CN110607486A - Iron-based bone scaffold with degradable and antibacterial activities and preparation method thereof - Google Patents
Iron-based bone scaffold with degradable and antibacterial activities and preparation method thereof Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F10/00—Additive manufacturing of workpieces or articles from metallic powder
- B22F10/20—Direct sintering or melting
- B22F10/28—Powder bed fusion, e.g. selective laser melting [SLM] or electron beam melting [EBM]
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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
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/02—Inorganic materials
- A61L27/04—Metals or alloys
- A61L27/042—Iron or iron alloys
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F10/00—Additive manufacturing of workpieces or articles from metallic powder
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F10/00—Additive manufacturing of workpieces or articles from metallic powder
- B22F10/30—Process control
- B22F10/32—Process control of the atmosphere, e.g. composition or pressure in a building chamber
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F10/00—Additive manufacturing of workpieces or articles from metallic powder
- B22F10/30—Process control
- B22F10/34—Process control of powder characteristics, e.g. density, oxidation or flowability
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F10/00—Additive manufacturing of workpieces or articles from metallic powder
- B22F10/30—Process control
- B22F10/36—Process control of energy beam parameters
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F5/00—Manufacture of workpieces or articles from metallic powder characterised by the special shape of the product
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y10/00—Processes of additive manufacturing
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y80/00—Products made by additive manufacturing
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C33/00—Making ferrous alloys
- C22C33/02—Making ferrous alloys by powder metallurgy
- C22C33/0257—Making ferrous alloys by powder metallurgy characterised by the range of the alloying elements
- C22C33/0278—Making ferrous alloys by powder metallurgy characterised by the range of the alloying elements with at least one alloying element having a minimum content above 5%
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/007—Ferrous alloys, e.g. steel alloys containing silver
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/25—Process efficiency
Abstract
The invention relates to an iron-based bone scaffold with both degradable and antibacterial activities and a preparation method thereof, wherein the preparation method comprises the following steps: taking silver powder, iron powder and manganese powder according to the distribution of a design group, mechanically stirring and mixing under the protection of argon, and then adopting a selective laser melting process to obtain the iron-based bone scaffold. The iron-based bone scaffold is composed of an iron matrix and manganese and silver which are uniformly distributed in the iron matrix, the melting point of the silver is low, the silver can be changed into a liquid phase firstly in the alloy melting process, not only can gaps among solid-phase particles be filled, but also the material migration can be accelerated through liquid phase flow, so that the problem of micro defects in the forming process is avoided, and the alloy density is improved; meanwhile, silver can be precipitated on a crystal boundary in the cooling process, so that not only can strong galvanic corrosion be formed with a matrix to accelerate degradation, but also good antibacterial activity can be given to the support, and meanwhile, a precipitation phase can play a role in precipitation strengthening. The iron-based bone scaffold with both degradable and antibacterial activities has potential application value in the field of tissue repair.
Description
Technical Field
The invention relates to an iron-based bone scaffold with both degradable and antibacterial activity and a preparation method thereof, belonging to the technical field of biomedical implant design and manufacture.
Background
Stainless steel, titanium-based alloys and cobalt-based alloys are used as representative traditional metal biomaterials for human body bearing parts, but are difficult to degrade in the human body, cause some complications after long-term implantation, and need to be taken out after failure through a secondary operation. Biodegradable metals are a new generation of biomedical materials, and these metal implants not only can complete the repair function in vivo, but also can gradually degrade through corrosion until finally disappear. Therefore, the chemical composition of biodegradable metals should be an important element that the human body can metabolize. Under such circumstances, biodegradable magnesium-based alloys and iron-based alloys are very promising for applications, and iron-based alloys have great advantages as degradable implants compared to the excessively rapid degradation of magnesium alloys in physiological solutions with the concomitant production of large amounts of hydrogen. The pure iron is a corrosion-prone material, the iron element is one of indispensable microelements for human bodies, has good biocompatibility and is a good carrier of oxygen in blood; the ferrous ions and the hemoglobin are inseparable, which plays a critical role in the formation of the hemoglobin, and the iron content in an adult male is about 45mg/Kg, and the iron content in a female is about 35 mg/Kg; and the iron has good plasticity and toughness, and is beneficial to plastic deformation in the process of implanting the stent. In addition, the iron is not light penetrable, so that the position of the bracket in a human body can be observed conveniently in an operation.
Although animal experiments show that pure iron is biologically safe when applied to the implant, the implant still maintains better integrity after several months, the degradation speed is slow, and part of the iron-based implant still remains in vivo after bone tissue healing, so that the application of the iron-based implant is greatly limited, the potential of an iron matrix can be reduced by adding low-potential manganese, corrosion is accelerated, solid solution of manganese is limited, and the addition of a large amount of manganese easily causes microstructure defects such as gaps, cracks and the like. Furthermore, the implant is susceptible to bacterial infection after implantation into tissue, which also requires that the implant has some antibacterial activity.
Some studies have been carried out on Fe-Mn-Ag at present: such as patent CN 108677099 a; in this patent it is designed for Mn: 30 wt%, Ag: 1-10 wt% and the balance Fe, but the degradation rate of the obtained product is only 0.143mm/year at the highest. Meanwhile, the adopted method is still the traditional fusion casting method.
Disclosure of Invention
Aiming at the problems of slow degradation and lack of antibacterial activity of iron-based alloy in the prior art, the invention provides an iron-based bone scaffold with both degradable and antibacterial activity and a preparation method thereof. The iron-based bone scaffold is composed of an iron matrix and manganese and silver which are uniformly distributed in the iron matrix, the melting point of the silver is low, the silver can be changed into a liquid phase firstly in the alloy melting process, not only can gaps among solid-phase particles be filled, but also the material migration can be accelerated through liquid phase flow, so that the problem of micro defects in the forming process is avoided, and the alloy density is improved; meanwhile, silver can be precipitated and dispersed on a crystal boundary in the process of rapid cooling, so that not only can strong galvanic corrosion be formed with a matrix to accelerate degradation, but also the support can be endowed with good antibacterial activity, and meanwhile, a precipitation phase can play a role in precipitation strengthening.
The invention relates to an iron-based bone scaffold with both degradable and antibacterial activities, which comprises the following components in percentage by mass:
20% of manganese;
silver is 1 to 6%, preferably 2 to 5%, and more preferably 3%;
the amount of iron is 74 to 79%, preferably 75 to 78%, and more preferably 77%.
The invention discloses a preparation method of an iron-based bone scaffold with both degradable and antibacterial activities, which comprises the following steps:
step one
Step one
Under the protective atmosphere, silver powder, iron powder and manganese powder are distributed according to a design group; uniformly mixing the silver powder, the iron powder and the manganese powder to obtain uniformly dispersed mixed powder;
and step two, taking the uniformly dispersed mixed powder obtained in the step one as a raw material, taking selective laser melting as a process, wherein the laser power is 70-120W, the scanning speed is 20-40mm/s, the laser spot diameter is 0.1-0.3mm, the powder spreading thickness is 100-150 mu m, and melting and solidifying under the protection of argon to obtain the iron-based alloy.
Further, the particle size of the silver powder is 1-10 μm, the particle size of the manganese powder is 15-40 μm, the particle size of the iron powder is 20-60 μm, and the shape of the iron powder is spherical to ensure that the iron powder has better fluidity.
According to the invention, the melting point of silver is low, so that the silver can be changed into a liquid phase firstly in the laser melting process, not only can the gaps among solid-phase particles be filled, but also the migration of substances can be accelerated through the flow of the liquid phase, thereby avoiding the problem of micro defects in the forming process and improving the density of the alloy; meanwhile, silver can be precipitated and dispersed on a crystal boundary in the process of rapid cooling, and the silver has a much higher electrode potential than iron, can form strong galvanic corrosion with an iron matrix, and accelerates the degradation of the bracket; the silver/silver ions have excellent antibacterial performance and can endow the stent with good antibacterial activity; meanwhile, the precipitated phase can play a role in precipitation strengthening, so that the yield strength of the alloy bracket is remarkably increased, and the high strength is a necessary condition for ensuring the supporting function of the bracket structure.
The silver powder content is too high, which can cause the concentration of silver ions around cells or tissues to be too high, inhibit the activity of the cells and even cause toxicity; the content of the silver powder is too low, so that the silver powder cannot generate obvious antibacterial action and cannot exert the antibacterial effect easily.
In addition, the present invention must strictly control other parameters of the laser melting process, such as: laser power, scanning speed, powder spreading thickness, scanning interval and the like. The laser power is too high, the powder laying thickness is reduced, the scanning distance is reduced, the energy input is too high, the gasification splashing is serious, the powder ablation is caused, and the forming quality is reduced; the laser power is too low, the powder spreading thickness is increased, the scanning distance is increased, the laser energy input is low, the powder cannot be fully melted, and the bone scaffold has low density and even cannot be molded.
Meanwhile, the size of the silver powder needs to be strictly controlled, and if the size of the silver powder particles is too small, the dispersion technical requirement and the cost are too high; if the particle size of the silver powder is too large, the distribution of the added silver powder in the matrix becomes too concentrated, and it becomes difficult to obtain a silver pasteThe function of the added phase is fully exerted. The selective laser melting of the present invention has the features of fast melting and fast cooling, and very fast cooling rate (10)5-106K/s) can control the flowing of molten metal and the heat and mass transfer processes in the solidification process, thereby being beneficial to reducing the size of crystal grains and improving the uniformity of microscopic structures, and further ensuring that silver is uniformly precipitated and dispersed on the crystal boundary.
Compared with the prior art, the invention has the following advantages:
(1) in the invention, the silver can be changed into liquid state firstly in the laser melting process, thereby avoiding the problem of micro defects in the laser forming process and improving the density of the iron-based alloy.
(2) Silver can be precipitated and dispersed on a crystal boundary in the process of rapid cooling, and a large number of microcosmic galvanic corrosion units are formed with an iron matrix, so that rapid degradation is carried out macroscopically, and the problems of new bone growth and secondary operation obstruction are avoided.
(3) Silver is uniformly dispersed and precipitated on a crystal boundary, so that the precipitation strengthening effect can be achieved, the strength of the bone scaffold is improved, and sufficient structural support is provided for the bone defect part.
(4) The invention has simple preparation process and short production period, adopts selective laser melting for one-step molding after mechanically mixing the powder, and has good antibacterial activity because of the existence of silver/silver ions in the degradation process.
(5) The iron-based bone scaffold with both degradable and antibacterial activity and the preparation method thereof are simple and reliable, and can realize personalized implant customization, thereby meeting the requirements of different patients.
Detailed Description
Example 1
Silver powder, iron powder and manganese powder are used as raw materials, the particle size of the silver powder is 3 mu m, the particle size of the manganese powder is 15-40 mu m, the particle size of the iron powder is 20-60 mu m, and the silver powder, the iron powder and the manganese powder are mixed according to the proportion of 3: 77: weighing 3g of silver powder, 77g of iron powder and 20g of manganese powder according to the mass ratio of 20, and mechanically stirring and mixing the mixed powder for 30 minutes under the protection of argon; the iron-based bone scaffold is obtained by using the mixed powder as a raw material, using selective laser melting as a process, wherein the laser power is 95W, the diameter of a laser spot is 0.1mm, the powder spreading thickness is 100 mu m, and melting and solidifying the mixed powder under the protection of argon.
The implementation effect is as follows: tests on the prepared iron-based bone scaffold show that the silver is uniformly dispersed in an iron matrix, the microstructure has no obvious defects such as cracks, pores and the like, the degradation rate is 0.26mm/y after the iron-based bone scaffold is soaked in a human body simulation body liquid, and antibacterial experiments show that the concentration is 106The sterilization rates of the staphylococcus and the escherichia coli in the CFU/mL respectively reach 95.3 percent and 96.2 percent, and the compressive yield strength is 300 MPa.
Example 2
Silver powder, iron powder and manganese powder are used as raw materials, the particle size of the silver powder is 3 mu m, the particle size of the manganese powder is 15-40 mu m, the particle size of the iron powder is 20-60 mu m, and the ratio of the silver powder to the manganese powder is 1: 79: weighing 1g of silver powder, 79g of iron powder and 20g of manganese powder according to the mass ratio of 20, and mechanically stirring and mixing the mixed powder for 30 minutes under the protection of argon; the iron-based bone scaffold is obtained by using the mixed powder as a raw material, using selective laser melting as a process, wherein the laser power is 95W, the diameter of a laser spot is 0.1mm, the powder spreading thickness is 100 mu m, and melting and solidifying the mixed powder under the protection of argon.
The implementation effect is as follows: tests on the prepared iron-based bone scaffold show that silver is uniformly dispersed in an iron matrix, defects such as obvious cracks and small holes do not exist in a microstructure, the degradation rate is calculated to be 0.17mm/y after the iron-based bone scaffold is soaked in human body simulated body fluid, and antibacterial experiments show that the concentration is 106The sterilization rates of the staphylococcus and the escherichia coli in the CFU/mL respectively reach 85.4 percent and 86.9 percent, and the compressive yield strength is 240 MPa.
Example 3
Silver powder, iron powder and manganese powder are used as raw materials, the particle size of the silver powder is 10 mu m, the particle size of the manganese powder is 15-40 mu m, the particle size of the iron powder is 20-60 mu m, and the ratio of the silver powder to the manganese powder is 3: 77: weighing 3g of silver powder, 77g of iron powder and 20g of manganese powder according to the mass ratio of 20, and mechanically stirring and mixing the mixed powder for 30 minutes under the protection of argon; the iron-based bone scaffold is obtained by using the mixed powder as a raw material, using selective laser melting as a process, wherein the laser power is 95W, the diameter of a laser spot is 0.1mm, the powder spreading thickness is 100 mu m, and melting and solidifying the mixed powder under the protection of argon.
The implementation effect is as follows: tests on the prepared iron-based bone scaffold show that the silver is uniformly dispersed in an iron matrix, the microstructure has no obvious defects such as cracks, pores and the like, the degradation rate is 0.23mm/y after the iron-based bone scaffold is soaked in a human body simulation body liquid, and antibacterial experiments show that the concentration is 106The sterilization rates of the staphylococcus and the escherichia coli in the CFU/mL respectively reach 91.4 percent and 92.5 percent, and the compressive yield strength is 260 MPa.
In the process of developing the technology of the invention, the following schemes (such as comparative example 1, comparative example 2 and comparative example 3) are also tried, but the performance of the obtained product is far worse than that of the examples.
Comparative example 1
The other conditions were the same as in example 1 except that: according to the following steps of 8: 72: weighing 8g of silver powder, 72 g of iron powder and 20g of manganese powder according to the mass ratio of 20 to obtain the iron-based bone scaffold, and testing shows that part of silver is continuously distributed in a matrix, the dispersion strengthening effect is not obvious, more importantly, the silver ion concentration is too high, although the antibacterial effect is obvious, the antibacterial effect is 10 g6The sterilization rates of the staphylococcus and the escherichia coli of CFU/mL respectively reach 97.5% and 98.6%, but the high cytotoxicity is generated at the same time, and the compressive yield strength is 208 MPa.
Comparative example 2
The other conditions were the same as in example 1 except that: according to the weight ratio of 0.5: 79.5: 20 weight ratio of 0.5g silver powder, 79.5 g iron powder and 20g manganese powder, to obtain an iron-based bone scaffold, it was found that after immersion in a human simulated body fluid, the calculated degradation rate was 0.11mm/y, and too slow degradation resulted in a concentration of 106The sterilization rate of the staphylococcus and the escherichia coli of CFU/mL is only 14.4 percent and 32.8 percent, and the compressive yield strength is 160 MPa.
Comparative example 3
The other conditions were the same as in example 1 except that: the granularity of the silver powder is 30 mu m, an iron-based bone scaffold is obtained, the microstructure shows that the silver phase is distributed in a matrix in a semicontinuous way and is not uniformly distributed, and the calculated degradation rate is 0.17mm/y after the silver phase is soaked in human body simulation body fluid, but local corrosion, uneven corrosion surface, serious pitting and pits along with the pitting corrosion are generatedIn progress, severe gaps occur which may cause implant failure. Antibacterial experiments show that the concentration is 106The sterilization rates of the staphylococcus and the escherichia coli in the CFU/mL respectively reach 71.7 percent and 73.6 percent, and the compressive yield strength is 140 MPa.
Comparative example 4
The other conditions were the same as in example 1 except that: the laser power is 50W, only the silver powder is completely melted in the forming process, the iron powder and the manganese powder are partially melted, a large amount of unmelted particles are mixed in the obtained iron-based bone scaffold, the forming quality is poor, the compressive yield strength is 95MPa, and the mechanical strength requirement of the bone scaffold is difficult to meet.
As can be seen from example 1 and comparative examples 1, 2, 3 and 4, the components and preparation process of the present invention are an organic whole, and the effect is significantly reduced when any one or more of the key parameters is out of the scope of the present invention. The inherent comparison of example 1 and examples 2 and 3 of the present invention shows that the preferred embodiment of the present invention has unexpected advantages.
Claims (8)
1. An iron-based bone scaffold with both degradable and antibacterial activity; it is characterized in that; the iron-based bone scaffold comprises the following components in percentage by mass:
manganese accounts for 20%
1-6% of silver;
the content of iron is 74-79%.
2. A degradable and antibacterial iron-based bone scaffold according to claim 1; it is characterized in that; the iron-based bone scaffold comprises the following components in percentage by mass:
manganese accounts for 20%
2-5% of silver;
the iron content is 75-78%.
3. A degradable and antibacterial iron-based bone scaffold according to claim 2; it is characterized in that; the iron-based bone scaffold comprises the following components in percentage by mass:
manganese accounts for 20%
3% of silver;
the iron content is 77%.
4. A degradable and antibacterial iron-based bone scaffold according to claim 1; it is characterized in that; the iron-based bone scaffold is soaked in human body simulated body fluid to obtain a degradation rate of 0.17-0.26 mm/y.
5. A degradable and antibacterial iron-based bone scaffold according to claim 1; it is characterized in that; silver in the iron-based bone scaffold is attached to a crystal boundary and is dispersed and distributed.
6. A method for preparing an iron-based bone scaffold having both degradable and antibacterial activity according to any one of claims 1-5, comprising the steps of:
step one
Under the protective atmosphere, silver powder, iron powder and manganese powder are distributed according to a design group; uniformly mixing the silver powder, the iron powder and the manganese powder to obtain uniformly dispersed mixed powder;
step two
And (3) taking the uniformly dispersed mixed powder obtained in the step one as a raw material, taking selective laser melting as a process, wherein the laser power is 70-120W, the scanning speed is 20-40mm/s, the diameter of a laser spot is 0.1-0.3mm, the powder spreading thickness is 100-150 mu m, and melting and curing under the protection of argon to obtain the iron-based bone scaffold.
7. The method for preparing an iron-based bone scaffold with both degradable and antibacterial activities as claimed in claim 6, wherein; the granularity of the silver is 1-10 mu m, the granularity of the manganese powder is 15-40 mu m, and the granularity of the iron powder is controlled to be 20-60 mu m.
8. The method for preparing an iron-based bone scaffold with both degradable and antibacterial activities as claimed in claim 6, wherein; mechanically stirring and mixing the silver powder, the iron powder and the manganese powder for 10-40 minutes; a uniformly dispersed mixed powder was obtained.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114606433A (en) * | 2020-12-08 | 2022-06-10 | 香港大学 | Method for preparing antibacterial stainless steel by utilizing rapid solidification process and application thereof |
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| CN107648676A (en) * | 2017-11-08 | 2018-02-02 | 谭思暄 | A kind of degradable iron-based angiocarpy bracket material and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114606433A (en) * | 2020-12-08 | 2022-06-10 | 香港大学 | Method for preparing antibacterial stainless steel by utilizing rapid solidification process and application thereof |
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