CN112843329B - Degradable metal patch and preparation method thereof - Google Patents

Degradable metal patch and preparation method thereof Download PDF

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Publication number
CN112843329B
CN112843329B CN202011613411.XA CN202011613411A CN112843329B CN 112843329 B CN112843329 B CN 112843329B CN 202011613411 A CN202011613411 A CN 202011613411A CN 112843329 B CN112843329 B CN 112843329B
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degradable metal
degradable
metal
patch
metal patch
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CN112843329A (en
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白晶
程兆俊
邵怡
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Suzhou Jingjun New Material Technology Co ltd
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Suzhou Jingjun New Material Technology Co ltd
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    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS 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
    • A61L27/00Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/50Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • A61L27/58Materials at least partially resorbable by the body
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS 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
    • A61L27/00Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/02Inorganic materials
    • A61L27/04Metals or alloys
    • A61L27/047Other specific metals or alloys not covered by A61L27/042 - A61L27/045 or A61L27/06
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS 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
    • A61L27/00Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/50Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • A61L27/56Porous materials, e.g. foams or sponges
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS 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
    • A61L31/00Materials 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
    • A61L31/02Inorganic materials
    • A61L31/022Metals or alloys
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS 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
    • A61L31/00Materials 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
    • A61L31/14Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • A61L31/146Porous materials, e.g. foams or sponges
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS 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
    • A61L31/00Materials 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
    • A61L31/14Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • A61L31/148Materials at least partially resorbable by the body
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F7/00Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression
    • B22F7/02Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of composite layers
    • B22F7/04Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of composite layers with one or more layers not made from powder, e.g. made from solid metal

Abstract

The invention provides a degradable metal patch and a preparation method thereof, wherein the metal patch has a through hole structure with 20% -50% of porosity. The preparation method of the degradable metal patch comprises the following steps: preparing wires; pretreating wires; cutting, dispersing and mixing the silk materials; performing cold pressing and preforming; and (5) hot-press forming. The metal patch has excellent mechanical property and biocompatibility, realizes the delivery of substances such as nutrient substances, metabolites and the like while protecting damaged tissues, and gradually degrades along with the healing process of the tissues.

Description

Degradable metal patch and preparation method thereof
Technical Field
The invention relates to the field of medical materials, in particular to a medical degradable metal patch and a preparation method thereof.
Background
The patch is widely applied to craniofacial repair, pleural repair, skin repair, plastic surgery and other operations, and is implanted into a wound position to fix and protect a focus part. The current clinical traditional artificial patch material is non-degradable material such as polypropylene, polytetrafluoroethylene, polyester, silica gel and the like, and the patch is permanently retained or taken out for secondary operation on parts which only need temporary wound closure repair, wrapping, support and the like. This will greatly increase postoperative wound infection, foreign body reaction's risk, macromolecular material's intensity is not enough simultaneously, support ability is relatively poor, is unfavorable for providing the stable space of tissue repair.
In view of the above problems, various degradable patches have been disclosed to replace existing patches. Patent CN108853608A discloses a biodegradable medical magnesium alloy patch and a preparation method and application thereof, the mesh patch is obtained by weaving magnesium alloy wires, can be degraded after operation, and has better strength and supporting force compared with high polymer materials. However, because the patch has a larger mesh, the application range of the patch is limited, for example, in abdominal incisional hernia operation, and the abdominal cavity inner wall can cause intestinal perforation by adhesion of the mesh of the patch and the intestinal canal. CN102908668A discloses a preparation method of an induced growth type absorbable patch, wherein an electrostatic spinning technology is adopted to obtain a degradable polymer patch with a through hole structure, and the through hole structure of the patch can ensure the transportation of nutrients and metabolites, and simultaneously effectively protect a wound part and prevent adhesion. However, the patch is not strong enough to provide effective support, and thus has a limited range of applications.
Therefore, the existing technology can not meet and solve the above problems at the same time, and it is a significant task to develop a patch which is degradable in vivo, has good support performance and prevents adhesion.
Disclosure of Invention
The invention aims to solve one of the prior technical problems and provides a degradable metal patch and a preparation method thereof.
Specifically, the technical scheme provided by the invention is as follows:
a preparation method of a degradable metal patch comprises the following specific preparation steps:
s1, carrying out hot extrusion on the degradable metal cast ingot to obtain a degradable metal thick wire with the diameter of less than 1.5mm, and carrying out multi-pass drawing and heat treatment on the degradable metal thick wire until obtaining a degradable metal thin wire with the diameter of 30-100 mu m;
s2, performing surface treatment on the degradable metal filament obtained in the step S1, wherein the treatment mode comprises the following steps: one of fluorination treatment, anodic oxidation treatment and micro-arc oxidation treatment;
s3, cutting and dispersing the surface-treated degradable metal filament obtained in the step S2 into segments with the length-diameter ratio of 100:1 to 1000:1, and selecting degradable metal filament segments with the same filament diameter to be uniformly mixed;
s4, putting the mixed degradable metal wire section obtained in the step S3 into a cold pressing die, and pressing the mixed degradable metal wire section into a metal sheet monomer at room temperature until the thickness of the metal sheet monomer reaches 0.1-0.5 mm;
s5, selecting metal sheet monomers with different average pore diameters and porosities obtained in the step S4, respectively placing the metal sheet monomers into degradable metal powder, sequentially placing the metal powder into a hot-pressing die after the metal powder is attached, and then pressing the metal sheet monomers at the high temperature of 200-400 ℃ for 2-5 hours to obtain a degradable metal patch original sheet with the thickness of 0.2-1 mm;
and S6, sequentially carrying out alcohol ultrasonic cleaning, oven drying and epoxy hexane sterilization on the degradable metal patch original sheet obtained in the step S5 to obtain the degradable metal patch.
Preferably, the average pore diameter of the metal flake monomer is 20 to 150 μm, and the porosity is 20 to 50%.
Preferably, the metal sheet monomers are stacked in a manner that the central density decreases outwards, that is, the outer surface is the metal sheet monomer with the smallest average pore diameter, and the center is the metal sheet monomer with the largest average pore diameter.
Preferably, before the high-temperature pressing process of step S5, one or more of argon, sulfur hexafluoride, or carbon dioxide is introduced as a protective gas, and the introduction time is not less than 5 minutes.
Preferably, the degradable metal patch is made of a degradable metal material selected from any one of pure magnesium, magnesium alloy, pure zinc and zinc alloy.
In addition, the invention also provides a degradable metal patch which is prepared by adopting the preparation method.
Preferably, the degradable metal patch is made of a degradable metal material, and the degradable metal material is selected from any one of pure magnesium, magnesium alloy, pure zinc and zinc alloy.
Preferably, the cross section of the degradable metal patch has an increasing average pore size from outside to inside.
The invention has the following beneficial effects:
(1) the patch is made of metal wires, has communicated pores and presents a gradient through hole structure, and the outer surface of the patch has a smaller average pore diameter, so that the patch is beneficial to cell adhesion and can prevent cells from growing into the patch to cause blockage; the core part has large average pore size, provides a channel for the transportation of nutrient substances and metabolites, and can effectively prevent the tissues on the two sides of the patch from being adhered;
(2) the patch is formed by two steps of cold pressing and hot pressing, and prefabricated metal sheet monomers with different specifications can be obtained by cold pressing; sintering the metal sheet monomers by hot press molding, pressing the metal sheet monomers into the thickness of a final finished product, and regulating and controlling parameters such as gradient rate, thickness, porosity and the like of the patch through the combination of the metal sheet monomers;
(3) the metal patch has good strength and toughness, can provide effective support for a wound part, and is not easy to generate inflammatory reaction;
(4) the patch can be gradually degraded in the human body environment, can not be stored for a long time, and can adjust the degradation time of the patch by adjusting the components of the metal wire or the surface treatment process, thereby meeting the requirements of wound repair in different healing cycles.
Drawings
Fig. 1 is a schematic view of a method for preparing a degradable metal patch according to the present invention.
FIG. 2 is a schematic view of a cold press forming process of a magnesium alloy sheet monolith according to a first embodiment of the present invention;
FIG. 3 is a schematic view of a hot press forming process of a degradable pure magnesium patch according to a second embodiment of the invention;
fig. 4 is a schematic cross-sectional view of a degradable zinc alloy patch according to the present invention.
Fig. 5 is a schematic diagram of the macro-morphology of the degradable magnesium alloy patch according to the present invention.
Fig. 6 is a schematic view of the micro-topography of the degradable magnesium alloy patch according to the present invention.
The meaning of the reference symbols in the attached figures 1-6 is explained as follows:
1 is a compression bar, 2 is a forming die, 3 is a magnesium alloy wire section, 41 is a 20 mu m average aperture magnesium alloy sheet monomer, 51 is a 20 mu m average aperture pure magnesium sheet monomer, 52 is a 40 mu m average aperture pure magnesium sheet monomer, 53 is a 100 mu m average aperture pure magnesium sheet monomer, and 6 is a degradable pure magnesium patch.
Detailed Description
In order to make the technical solutions of the present invention better understood, the present invention will be described in further detail with reference to the accompanying drawings and specific embodiments.
The degradable metal patch manufactured according to the scheme of the invention has a through hole structure with 20% -50% of porosity.
Example 1
As shown in fig. 1, the preparation method of the degradable metal patch according to the present invention comprises the following specific steps:
s1 preparation of wire material
Specifically, for example, a magnesium alloy ingot with 2 wt% of Zn and the balance of Mg is subjected to hot extrusion to obtain a magnesium alloy thick wire with the diameter of less than 1.5mm, and the magnesium alloy thick wire is subjected to drawing and heat treatment for multiple times to obtain magnesium alloy filaments with two different diameters, wherein the first diameter is about 30 μm, and the second diameter is about 50 μm. Wherein the drawing and heat treatment process is a wire drawing and heat treatment process common in the art.
S2 pretreatment of wire material
And (4) performing surface treatment on the magnesium alloy filament obtained in the step S1, wherein the surface treatment adopts micro-arc oxidation treatment, the termination voltage is 200V, and the temperature is 4 ℃.
S3, cutting and dispersing the magnesium alloy filament obtained in the step S2 in a length-diameter ratio of 100:1 to 1000:1, and uniformly mixing magnesium alloy filament sections with the same filament diameter;
s4, putting the mixed magnesium alloy wire sections with the diameter of 30 microns and the mixed magnesium alloy wire sections with the diameter of 50 microns obtained in the step S3 into a cold pressing die respectively, wherein the putting amounts are 1.13g and 0.7g respectively, pressing the mixed magnesium alloy wire sections into two magnesium alloy sheet monomers at room temperature, the thickness of the mixed magnesium alloy sheet monomers is 0.1mm, and pores are generated when the magnesium alloy sheet monomers are pressed due to the fact that the magnesium alloy wire sections with different lengths are mixed, wherein the magnesium alloy sheet with the first diameter is formed after being pressed to have a first average pore diameter and a first average porosity, for example, the first average pore diameter is 20 microns, and the first average porosity is 20%; the magnesium alloy sheet having the second diameter is pressed to have a second average pore diameter and a second average porosity, for example, the second average pore diameter is 60 μm and the second average porosity is 40%. FIG. 2 is a schematic diagram of a cold press molding process of a single magnesium alloy sheet with an average pore diameter of 20 μm;
s5, selecting two magnesium alloy sheet monomers with a first average pore diameter and one magnesium alloy sheet monomer with a second average pore diameter obtained in the step S4, respectively placing the two magnesium alloy sheet monomers into magnesium alloy powder, attaching the magnesium alloy powder, placing the second magnesium alloy sheet monomer between the two magnesium alloy sheet monomers with the first average pore diameter, placing the two magnesium alloy sheet monomers into a hot-pressing die, and pressing the two magnesium alloy sheet monomers at a high temperature, such as 200 ℃ or above, for 3 hours to obtain a degradable magnesium alloy patch;
s6, carrying out alcohol ultrasonic cleaning, oven drying and epoxy hexane sterilization on the degradable magnesium alloy patch obtained in the step S5.
In the high-temperature pressing process, argon is used as a protective gas; the magnesium alloy powder comprises 2 wt% of Zn and the balance of Mg.
The degradable magnesium alloy patch obtained by the specific implementation steps has the thickness of 0.25mm and the overall porosity of 23.5%.
Example 2
The preparation method of the degradable metal patch in the example comprises the following specific steps:
s1, carrying out hot extrusion on the pure magnesium cast ingot to obtain pure magnesium thick wires with the diameter of less than 1.5mm, and carrying out multi-pass drawing and heat treatment on the pure magnesium thick wires to obtain pure magnesium thin wires with the diameters of 30 microns, 50 microns and 80 microns;
s2, carrying out surface fluorination treatment on the pure magnesium filament obtained in the step S1 at the temperature of 80 ℃ for 24 hours;
s3, cutting and dispersing the pure magnesium filaments obtained in the step S2 into segments according to the length-diameter ratio of 100:1 to 1000:1, and uniformly mixing the pure magnesium filaments with the same filament diameter;
s4, putting the mixed magnesium alloy wire sections with the thickness of 30 mu m, 50 mu m and 80 mu m obtained in the step S3 into a cold pressing die, wherein the putting amounts are 2.23g, 1.96g and 1.57g respectively, and pressing the mixed magnesium alloy wire sections into three pure magnesium sheet monomers with the thicknesses of 0.2mm, 0.2mm and 0.4mm at room temperature, the average pore diameters are 20 mu m, 40 mu m and 100 mu m respectively, and the average porosity is 20%, 30% and 50% respectively;
s5, selecting two pure magnesium sheet monomers with the average pore size of 20 microns, the average pore size of 40 microns and the average pore size of 100 microns obtained in the step S4, respectively placing the pure magnesium sheet monomers in pure magnesium powder, attaching the pure magnesium powder, sequentially placing the pure magnesium sheet monomers in a hot-pressing die according to the sequence of the pure magnesium sheet monomers with the average pore sizes of 20 microns, 40 microns, 100 microns, 40 microns and 20 microns, and then pressing the pure magnesium sheet monomers at a high temperature of 400 ℃ or above for 5 hours to obtain a degradable pure magnesium patch, wherein the hot-pressing forming process schematic diagram of the pure magnesium sheet monomers with three pore sizes is shown in figure 2;
s6, carrying out alcohol ultrasonic cleaning, oven drying and epoxy hexane sterilization on the degradable pure magnesium patch obtained in the step S5.
And in the high-temperature pressing process, sulfur hexafluoride is used as protective gas.
The thickness of the degradable magnesium alloy patch obtained by the specific implementation steps is 1mm, and the overall porosity is 25%.
Example 3
The preparation method of the degradable metal patch in the example comprises the following specific steps:
s1, carrying out hot extrusion on a zinc alloy cast ingot with the components of 0.5 wt% of Mg and the balance of Zn to obtain a zinc alloy thick wire with the diameter of less than 1.5mm, and carrying out multi-pass drawing and heat treatment on the zinc alloy thick wire to obtain a zinc alloy thin wire with the diameter of 30 and 100 micrometers;
s2, carrying out surface anodic oxidation treatment on the zinc alloy filament obtained in the step S1, wherein the current is 0.2A/dm 2 The temperature is 18 ℃ and the time is 3 min;
s3, cutting and dispersing the zinc alloy filaments obtained in the step S2 into segments according to the length-diameter ratio of 100:1 to 1000:1, and uniformly mixing the zinc alloy filaments with the same filament diameter;
s4, putting the mixed zinc alloy wire sections with the diameter of 30 mu m and the diameter of 100 mu m obtained in the step S3 into a cold pressing die, wherein the putting amount is 4.4g and 3.02g respectively, pressing the mixed zinc alloy wire sections into two zinc alloy sheet monomers at room temperature, the thicknesses of the zinc alloy sheet monomers are 0.1mm and 0.5mm, the average pore diameters of the zinc alloy sheet monomers are 20 mu m and 150 mu m respectively, and the average porosity of the zinc alloy sheet monomers is 20 percent and 45 percent respectively;
s5, selecting two zinc alloy sheet monomers with the average pore size of 20 micrometers and one zinc alloy sheet monomer with the average pore size of 150 micrometers obtained in the step S4, respectively placing the two zinc alloy sheet monomers in zinc alloy powder, attaching the zinc alloy powder, placing the zinc alloy sheet monomers with the average pore size of 150 micrometers between the two zinc alloy sheet monomers with the average pore size of 20 micrometers, placing the zinc alloy sheet monomers in a hot-pressing die, and then pressing the zinc alloy sheet monomers at a high temperature of 300 ℃ for 2 hours to obtain the degradable zinc alloy patch;
s6, carrying out alcohol ultrasonic cleaning, oven drying and epoxy hexane sterilization on the degradable zinc alloy patch obtained in the step S5, and obtaining a schematic cross-sectional view of the degradable alloy patch as shown in FIG. 4.
In the high-temperature pressing process, 10% of sulfur hexafluoride and 90% of carbon dioxide are used as protective gases; the zinc alloy powder comprises 0.5 wt% of Mg and the balance of Zn.
The degradable zinc alloy patch obtained by the specific implementation steps has the thickness of 0.6mm and the overall porosity of 27%.
Further preferably, the degradable metal powder has a particle size of 20 to 40 μm.
Fig. 5 and 6 respectively show a macro-morphology and a micro-morphology schematic diagram of the degradable magnesium alloy patch prepared according to the embodiment 1 of the invention. It can be seen from the figure that the degradable metal wires are stacked and tightly combined with each other, and a large number of irregular and dense pores exist among the degradable metal wires, so that a channel is provided for in vivo substance transportation.
It will be understood that the above embodiments are merely exemplary embodiments taken to illustrate the principles of the present invention, which is not limited thereto. It will be apparent to those skilled in the art that various modifications and improvements can be made without departing from the spirit and substance of the invention, and these modifications and improvements are also considered to be within the scope of the invention.

Claims (7)

1. The preparation method of the degradable metal patch is characterized by comprising the following specific preparation steps:
s1, carrying out hot extrusion on the degradable metal cast ingot to obtain a degradable metal thick wire with the diameter of less than 1.5mm, and carrying out multi-pass drawing and heat treatment on the degradable metal thick wire until obtaining a degradable metal thin wire with the diameter of 30-100 mu m;
s2, performing surface treatment on the degradable metal filament obtained in the step S1, wherein the treatment mode comprises the following steps: one of fluorination treatment, anodic oxidation treatment and micro-arc oxidation treatment;
s3, cutting and dispersing the surface-treated degradable metal filament obtained in the step S2 into segments with the length-diameter ratio of 100:1 to 1000:1, and selecting degradable metal filament segments with the same filament diameter to be uniformly mixed;
s4, putting the mixed degradable metal wire section obtained in the step S3 into a cold pressing die, and pressing the mixed degradable metal wire section into a metal sheet monomer at room temperature until the thickness of the metal sheet monomer reaches 0.1-0.5 mm;
s5, selecting the metal sheet monomers with different average pore diameters and porosities obtained in the step S4, respectively placing the metal sheet monomers into degradable metal powder, sequentially placing the metal powder into a hot-pressing die after the metal powder is attached, and then pressing the metal sheet monomers at the high temperature of 200-400 ℃ for 2-5 hours to obtain a degradable metal patch original sheet with the thickness of 0.2-1 mm;
and S6, sequentially carrying out alcohol ultrasonic cleaning, oven drying and epoxy hexane sterilization on the degradable metal patch raw sheet obtained in the step S5 to obtain the degradable metal patch.
2. The method for preparing a degradable metal patch according to claim 1, wherein the average pore diameter of the metal sheet monomer is 20-150 μm and the porosity is 20-50%.
3. The method for preparing a degradable metal patch according to claim 1, wherein the metal sheet monomers are stacked in such a manner that the density of the center decreases outward, that is, the outer surface is the metal sheet monomer with the smallest average pore size and the center is the metal sheet monomer with the largest average pore size.
4. The method for preparing a degradable metal patch according to claim 1, wherein one or more of argon, sulfur hexafluoride or carbon dioxide is introduced as a protective gas for not less than 5 minutes before the high temperature pressing process of step S5.
5. The method for preparing a degradable metal patch according to claim 1, wherein the degradable metal patch is made of a degradable metal material selected from any one of pure magnesium, magnesium alloy, pure zinc and zinc alloy.
6. A degradable metal patch, characterized by being produced by the production method according to any one of claims 1 to 5.
7. The degradable metal patch of claim 6, wherein the degradable metal patch has a cross-section with increasing average pore size from outside to inside.
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CN101181646A (en) * 2007-12-06 2008-05-21 上海交通大学 Method for preparing toughened cemented metal netted polyporous material
DE102008037204B4 (en) * 2008-08-11 2016-01-07 Alfred Buck Plate for fixation of bone fragments and process for their preparation
CN108853608B (en) * 2017-05-10 2021-08-06 上海交通大学 Biodegradable medical magnesium alloy patch and preparation method and application thereof
CN111304495B (en) * 2020-03-12 2021-06-01 东南大学 Medical zinc alloy stent and production method thereof

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