc plate with loops 1 and the bone joint is adjusted.

[0125] The zinc plate with loops 1 is provided with multiple loop holes 14. A bone tunnel is created in the joint, and a tightening wire is connected to the zinc plate with loops 1 through the loop holes 14. By passing the tightening wire through the bone tunnel, the zinc plate with loops 1 is secured to the joint. A zinc plate with loops 1 with a different number of loop holes 14 can be selected for use according to different needs.

[0126] In one example, the zinc plate with loops 1 is provided with two lead holes 13 and two wire loop holes 14 , and the two wire loop holes 14 are located between the two lead holes 13 .

[0127] As shown in Figures 1 and 2, the zinc plate with loops 1 is provided with two lead holes 13 and two loop holes 14. The loop holes 14 are located between the lead holes 13. Placing the lead holes 13 at either end of the zinc plate 1 facilitates adjustment of the orientation and position of the zinc plate 1 against the joint using traction wires. The lead holes 13 allow for rough positioning of the zinc plate 1 against the joint, while the tightening wires in the loop holes 14 allow for precise positioning and tightening of the zinc plate 1 against the joint, securing the ligaments and other structures.

[0128] Of course, in the embodiment of the present application, the number of lead holes 13 and wire loop holes 14 is not limited to the above structure, and those skilled in the art can set them according to actual needs. For example, the number of lead holes 13 is two, the number of wire loop holes 14 is four, and the four wire loop holes 14 are located between the two lead holes 13.

[0129] In one example, the surface of the zinc plate with loop 1, the lead hole 13 and the wire loop hole 14 are all chamfered.

[0130] As shown in FIG1 to FIG3, the surface of the zinc plate with loop 1, the lead hole 13 and the wire loop hole 14 are all chamfered to prevent the sharp edges from causing damage to the patient's joint tissue and skin tissue.

[0131] The above embodiments focus on the differences between the various embodiments. As long as the different optimization features between the various embodiments are not contradictory, they can be combined to form a better embodiment. Considering the simplicity of the text, they will not be repeated here.

[0132] Although some specific embodiments of the present application have been described in detail by way of example, it should be understood by those skilled in the art that the above examples are for illustration only and are not intended to limit the scope of the present application. It should be understood by those skilled in the art that the above examples may be modified without departing from the scope and spirit of the present application. The scope of the present application is defined by the appended claims.

Claims

1. A zinc plate with loops, characterized in that: The material of the zinc plate (1) includes, in addition to Zn, at least one of Mn, Mg, Li, Ti, Cu, Ca, Sr, Fe, Ag, Co, Cr, Ce, Zr, Ge and Sn; Wherein, calculated by weight percentage, the Mn is 0.01wt.% to 10wt.%, the Mg is 0.01wt.% to 8.5wt.%, the Li is 0.1wt.% to 1.5wt.%, the Ti is 0.01wt.% to 5wt.%, the Cu is 0.1wt.% to 2.75wt.%, the Ca is 0.01wt.% to 5wt.%, the Sr is 0.01wt.% to 5wt.%, and the Fe is 0.01wt.% to 5wt.%, Ag is 0.01wt.% to 10wt.%, Co is 0.01wt.% to 5wt.%, Cr is 0.01wt.% to 5wt.%, Ce is 0.01wt.% to 10wt.%, Zr is 0.01wt.% to 5wt.%, Ge is 0.01wt.% to 5wt.%, Sn is 0.01wt.% to 5wt.%, and Zn is the balance; The material of the zinc plate with loop (1) has an elongation greater than or equal to 20%, a yield strength greater than or equal to 250 MPa, and a tensile strength greater than or equal to 300 MPa; The zinc plate with loops (1) is made of a medical degradable zinc alloy material, and comprises a first surface (11) and a second surface (12). The first surface (11) and the second surface (12) are arranged opposite to each other, and the first surface (11) is used to be close to the bone surface. The degradation rate of the first surface (11) is greater than the degradation rate of the second surface (12).

2. The zinc plate with loop according to claim 1, characterized in that: The material of the zinc plate with loop (1) includes, in addition to Zn, the following: Mn, Cu and Ag are configured to improve the ductility of the zinc-tab plate; Mg, Li, Cu, Ca and Fe, configured to increase the strength of the zinc ring plate; or Mg, Ca and Sr, formulated to enhance osteogenic properties.

3. The zinc plate with loop according to claim 1 or 2, characterized in that: Mn, Mg, Li, Ti, Cu, Ca, Sr, Fe, Ag, Co, Cr and Ce elements all have eutectic reactions in the above element ranges, forming nano-scale densely distributed MnZn13 phase, Mg2Zn11 phase, LiZn4 phase, TiZn16 phase, Cu5Zn8 phase, CaZn13 phase, SrZn13 phase, FeZn13 phase, Ag5Zn8 phase, CoZn13 phase, CrZn19 phase and CeZn3 phase; Sn, Si, Se, and Ge elements do not react with the Zn matrix to form intermetallic compounds, and a uniform alloy is obtained through eutectic reaction.

4. The zinc plate with loop according to any one of claims 1 to 3, characterized in that: The manner of making the degradation rate of the first surface (11) greater than the degradation rate of the second surface (12) includes at least one of the following manners: The first surface (11) has a plurality of micro protrusions distributed in an array; The first surface (11) is a frosted surface; The first surface (11) is formed with a coating for accelerating degradation of the first surface (11); or The first surface (11) is a surface that has been subjected to micro-arc oxidation treatment.

5. The zinc plate with loop according to claim 4, characterized in that: When the first surface (11) has a plurality of micro protrusions distributed in an array, the substance released by the first surface is Zn 2+ Mg 2+ 、Mn 2+ , Ca 2+ 、Sr 2+ or Li + .

6. The zinc plate with loop according to claim 4, characterized in that: The coating is a chemical conversion coating formed by immersing the first surface (11) in a saturated NaHCO3 solution.

7. The zinc plate with loop according to claim 4, characterized in that: The electrolyte for the micro-arc oxidation treatment includes KOH, NaHCO3 and NaF; Wherein, the concentration of KOH is 0.5 g / L to 3 g / L, the concentration of NaHCO3 is 10 g / L to 60 g / L, and the concentration of NaF is 0 g / L to 60 g / L.

8. The zinc plate with loop according to claim 4, characterized in that: The electrolyte for the micro-arc oxidation treatment includes NaOH and hydrated calcium glycerophosphate; Wherein, the concentration of the NaOH is 0.5 g / L to 3 g / L, and the concentration of the hydrated calcium glycerophosphate is 1 g / L to 10 g / L.

9. The zinc plate with loop according to claim 4, characterized in that: The electrolyte for the micro-arc oxidation treatment includes Na2SiO3 and NaOH; Wherein, the concentration of the Na2SiO3 is 10g / L to 60g / L, and the concentration of the NaOH is 0.5g / L to 3g / L.

10. The zinc plate with loop according to any one of claims 1 to 9, characterized in that: The zinc plate with a loop (1) is in the shape of a plate, and the cross section of the zinc plate with a loop (1) is a rounded rectangle; The length of the zinc plate with a loop (1) is 8 mm to 15 mm, and the thickness of the zinc plate with a loop (1) is 1 mm to 3 mm.

11. The zinc plate with loop according to claim 10, characterized in that: The zinc plate with loop (1) is provided with a lead-in hole (13) and a wire loop hole (14), and the diameter of the lead-in hole (13) is smaller than the diameter of the wire loop hole (14).

12. The zinc plate with loop according to claim 11, characterized in that: The diameter of the lead hole (13) is 1.4 mm to 1.6 mm, and the diameter of the wire loop hole (14) is 1.8 mm to 2.0 mm.

13. The zinc plate with loop according to claim 11, characterized in that: The lead-in holes (13) and the wire loop holes (14) are distributed along the length direction of the zinc plate with loop (1).

14. The zinc plate with loop according to claim 13, characterized in that: The zinc plate with loops (1) is provided with a plurality of lead holes (13) and a plurality of wire loop holes (14).

15. The zinc plate with loop according to claim 14, characterized in that: The zinc plate with loops (1) is provided with two lead holes (13) and two wire loop holes (14), and the two wire loop holes (14) are located between the two lead holes (13).

16. The zinc plate with loop according to claim 15, characterized in that: The surface of the zinc plate with loop (1), the lead-in hole (13) and the wire loop hole (14) are all chamfered.

17. A method for preparing a zinc alloy, wherein the zinc alloy is used to manufacture the zinc plate with a loop according to any one of claims 1 to 16, the method comprising: The raw materials are placed into the crucible of the vacuum induction melting furnace according to the set weight percentage; The vacuum induction melting furnace is evacuated to a vacuum degree of 5 Pa to 20 Pa; A protective gas is introduced into the vacuum induction melting furnace, and a set vacuum degree is maintained in the vacuum induction melting furnace, wherein the protective gas is argon or nitrogen, and the set vacuum degree is 0.03 MPa-0.6 MPa; The raw materials are heated in a crucible to form a metal melt and to make the metal melt reach a clear state. During the process, the metal melt is electromagnetically stirred and refined and kept warm. The heating temperature is 400° C. to 900° C., the holding temperature is 300° C. to 600° C., and the holding time is 0.5 hour to 24 hours. The molten metal is poured to form an ingot to be cast.

18. The method for preparing a zinc alloy according to claim 17, wherein: The purity of raw materials used for smelting zinc alloy is 99.9wt.%; The Zn and Cu raw materials are placed in a crucible of a vacuum induction melting furnace.

19. The method for preparing a zinc alloy according to claim 17, wherein: The purity of raw materials used for smelting zinc alloy is 99.9wt.%; The two raw materials, Zn and Fe, are placed in a crucible of a vacuum induction melting furnace.

20. The method for preparing a zinc alloy according to claim 17, wherein: The purity of raw materials used for smelting zinc alloy is 99.9wt.%; The three raw materials of Zn, Cu and Mg are placed in a crucible of a vacuum induction melting furnace.

Citation Information

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