CN114086045A - Preparation method of medical magnesium-silver alloy with controllable degradation rate - Google Patents
Preparation method of medical magnesium-silver alloy with controllable degradation rate Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C23/00—Alloys based on magnesium
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- A—HUMAN NECESSITIES
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- 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
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- 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
- A61L31/14—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
- A61L31/148—Materials at least partially resorbable by the body
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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
- A61L31/14—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
- A61L31/16—Biologically active materials, e.g. therapeutic substances
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/06—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of magnesium or alloys based thereon
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- A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
- A61L2300/10—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices containing or releasing inorganic materials
- A61L2300/102—Metals or metal compounds, e.g. salts such as bicarbonates, carbonates, oxides, zeolites, silicates
- A61L2300/104—Silver, e.g. silver sulfadiazine
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- A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
- A61L2300/40—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices characterised by a specific therapeutic activity or mode of action
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Abstract
本发明属于生物医用材料领域，具体涉及一种降解速率可控的医用镁银合金的制备方法。镁银合金中银的质量百分含量为3‑6％，Fe<0.0022％,Cu<0.001％,Ni<0.001％,其余为镁。本发明通过在镁中加入银元素，提升镁合金的强度与抗菌性能，并利用不同合金元素配比、不同挤压比调控合金晶粒大小、第二相尺寸与体积占比等微观组织参数，进而调控镁银合金降解速率，以满足不同植入部位对于力学、降解性能的差异化需求。本发明制备所得镁银合金应用范围包括但不限于口腔屏障膜、骨钉、骨板等植入体。
The invention belongs to the field of biomedical materials, in particular to a preparation method of a medical magnesium-silver alloy with a controllable degradation rate. The mass percentage content of silver in the magnesium-silver alloy is 3-6%, Fe<0.0022%, Cu<0.001%, Ni<0.001%, and the rest is magnesium. The present invention improves the strength and antibacterial properties of magnesium alloys by adding silver elements to magnesium, and uses different alloying element ratios and different extrusion ratios to control microstructure parameters such as alloy grain size, second phase size and volume ratio, etc. Then, the degradation rate of magnesium-silver alloys is regulated to meet the differentiated requirements of different implanted parts for mechanical and degradation properties. The application scope of the magnesium-silver alloy prepared by the present invention includes but is not limited to implants such as oral barrier membrane, bone nail, bone plate and the like.
Description
Technical Field
The invention relates to the field of biomedical materials, in particular to a preparation method of a medical magnesium-silver alloy with controllable degradation rate.
Background
In recent years, with the improvement of living standard and the rapid development of medical science and technology, stomatological clinical restoration means such as oral implant are widely applied. However, the problem of insufficient bone mass in and around the implant is urgently needed to be solved, and the Guided Bone Regeneration (GBR) is a new approach and is more and more widely accepted in clinic. The basic principle of the GBR technology is based on the characteristics of rapid fibroblast migration and slow osteoblast migration, a barrier membrane is implanted between soft and hard tissues to mechanically isolate bone defects from surrounding connective tissues, and soft tissue ingrowth is avoided to interfere with the progress of an osteogenesis process. Thus, five fundamental design requirements are placed on barrier membranes: good biocompatibility, maintenance of adequate osteogenic space, selective isolation of cells, ability to integrate tissue, and clinical operability.
The barrier membranes applied to clinic at present can be mainly divided into two types, one type is an absorbable membrane, and the common types comprise a collagen membrane, a polylactic acid membrane, a polyvinyl alcohol acetate membrane and a polypropylene ester lactic acid membrane; the other is that the non-absorbable membrane comprises a polytetrafluoroethylene membrane, a titanium reinforced polytetrafluoroethylene membrane, a titanium net and a microporous filter membrane. The absorbable membrane has good biocompatibility and easy operation, can avoid secondary operation, but has unpredictable absorption degree and short strength maintenance time after implantation, and simultaneously, the acidic environment caused by degradation of most organic materials can easily induce inflammatory reaction, and finally leads to bone reconstruction failure. The non-absorbable membrane has good biological stability, can be taken out at any time, basically does not influence the regeneration process, has higher mechanical strength, can maintain enough osteogenesis space, has the defect of needing to be taken out by a secondary operation, can bring pain to patients in the process, has potential risks, and does not have osteoinductivity.
The magnesium alloy has wide application prospect in the aspect of implanting medical instruments, and has the following advantages: (1) the magnesium alloy has good biocompatibility. Magnesium is the fourth major mineral element required by human body, and the content of magnesium is only calcium, sodium and potassium. Magnesium can regulate cell growth and maintain stable membrane structure, promote growth and stability of osteoblast tissue, and balance activity of osteoblast and osteoclast. (2) The magnesium alloy has good mechanical compatibility. The strength of the magnesium alloy meets the implantation requirement, the elastic modulus is most similar to that of natural bones, and the generation of stress barrier effect caused by mismatching of the elastic modulus of an implant body and human bone tissues is avoided. (3) The magnesium alloy has degradable performance. The secondary operation in the implantation operation is avoided, and the risk of the patient and the medical cost are effectively reduced. (4) The magnesium alloy has low cost and abundant resources.
However, in a complex environment in vivo, the change of mechanical properties and degradation rate of the magnesium alloy material is uncontrollable, and the magnesium alloy material also lacks adaptability to an implantation environment, so that the adaptability of material properties and tissue regeneration is poor, the repair effect is directly influenced, and the clinical application is limited. How to realize the degradation regulation of magnesium alloy materials to adapt to the regeneration of different tissues in vivo is a key scientific problem of poor adaptability of the current magnesium alloy in the regeneration and repair process of hard tissues.
According to the invention, the silver element is added into the magnesium alloy, so that the strength and antibacterial property of the alloy are improved. The microstructure of the alloy material is adjusted by regulating the silver content and the extrusion ratio (deformation), so that the mechanical property and the degradation rate of the material are predicted and regulated, and the requirements of different implantation parts on the mechanical property and the degradation property are met.
Disclosure of Invention
The invention aims to design a preparation method for realizing a magnesium-silver alloy material with controllable degradation rate by utilizing different extrusion ratios aiming at the condition that the prior implant material degradation and the implant site tissue growth adaptability are poor so as to meet the specific requirements of different implant sites on the alloy degradation performance.
In order to achieve the above object, the present invention can be achieved by the following technical solutions.
The preparation method of the medical magnesium-silver alloy with the controllable degradation rate comprises the following components of 3.0-6.0% of Ag element by mass, less than 0.0022% of impurity elements Fe, less than 0.001% of Cu, less than 0.001% of Ni and the balance of Mg, and is characterized by comprising the following steps of:
(1) weighing more than or equal to 99.9 percent of magnesium ingot and more than or equal to 99.9 percent of silver ingot according to the mass percentage, refining the magnesium ingot and the silver ingot to obtain high-purity magnesium ingot and high-purity silver ingot with the purity of more than or equal to 99.99 percent, and melting the high-purity magnesium ingot and the high-purity silver ingot as furnace burden;
(2) putting the high-purity magnesium ingot and the high-purity silver ingot into a crucible together, melting under the protection of protective gas at the temperature of 730-;
(3) after the temperature is reduced to 700-750 ℃, pouring the melt into a low-carbon steel mold preheated to 550-600 ℃, and separating the casting from the mold by using a release agent; keeping the mold at the temperature of 650-700 ℃ for 15-20 min under the protective atmosphere, and directly cooling the mold in flowing room-temperature water at the speed of 100-120cm/min, wherein when the liquid level in the mold rises, the height of the melt is aligned with that of the external water, and the solidification process is finished;
(4) removing the top and the bottom of the cast ingot with the shrinkage cavity and impurities to obtain an as-cast magnesium-silver alloy;
(5) homogenizing the as-cast magnesium-silver alloy;
(6) and extruding the homogenized alloy according to different extrusion ratios to regulate and control the grain size, the second phase size and the volume ratio of the alloy, and further regulating and controlling the degradation rate of the magnesium-silver alloy to meet the specific requirements of different implantation parts on the degradation performance of the alloy, so as to obtain the extruded magnesium-silver alloy with the controllable degradation rate.
Further, the crucible material includes but is not limited to steel material, corundum, etc., but the content of impurity elements is ensured to meet the requirement.
Further, the shielding gas is Ar and SF6The volume ratio of the mixed gas is 49: 1.
Further, the release agent is hexagonal boron nitride.
Further, the homogenization treatment temperature is 400-450 ℃, and the time is 10-20 h. The extrusion temperature is 300-350 ℃, the extrusion ratio is 5-70, and the extrusion speed is 5-7 mm/s.
Further, the application range includes but is not limited to oral barrier membranes, bone screws, bone plates.
Compared with the prior magnesium alloy implantation medical apparatus, the invention has the following advantages:
(1) the magnesium-silver alloy with different silver contents is extruded by utilizing different extrusion ratios so as to regulate and control the grain size, the second phase size and the volume ratio of the alloy, further regulate and control the degradation rate of the magnesium-silver alloy so as to meet the specific requirements of different implantation parts on the degradation performance of the alloy, realize the precise regulation and control of tissues and further realize the refined regulation and control of the mechanical property and the degradation characteristic of the magnesium-silver alloy.
(2) The addition of silver element into the magnesium matrix can produce obvious solid solution strengthening and fine crystal strengthening effects. The degradation rate of the alloy is controllable, and the silver element has certain antibacterial property, so that the biocompatibility of the alloy is improved.
Drawings
FIG. 1 is a macro-topography of alloys at different extrusion ratios.
FIG. 2 is the microstructure of alloy samples with different extrusion ratios and different silver contents observed by a scanning electron microscope.
FIG. 3 shows the results of tensile tests on alloy samples with different extrusion ratios and different silver contents.
FIG. 4 shows the results of electrochemical corrosion tests on alloy samples with different extrusion ratios and different silver contents.
FIG. 5 is a surface macro morphology of alloy samples with different extrusion ratios and different silver contents after in-vitro corrosion.
FIG. 6 shows the XPS test results of alloy samples with different extrusion ratios and different silver contents after in-vitro corrosion.
FIG. 7 shows the micro-CT analysis results of alloy samples with different extrusion ratios and different silver contents implanted in vivo for 1 month.
Detailed Description
The following detailed description of the claimed invention is provided in connection with specific examples, but the scope of the invention is not limited thereto.
Example 1
The preparation method of the Mg-3Ag alloy with different extrusion ratios comprises the following steps:
(1) and determining that the mass fraction of the silver in the magnesium-silver alloy is 3%.
(2) The mass of the required elements is calculated in advance before smelting, and the elements are weighed and prepared by an electronic balance according to the calculation result.
(3) High purity magnesium is placed in a steel crucible along with a corresponding amount of silver. At 750 deg.C, in 98% argon (Ar) and 2% sulfur hexafluoride (SF)6) Was melted under protection of (1) and then stirred at 200rpm for half an hour.
(4) After the temperature is reduced to 730 ℃, the melt is poured into a low-carbon steel die preheated to 550 ℃, and hexagonal boron nitride is used as a release agent for better separating the casting from the die. The mold was kept at 680 ℃ for 15 minutes under a protective atmosphere and cooled directly in flowing room temperature water at a rate of 100 cm/min. When the liquid level in the melt rises, the melt is aligned with the height of the external water, and the solidification process is finished.
(5) And removing the top and the bottom of the ingot with the shrinkage cavity and impurities.
(6) The diameter of the cast ingot is 92mm, and the cast ingot is machined to 85mm and 360mm by a lathe.
(7) The ingot homogenization treatment was carried out in a resistance furnace at 430 ℃ for 16 hours, and then quenched in water at room temperature.
(8) The alloy is cut into three equal sections along the length direction, each section is 100mm, one section is taken as an as-cast group (the extrusion ratio is 1), the other two sections are taken for extrusion, an ingot is heated to 300 ℃, the temperature of a container and a steel die is 300 ℃, the hot extrusion is carried out for processing, the extrusion is carried out until the diameter is 32mm (the extrusion ratio is about 7.1) and the diameter is 10mm (the extrusion ratio is about 72.2), and the stamping advancing speed is 5 mm/s.
Example 2: the preparation method of the Mg-6Ag alloy with different extrusion ratios comprises the following steps:
(1) and determining that the mass fraction of the silver in the magnesium-silver alloy is 6%.
(2) The mass of the required elements is calculated in advance before smelting, and the elements are weighed and prepared by an electronic balance according to the calculation result.
(3) High purity magnesium is placed in a steel crucible along with a corresponding amount of silver. At 750 deg.C, in 98% argon (Ar) and 2% sulfur hexafluoride (SF)6) Was melted under protection of (1) and then stirred at 220rpm for half an hour.
(4) After the temperature is reduced to 750 ℃, the melt is poured into a low-carbon steel die preheated to 550 ℃, and hexagonal boron nitride is used as a release agent for better separating the casting from the die. The mold was kept at 680 ℃ for 20 minutes under a protective atmosphere and cooled directly in flowing room temperature water at a rate of 120 cm/min. When the liquid level in the melt rises, the melt is aligned with the height of the external water, and the solidification process is finished.
(5) And removing the top and the bottom of the ingot with the shrinkage cavity and impurities.
(6) The diameter of the cast ingot is 92mm, and the cast ingot is machined to 85mm and 360mm by a lathe.
(7) The alloy ingots were all homogenized in a resistance furnace at 450 ℃ for 16 hours and then quenched in water at room temperature.
(8) The alloy is cut into three equal sections along the length direction, each section is 100mm, one section is taken as an as-cast group (the extrusion ratio is 1), the other two sections are taken for extrusion, an ingot is heated to 350 ℃, the temperature of a container and a steel die is 350 ℃, the alloy is processed by hot extrusion, the extrusion is carried out until the diameter is 32mm (the extrusion ratio is about 7.1) and the diameter is 10mm (the extrusion ratio is about 72.2), and the stamping advancing speed is 7 mm/s.
Comparative example 1:
the steps for preparing pure magnesium with different extrusion ratios are as follows:
(1) high purity magnesium is placed in a steel crucible. At 750 deg.C, in 98% argon (Ar) and 2% sulfur hexafluoride (SF)6) Was melted under protection of (1) and then stirred at 200rpm for half an hour.
(2) After the temperature is reduced to 730 ℃, the melt is poured into a low-carbon steel die preheated to 550 ℃, and hexagonal boron nitride is used as a release agent for better separating the casting from the die. The mold was kept at 680 ℃ for 20 minutes under a protective atmosphere and cooled directly in flowing room temperature water at a rate of 120 cm/min. When the liquid level in the melt rises, the melt is aligned with the height of the external water, and the solidification process is finished.
(3) And removing the top and the bottom of the ingot with the shrinkage cavity and impurities.
(4) The diameter of the cast ingot is 92mm, and the cast ingot is machined to 85mm and 360mm by a lathe.
(5) The ingot was all homogenized in a resistance furnace at 420 ℃ for 16 hours and then quenched in water at room temperature.
(6) The ingot is cut into three equal sections along the length direction, each section is 100mm, one section is taken as an as-cast group (the extrusion ratio is 1), the other two sections are taken for extrusion, the ingot is heated to 300 ℃, the temperature of a container and a steel die is 300 ℃, the ingot is processed by hot extrusion, the extrusion is carried out until the diameter is 32mm (the extrusion ratio is about 7.1) and the diameter is 10mm (the extrusion ratio is about 72.2), and the advancing speed of stamping is 5 mm/s.
Through detection, the addition of the silver can refine grains, the strength of the alloy is improved, and the degradation rate can be regulated and controlled through different extrusion ratios.
The microstructure and properties of the magnesium-silver alloy were tested and analyzed for three extrusion ratios (1, 7.1,72.2) and three silver contents (0, 3, 6% silver mass fraction):
FIG. 1 is a macro-topography of alloys at different extrusion ratios. As can be seen from the figure, the diameter of the as-cast alloy ingot was 85mm, the diameter of the alloy rod with an extrusion ratio of 7.1 was 32mm, and the diameter of the alloy rod with an extrusion ratio of 72.2 was 10 mm.
FIG. 2 is the microstructure of alloy samples with different extrusion ratios and different silver contents observed by a scanning electron microscope. It can be seen from the figure that as the extrusion ratio increases, the alloy grain size decreases and then increases by a small amount, the second phase content increases and then decreases; as the silver content increases, the alloy size decreases and the second phase content increases.
FIG. 3 shows the results of tensile tests on alloy samples with different extrusion ratios and different silver contents. As can be seen from the figure, the yield strength of the pure magnesium group after extrusion is increased by more than 35 percent, and the plasticity is reduced by half. The yield strength of the Ag group is increased by more than 50 percent, and the plasticity is basically unchanged. The silver content is increased, the yield strength is increased by more than 1.5 times, the plastic cast state group is reduced by half, and the extrusion group is improved by more than 10%.
FIG. 4 shows the results of electrochemical corrosion tests on alloy samples with different extrusion ratios and different silver contents. It can be seen that the increased Ag content and the increased self-corrosion current indicate that Ag accelerates corrosion, forming a second phase, which forms a microcell with the substrate. The extrusion ratio is increased, the self-corrosion current is reduced, and the corrosion rate is reduced after extrusion.
FIG. 5 is a surface macro morphology of alloy samples with different extrusion ratios and different silver contents after in-vitro corrosion. White matter is a corrosion product. After addition of Ag, the second phase is distributed along the grains due to the generation of the second phase, resulting in a local corrosion phenomenon.
FIG. 6 shows the XPS test results of alloy samples with different extrusion ratios and different silver contents after in-vitro corrosion. It can be seen that the surface deposition elements after corrosion are mainly C, N, O, Na, P, S, Cl and Ca, and the amount of the deposition elements is related to the silver content in the magnesium-silver alloy.
FIG. 7 shows the micro-CT analysis results of alloy samples with different extrusion ratios and different silver contents implanted in vivo for 1 month. It can be seen that the in vivo corrosion rate is also related to the extrusion ratio and silver content, the more the material degrades, the more Mg is released2+More leads to higher bone formation, but too rapid degradation leads to a local increase in pH, producing excess H2These are not conducive to osteogenesis.
Claims (8)
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