CN113755738A - Degradable iron-based alloy material and preparation method and application thereof - Google Patents
Degradable iron-based alloy material and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to a degradable iron-based alloy material and a preparation method and application thereof. The degradable iron-based alloy material comprises the following raw material components of Fe-Mn-C pre-alloy powder and graphite; wherein the Fe-Mn-C pre-alloyed powder comprises the following components in percentage by mass: 16 to 25 percent of Mn, 0.6 to 0.77 percent of C and 74.23 to 83.4 percent of Fe; the graphite accounts for 0.3-0.6% of the total mass of the raw material components. The degradable iron-based alloy material has high degradation rate and can meet the degradation requirement of an implant material.
Description
Technical Field
The invention relates to the technical field of biomedical materials, in particular to a degradable iron-based alloy material and a preparation method and application thereof.
Background
Biomedical metal materials are the most widely used implant materials in clinical applications. With the development of materials and medical fields, there are a series of metal complex parts such as pure metal, stainless steel, cobalt-chromium alloy, titanium alloy and the like, however, the long-term retention of these metals as implants in the body often causes some complications. Some adverse consequences may occur for a certain type of stent, such as cardiovascular stents, bone stents, etc., for example: the fixed stainless steel plate and the screws used after fracture need to be taken out again after the affected part is healed, so that the pain of a patient is increased, and the additional economic cost is increased; the long-term retention of the human vascular stent can cause hyperplasia of vascular intima, thereby increasing the incidence of vascular restenosis.
Later, researchers became increasingly aware that inert biomaterials are not the only implantable materials, but are replaced by degradable implant materials, especially in the orthopedic and cardiovascular fields where this demand is rapidly increasing. In traditional research, degradable biomedical metals are mainly concentrated on magnesium and magnesium alloys, zinc and zinc alloys. However, it has been reported that magnesium alloy has poor mechanical properties compared with stainless steel and other materials, and is difficult to support, and that magnesium alloy scaffolds and bone implants have a rapid degradation rate and a rapid mechanical loss, and have failed before the injured tissue is remodeled.
On the basis, iron-based metal is developed as a novel degradable cardiovascular stent. The Fe element is a trace element necessary for human body and has a plurality of physiological functions, such as electron transfer, oxygen transportation and the like. Research shows that the iron-based material is safe and reliable as a biodegradable cardiovascular stent material.
Although the iron-based alloy has a good application prospect in the field of degradable biological materials, the degradation rate of pure iron is too low to adapt to the degradation requirement of an implanted material, and the iron-based alloy still faces the adverse effect of long-term retention.
Disclosure of Invention
Based on the above, the invention provides the degradable iron-based alloy material which is high in degradation rate and can meet the degradation requirement of the implant material, and the preparation method and the application thereof.
The specific technical scheme is as follows:
the invention provides a degradable iron-based alloy material, which comprises the following raw material components of Fe-Mn-C pre-alloy powder and graphite;
wherein the Fe-Mn-C pre-alloyed powder comprises the following components in percentage by mass: 16 to 25 percent of Mn, 0.6 to 0.77 percent of C and 74.23 to 83.4 percent of Fe;
the graphite accounts for 0.3-0.6% of the total mass of the raw material components.
In one embodiment, the graphite accounts for 0.3-0.4% of the total mass of the raw material components.
In one embodiment, the graphite is colloidal graphite, and the particle size of the powder is less than or equal to 2.5 microns.
In one embodiment, the Fe-Mn-C pre-alloyed powder comprises the following components: 17.5 to 18.5 percent of Mn, 0.6 to 0.65 percent of C and the balance of Fe.
In one embodiment, the Fe-Mn-C prealloyed powder has a particle size less than 320 mesh.
In one embodiment, the feedstock components further comprise copper powder; the copper powder accounts for 0.1-9% of the total mass of the raw material components.
In one embodiment, the copper powder is electrolytic copper powder, and the particle size of the powder is less than or equal to 25 mu m.
In a second aspect of the present invention, there is provided a method for preparing the degradable iron-based alloy material, comprising the following steps:
mixing the raw material components to prepare composite powder;
pressing and molding the composite powder to prepare a green body;
and sintering the green body.
In one embodiment, the pressure for compression molding is 600MPa to 750 MPa; and/or
The sintering is carried out in a reducing atmosphere or a vacuum environment, the sintering temperature is 1150-1200 ℃, and the sintering time is 1-1.5 h.
In a third aspect of the invention, the application of the degradable iron-based alloy material in manufacturing an implant is provided.
According to the degradable iron-based alloy material, Fe-Mn-C pre-alloyed powder and graphite are used as raw material components, C element and Mn element are introduced on the basis of pure iron, the standard electrode potential of the Mn element is-1.18V and is far lower than that of the pure iron, and the degradation rate of the powder metallurgy non-magnetic steel is greatly improved by adding the Mn element. Meanwhile, the introduction of Mn element can increase the degradation rate in principle, but it has a problem that it is difficult to uniformly distribute, and thus it is difficult to substantially increase the degradation rate of the entire material. Based on this, the degradable iron-based alloy material further adds the element C in different adding forms, on one hand, the element C is added in the form of Fe-Mn-C pre-alloyed powder, which is beneficial to uniform distribution of the element Mn and reduction of burning loss and evaporation of the element Mn in the sintering process, the degradable material can be uniformly degraded due to uniform distribution of the element Mn, the influence on the use performance caused by non-uniform degradation rate of the material due to non-uniform distribution of the element is prevented, on the other hand, the element C is added in the form of graphite, which can perform the functions of deoxidation and reduction of certain oxides, and the uniformity of the material is further improved. Therefore, the degradable iron-based alloy material has high degradation rate and can meet the degradation requirement of an implanted material.
Meanwhile, in the research process, the degradable iron-based alloy material also has the following characteristics:
(1) pure iron has a certain ferromagnetism, which reduces the compatibility of nuclear magnetic resonance. The degradable iron-based alloy material is paramagnetic through reasonable compatibility of elements, and can effectively enhance the compatibility of nuclear magnetic resonance imaging;
(2) the mechanical property of the pure iron is poor, and the mechanical property of the obtained degradable iron-based alloy material is effectively improved by introducing C element and Mn element into Fe-Mn-C pre-alloy powder and graphite;
(3) the degradable iron-based alloy material has better hydrophilicity, is beneficial to cell adhesion, and can meet the biological requirement of an implant material.
Further, the bio-alloy material itself is a bio-inert material as a foreign material, and is easily implanted to cause bacterial infection and urinary calculi. The invention also provides a research processIt is found that a certain amount of Cu element is also introduced into the degradable iron-based alloy material, and the alloy material has high degradation rate and can release Cu in the degradation process by combining the raw material components2+Thus, the growth of bacteria can be obviously inhibited, and the generation of calculus can be reduced.
In addition, since the implantable biomaterial has a relatively complicated shape, it is difficult to perform a mass production at a low cost by the conventional casting method. The degradable iron-based alloy material can be produced by adopting a powder metallurgy mode, and is convenient for industrial mass production and application. Meanwhile, a certain pore space can be formed in the material by adopting a powder metallurgy mode, and the degradation rate of the material can be further improved due to the existence of the pore space.
Drawings
FIG. 1 is a polarization curve of materials of examples and comparative examples of the present invention in a simulated body fluid Hank, s;
FIG. 2 is a contact angle of materials of examples of the present invention and comparative examples;
FIG. 3 is a magnetization curve of materials of examples of the present invention and comparative examples;
FIG. 4 is a graph showing the growth of E.coli in the material solutions of the examples of the present invention and the comparative example;
fig. 5 is a graph showing the weight loss rate of the materials of the examples and comparative examples of the present invention after 1 day, 5 days and 10 days of immersion in Hank's solution.
Detailed Description
The degradable iron-based alloy material, the preparation method and the application thereof are further described in detail with reference to the following specific examples. The present invention may be embodied in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
As used herein, the term "and/or", "and/or" includes any one of two or more of the associated listed items, as well as any and all combinations of the associated listed items, including any two of the associated listed items, any more of the associated listed items, or all combinations of the associated listed items.
As used herein, "one or more" refers to any one, any two, or any two or more of the listed items.
In the present invention, "first aspect", "second aspect", "third aspect" and the like are used for descriptive purposes only and are not to be construed as indicating or implying a relative importance or quantity, nor are they to be construed as implicitly indicating the importance or quantity of the technical feature indicated. Also, "first," "second," "third," etc. are for non-exhaustive enumeration description purposes only and should not be construed as constituting a closed limitation to the number.
In the present invention, the technical features described in the open type include a closed technical solution composed of the listed features, and also include an open technical solution including the listed features.
In the present invention, the numerical intervals are regarded as continuous, and include the minimum and maximum values of the range and each value between the minimum and maximum values, unless otherwise specified. Further, when a range refers to an integer, each integer between the minimum and maximum values of the range is included. Further, when multiple range-describing features or characteristics are provided, the ranges may be combined. In other words, unless otherwise indicated, all ranges disclosed herein are to be understood to encompass any and all subranges subsumed therein.
The percentage contents referred to in the present invention mean, unless otherwise specified, mass percentages for solid-liquid mixing and solid-solid phase mixing, and volume percentages for liquid-liquid phase mixing.
The percentage concentrations referred to in the present invention refer to the final concentrations unless otherwise specified. The final concentration refers to the ratio of the additive component in the system to which the component is added.
The temperature parameter in the present invention is not particularly limited, and may be a constant temperature treatment or a treatment within a certain temperature range. The constant temperature process allows the temperature to fluctuate within the accuracy of the instrument control.
The invention provides a degradable iron-based alloy material, which comprises the following raw material components of Fe-Mn-C pre-alloy powder and graphite;
wherein the Fe-Mn-C pre-alloyed powder comprises the following components in percentage by mass: 16 to 25 percent of Mn, 0.6 to 0.77 percent of C and 74.23 to 83.4 percent of Fe;
the graphite accounts for 0.3 to 0.6 percent of the total mass of the raw material components.
It is understood that the above-described degradable iron-based alloy material or Fe-Mn-C pre-alloy powder inevitably contains some impurity elements.
In some specific examples, the degradable iron-based alloy material is non-magnetic steel with Austenite (Austenite) as a matrix. Austenite is a lamellar microstructure of steel, usually a non-magnetic solid solution of gamma-Fe with a small amount of carbon in solid solution, also known as austenite or gamma-Fe. In some specific examples, the degradable iron-based alloy material does not contain a binder, an activator, a lubricant and other auxiliaries in a traditional non-magnetic steel material.
In some specific examples, the degradable iron-based alloy material has an elemental composition including, in mass percent: 16 to 25 percent of Mn, 0.9 to 1.2 percent of C and 74.23 to 81.9 percent of Fe.
In some specific examples, the graphite accounts for 0.3-0.6% of the total mass of the raw material components. Specifically, the mass percentages of the graphite in the total mass of the raw material components include, but are not limited to: 0.3%, 0.35%, 0.4%, 0.45%, 0.5%, 0.55%, 0.6%. Further, the graphite accounts for 0.3-0.4% of the total mass of the raw material components.
In some specific examples, the graphite is colloidal graphite, and the powder particle size is less than or equal to 2.5 μm. Further, the purity of graphite is greater than 99.6%.
In some specific examples, the Fe-Mn-C prealloyed powder includes the following ingredients: 17.5 to 18.5 percent of Mn, 0.6 to 0.65 percent of C and the balance of Fe. It is understood that the Fe-Mn-C prealloyed powder inevitably contains some impurity elements.
In some specific examples, the Fe-Mn-C pre-alloyed powder has a particle size of less than 320 mesh.
Further, the bio-alloy material itself is a bio-inert material as a foreign material, and is easily implanted to cause bacterial infection and urinary calculi. Based on the above, in some specific examples, the degradable iron-based alloy material further comprises copper powder; copper powder accounts for 0.1-9% of the total mass of the raw material components. A certain amount of Cu element is introduced, and the raw material components are matched, so that the alloy material has high degradation rate and can release Cu in the degradation process2+Effectively inhibit the growth of bacteria and reduce the generation of calculus. Specifically, the mass percentage of the copper powder in the total mass of the raw material components includes but is not limited to: 0.1%, 0.5%, 1%, 2%, 2.5%, 3%, 3.5%, 4%, 5%, 6%, 7%, 8%, 9%.
In some specific examples, the copper powder accounts for 2-4% of the total mass of the raw material components.
In some specific examples, the copper powder is electrolytic copper powder, and the particle size of the powder is less than or equal to 25 μm. Further, the purity of the copper powder is greater than 99.8%.
In addition, since the implantable biomaterial has a relatively complicated shape, it is difficult to perform a mass production at a low cost by the conventional casting method. Based on the above, the invention also provides a preparation method of the degradable iron-based alloy material, which comprises the following steps:
mixing the raw material components to prepare composite powder;
pressing and molding the composite powder to prepare a green body;
and sintering the green body.
The degradable iron-based alloy material is produced by adopting a powder metallurgy mode, and is convenient for industrial mass production and application. Meanwhile, a certain pore space can be formed in the material by adopting a powder metallurgy mode, and the degradation rate of the material can be further improved due to the existence of the pore space.
In some specific examples, the conditions of mixing include: mixing for 3-8 h under the condition that the rotating speed is 100-300 r/min. Specifically, the time of mixing includes, but is not limited to: 3h, 4h, 4.5h, 5h, 5.5h, 6h, 7h and 8 h.
In some specific examples, the method of press forming is cold die press forming.
In some specific examples, the pressure for press forming is 600MPa to 750 MPa. Specifically, the pressure of the press forming includes, but is not limited to: 600MPa, 610MPa, 620MPa, 630MPa, 640MPa, 650MPa, 670MPa, 680MPa, 690MPa, 700MPa, 710MPa, 720MPa, 730MPa, 740MPa, 750 MPa.
In some specific examples, the sintering is performed in a reducing atmosphere or in a vacuum environment. The reducing atmosphere can be, for example, an ammonia decomposition atmosphere, wherein ammonia decomposition means that hydrogen and nitrogen are introduced at a flow ratio of 1 (2.5-3.5).
In some specific examples, the sintering temperature is 1150 ℃ to 1200 ℃. Specifically, the temperature of sintering includes, but is not limited to: 1150 deg.C, 1155 deg.C, 1160 deg.C, 1165 deg.C, 1170 deg.C, 1175 deg.C, 1180 deg.C, 1190 deg.C, 1195 deg.C, 1200 deg.C.
In some specific examples, the sintering temperature is 1h to 1.5 h. Specifically, the time of sintering includes, but is not limited to: 1h, 1.25h and 1.5 h.
In some specific examples, the sintering is performed in a reducing atmosphere or a vacuum environment, the sintering temperature is 1150-1200 ℃, and the sintering time is 1-1.5 h.
In some specific examples, the sintering is carried out in an ammonia decomposing atmosphere, the sintering temperature is 1170-1180 ℃, and the sintering time is 1 h.
In some specific examples, after sintering, the method further comprises the step of cooling: cooling to room temperature along with the furnace.
The invention also provides application of the degradable iron-based alloy material in manufacturing an implant.
In some specific examples, the implant is a biodegradable implant.
In some specific examples, the implant refers to orthopedic and cardiovascular implants. Further, the implant may be a cardiovascular stent, a bone implant.
Specific examples are as follows.
The preparation method of the Fe-Mn-C prealloying powder adopted in the embodiment is that the Fe-Mn-C prealloying powder is prepared by melting and mixing A3 steel, medium-carbon ferromanganese and high-carbon ferromanganese and adopting a water atomization method.
Comparative example 1
The comparative example is a preparation method of a degradable material, and the steps are as follows:
(1) preparing a green embryo:
carrying out cold die pressing (the pressure is 680MPa) on pure iron powder under a press, and forming and pressing to obtain a green body, wherein the granularity of the pure iron powder is 200 meshes;
(2) and (3) sintering:
subjecting the green body obtained in step (1) to ammonia decomposition atmosphere (flow ratio N)2:H2And (3: 1) carrying out normal-pressure high-temperature sintering in a push rod type sintering furnace, wherein the sintering temperature is 1175 ℃, and the high-temperature sintering time is 1 h. And then cooling to room temperature along with the furnace to obtain the degradable material.
The degradable material of this comparative example (noted as Pure iron or Pure Fe) was subjected to a performance test:
the room temperature tensile property test is carried out according to the GB/T7964 standard, and as shown in Table 1, the mechanical property of pure iron is poor, the yield tensile strength is 238 +/-16 MPa, and the elongation after fracture is 18.2 +/-1.7%.
Fig. 1 shows the polarization curve of pure iron in a simulated body fluid Hank, s.
Fig. 2 shows the contact angle of pure iron in pure water, which is 70.3 °.
Fig. 3 shows the magnetization curve of pure iron, which is shown to be ferromagnetic and not conducive to nmr compatibility.
FIG. 4 shows the growth curve of E.coli in pure iron. Wherein the pure iron solution is prepared by dispersing bacteria in PBS buffer solution, adjusting pH to 7.4 to ensure bacteria concentration of about 1 × 10/ml5And (4) bacterial cells. Subsequently, 500. mu.L of the bacterial suspension was mixed with the test material and 500. mu.L of PBS buffer solution, and incubated in a constant temperature incubator (37 ℃ C.) for 4 hours. 100 mu L of the solution is poured into 500 mu L of tryptone soy broth, mixed evenly and poured into a 96-well plate, and incubated at a constant temperature of 37 ℃. Bacteria cultured in PBS buffer solution were used as a control group. Pure iron has little bacteriostatic activity.
FIG. 5 shows the weight loss rates of Fe-Mn-C-3Cu high-manganese non-magnetic steel soaked in Hank's solution for 1 day, 5 days and 10 days, which are faster than pure iron, indicating that the steel has a faster degradation rate in physiological environment.
Example 1
The embodiment is a preparation method of a degradable iron-based alloy material, which comprises the following steps:
(1) preparing composite powder:
uniformly mixing Fe-Mn-C pre-alloy powder and graphite in a V-shaped mixer (the rotating speed is 180r/min), wherein the mixing time is 5h, and the mass fraction of each component in the Fe-Mn-C pre-alloy powder is as follows: mn: 18 wt%, C: 0.6 wt% and the balance Fe, the particle size is less than 320 meshes; the graphite is colloidal graphite (the mass content is more than 99.6 percent, and the particle size of the powder is less than or equal to 2.5 mu m), and the mass of the graphite accounts for 0.3 percent of the total weight of the raw material components.
(2) Preparing a green embryo:
pressing the composite powder obtained in the step (1) by a cold die under a press to obtain a green body (the pressure is 680 MPa);
(3) and (3) sintering:
subjecting the green body obtained in step (2) to ammonia decomposition atmosphere (flow ratio N)2:H2And (3: 1) carrying out normal-pressure high-temperature sintering in a push rod type sintering furnace, wherein the sintering temperature is 1175 ℃, and the high-temperature sintering time is 1 h. And then cooling to room temperature along with the furnace to prepare the degradable iron-based alloy material (austenite biodegradable material).
The degradable iron-based alloy material (noted as Fe-18Mn-C or Fe-18Mn-C-0Cu) of this example was subjected to a performance test and compared with comparative example 1:
the room temperature tensile properties test was performed according to GB/T7964 standard, and as shown in Table 1, Fe-18Mn-C has better mechanical properties than pure iron (comparative example 1), tensile strength of 503 + -20, twice as high as pure iron, and elongation after fracture of 11.6 + -2.1.
FIG. 1 shows the polarization curve of Fe-18Mn-C in simulated body fluid Hank's, and Fe-18Mn-C has a better corrosion current density of 54.72uA/cm compared to pure iron2About 10 times of pure iron, which shows that the iron has faster degradation speed in physiological environment.
FIG. 2 shows the contact angle of Fe-18Mn-C in pure water, which is 69.6 deg., and is smaller than that of pure iron, thus having higher hydrophilicity and significantly improved cell adhesion ability.
FIG. 3 shows the magnetization curve of Fe-18Mn-C, which shows that it is paramagnetic, and the paramagnetic Fe-18Mn-C is more favorable for improving the nuclear magnetic resonance compatibility compared with the ferromagnetism of pure iron.
FIG. 4 is a graph showing the growth of E.coli in each alloy solution prepared by dispersing the bacteria in PBS buffer and then adjusting the pH of the solution to 7.4 to a concentration of about 1X 10 bacteria per ml5And (4) bacterial cells. Subsequently, 500. mu.L of the bacterial suspension was mixed with the test material and 500. mu.L of PBS buffer solution, and incubated in a constant temperature incubator (37 ℃ C.) for 4 hours. 100 mu L of the solution is poured into 500 mu L of tryptone soy broth, mixed evenly and poured into a 96-well plate, and incubated at a constant temperature of 37 ℃. Bacteria cultured in PBS buffer solution were used as a control group. As can be seen from the figure, pure iron has almost no bacteriostatic activity, Fe-18Mn-C has certain bacteriostatic activity, but the bacteriostatic action is longer and the effect is weaker.
FIG. 5 shows the weight loss rates of Fe-18Mn-C after 1 day, 5 days and 10 days of immersion in Hank's solution, which are faster than pure iron, indicating a faster degradation rate in physiological environment.
Example 2
The embodiment is a preparation method of a degradable iron-based alloy material, which comprises the following steps:
(1) preparing composite powder:
uniformly mixing Fe-Mn-C pre-alloy powder, copper powder and graphite in a V-shaped mixer (the rotating speed is 180r/min) for 5h, wherein the mass fraction of each component in the Fe-Mn-C pre-alloy powder is as follows: mn: 18 wt%, C: 0.6 wt% and the balance Fe, the particle size is less than 320 meshes; the graphite is colloidal graphite (the mass content is more than 99.6 percent, and the particle size of the powder is less than or equal to 2.5 mu m), and the mass of the graphite accounts for 0.3 percent of the total weight of the raw material components; the copper powder is electrolytic copper powder (the mass content is more than 99.8%, and the particle size of the powder is less than or equal to 25 μm), and the mass of the electrolytic copper powder accounts for 3% of the total weight of the raw material components.
(2) Preparing a green embryo:
pressing the composite powder obtained in the step (1) by a cold die under a press to obtain a green body (the pressure is 680 MPa);
(3) and (3) sintering:
subjecting the green body obtained in step (2) to ammonia decomposition atmosphere (flow ratio N)2:H2And (3: 1) carrying out normal-pressure high-temperature sintering in a push rod type sintering furnace, wherein the sintering temperature is 1175 ℃, and the high-temperature sintering time is 1 h. And then cooling to room temperature along with the furnace to prepare the degradable iron-based alloy material (austenite biodegradable material).
The degradable iron-based alloy material of the present example (designated as Fe-18Mn-C-3Cu) was subjected to a performance test and compared with comparative example 1:
the room temperature tensile property test was performed according to GB/T7964 standard, and as shown in Table 1, Fe-18Mn-C-3Cu has better mechanical properties than pure iron (comparative example 1), tensile strength of 524 + -18 MPa, and elongation after fracture of 12.8 + -1.6%.
FIG. 1 shows the polarization curve of Fe-18Mn-C-3Cu in simulated body fluids Hank's, Fe-18Mn-C-3Cu having a better corrosion current density of 9.18uA/cm compared to pure iron 22 times of pure iron. Indicating that the degradation rate is faster in the physiological environment.
FIG. 2 shows the contact angle of Fe-18Mn-C-3Cu in pure water, which is 73.1 degrees, has good hydrophilicity and is beneficial to cell adhesion.
The magnetization curve given in FIG. 3 shows that Fe-18Mn-C-3Cu is paramagnetic, which is more favorable for improving the nuclear magnetic resonance compatibility than pure ferromagnetic.
FIG. 4 is a graph showing the growth of E.coli in each alloy liquid. Wherein the alloy solution is prepared by dispersing bacteria in PBS buffer solution, adjusting pH to 7.4 to ensure bacteria concentration of about 1 × 10/ml5And (4) bacterial cells. Subsequently, 500. mu.L of the bacterial suspension was mixed with the test material and 500. mu.L of PBS buffer solution, and incubated in a constant temperature incubator (37 ℃ C.) for 4 hours. 100 mu L of the solution is poured into 500 mu L of tryptone soy broth, mixed evenly and poured into a 96-well plate, and incubated at a constant temperature of 37 ℃. Bacteria cultured in PBS buffer solution were used as a control group. As can be seen from the figure, Fe-18Mn-C-3Cu containing copper has significant bacteriostatic activity, while pure iron has little bacteriostatic activity, and Fe-18Mn-C containing no copper has very insignificant bacteriostatic activity.
FIG. 5 shows the weight loss rates of the high manganese non-magnetic steel after being soaked in Hank's solution for 1 day, 5 days and 10 days, and the rate of Fe-18Mn-C-3Cu is faster than that of pure iron, which indicates that the high manganese non-magnetic steel has a faster degradation rate in physiological environment.
Example 3
The embodiment is a preparation method of a degradable iron-based alloy material, which comprises the following steps:
(1) preparing composite powder:
uniformly mixing Fe-Mn-C pre-alloy powder, copper powder and graphite in a V-shaped mixer (the rotating speed is 180r/min) for 5h, wherein the mass fraction of each component in the Fe-Mn-C pre-alloy powder is as follows: mn: 18 wt%, C: 0.6 wt% and the balance Fe, the particle size is less than 320 meshes; the graphite is colloidal graphite (the mass content is more than 99.6 percent, and the particle size of the powder is less than or equal to 2.5 mu m), and the mass of the graphite accounts for 0.3 percent of the total weight of the raw material components; the copper powder is electrolytic copper powder (the mass content is more than 99.8%, and the particle size of the powder is less than or equal to 25 μm), and the mass of the electrolytic copper powder accounts for 6% and 9% of the total weight of the raw material components.
(2) Preparing a green embryo:
pressing the composite powder obtained in the step (1) by a cold die under a press to obtain a green body (the pressure is 680 MPa);
(3) and (3) sintering:
subjecting the green body obtained in step (2) to ammonia decomposition atmosphere (flow ratio N)2:H2And (3: 1) carrying out normal-pressure high-temperature sintering in a push rod type sintering furnace, wherein the sintering temperature is 1175 ℃, and the high-temperature sintering time is 1 h. And then cooling to room temperature along with the furnace to prepare the degradable iron-based alloy material (austenite biodegradable material).
The degradable iron-based alloy material of this example (calculated as Fe-18Mn-C-6Cu and Fe-18Mn-C-9Cu, respectively, based on the amount of copper powder added) was subjected to a performance test and compared with comparative example 1:
the room temperature tensile properties test was performed according to GB/T7964 standard, and as shown in Table 1, Fe-18Mn-C-6Cu and Fe-18Mn-C-9Cu both had better mechanical properties than pure iron (comparative example 1), tensile strengths of 486 + -11 MPa and 501 + -19 MPa, and elongations after fracture of 14.0 + -1.2% and 8.0 + -1.9%.
FIG. 1 shows polarization curves of Fe-18Mn-C-6Cu and Fe-18Mn-C-9Cu in simulated body fluid Hank's, both Fe-18Mn-C-6Cu and Fe-18Mn-C-9Cu have better corrosion current density than pure iron, 8.63uA/cm2And 7.91uA/cm2, which is 1.5 times or more greater than that of pure iron. Indicating that the degradation rate is faster in the physiological environment.
FIG. 2 shows the contact angles of Fe-18Mn-C-6Cu and Fe-18Mn-C-9Cu in pure water, which are 78.2 degrees and 81.2 degrees, have good hydrophilicity and are beneficial to cell adhesion.
FIG. 3 shows magnetization curves of Fe-18Mn-C-6Cu and Fe-18Mn-C-9Cu, which shows that they are paramagnetic, and paramagnetic Fe-18Mn-C-6Cu and Fe-18Mn-C-9Cu are more favorable for improving the nuclear magnetic resonance compatibility than pure ferromagnetism.
FIG. 4 is a graph showing the growth of E.coli in each alloy liquid. Wherein the alloy solution is prepared by dispersing bacteria in PBS buffer solution, adjusting pH to 7.4 to ensure bacteria concentration of about 1 × 10/ml5And (4) bacterial cells. Subsequently, 500. mu.L of the bacterial suspension was mixed with the test substance and 500. mu.L of PBS buffer solution, and the mixture was incubated in a constant temperature incubator (37 ℃ C.)And 4 h. 100 mu L of the solution is poured into 500 mu L of tryptone soy broth, mixed evenly and poured into a 96-well plate, and incubated at a constant temperature of 37 ℃. Bacteria cultured in PBS buffer solution were used as a control group. As can be seen from the figure, Fe-18Mn-C-6Cu and Fe-18Mn-C-9Cu containing copper have significant bacteriostatic activity, while pure iron has little bacteriostatic activity, and Fe-18Mn-C containing no copper has little bacteriostatic activity.
FIG. 5 shows the weight loss rates of Fe-18Mn-C-6Cu and Fe-18Mn-C-9Cu high-manganese nonmagnetic steel after being soaked in Hank's solution for 1 day, 5 days and 10 days, wherein the weight loss rates are faster than that of pure iron, and the degradation rate of the nonmagnetic steel in a physiological environment is faster.
TABLE 1
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, so as to understand the technical solutions of the present invention specifically and in detail, but not to be understood as the limitation of the protection scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. It should be understood that the technical solutions provided by the present invention, which are obtained by logical analysis, reasoning or limited experiments, are within the scope of the appended claims. Therefore, the protection scope of the present invention should be subject to the content of the appended claims, and the description and the drawings can be used for explaining the content of the claims.
Claims (10)
1. The degradable iron-based alloy material is characterized in that the raw material components comprise Fe-Mn-C pre-alloy powder and graphite;
wherein the Fe-Mn-C pre-alloyed powder comprises the following components in percentage by mass: 16 to 25 percent of Mn, 0.6 to 0.77 percent of C and 74.23 to 83.4 percent of Fe;
the graphite accounts for 0.3-0.6% of the total mass of the raw material components.
2. The degradable iron-based alloy material according to claim 1, wherein the graphite accounts for 0.3-0.4% of the total mass of the raw material components.
3. The degradable iron-based alloy material of claim 1, wherein the graphite is colloidal graphite and has a powder particle size of 2.5 μm or less.
4. The degradable iron-based alloy material of claim 1, wherein the Fe-Mn-C pre-alloyed powder comprises the following components: 17.5 to 18.5 percent of Mn, 0.6 to 0.65 percent of C and the balance of Fe.
5. The degradable iron-based alloy material of claim 1, wherein the particle size of the Fe-Mn-C pre-alloyed powder is smaller than 320 mesh.
6. The degradable iron-based alloy material according to any one of claims 1 to 5, wherein the raw material components further comprise copper powder; the copper powder accounts for 0.1-9% of the total mass of the raw material components.
7. The degradable iron-based alloy material of claim 6, wherein the copper powder is electrolytic copper powder, and the particle size of the powder is less than or equal to 25 μm.
8. The method for preparing the degradable iron-based alloy material according to any one of claims 1 to 7, which comprises the following steps:
mixing the raw material components to prepare composite powder;
pressing and molding the composite powder to prepare a green body;
and sintering the green body.
9. The method for preparing the degradable iron-based alloy material according to claim 8, wherein the pressure of the compression molding is 600MPa to 750 MPa; and/or
The sintering is carried out in a reducing atmosphere or a vacuum environment, the sintering temperature is 1150-1200 ℃, and the sintering time is 1-1.5 h.
10. Use of the degradable iron-based alloy material according to any one of claims 1 to 7 in the preparation of an implant.
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| WO2023035731A1 (en) * | 2021-09-10 | 2023-03-16 | 广东粤海华金科技股份有限公司 | Degradable iron-based alloy material, preparation method therefor and application thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102776435A (en) * | 2011-05-13 | 2012-11-14 | 中国科学院金属研究所 | Degradable Fe-Mn-C ternary iron alloy material and its application |
| CN104694848A (en) * | 2015-01-28 | 2015-06-10 | 燕山大学 | Biodegradable quaternary iron-based alloy material and preparation method thereof |
| CN109811265A (en) * | 2017-11-22 | 2019-05-28 | 中国科学院金属研究所 | A kind of Fe-Mn-Cu-C system alloy and its medical application |
| CN110477982A (en) * | 2019-07-24 | 2019-11-22 | 中国科学院金属研究所 | Anti- calculus anastomosis staple of degradable antibacterial suitable for urinary system and preparation method thereof |
| CN111187965A (en) * | 2019-12-31 | 2020-05-22 | 中南大学湘雅二医院 | FeMn biodegradable alloy and preparation method thereof |
| CN111235476A (en) * | 2018-11-29 | 2020-06-05 | 中国科学院金属研究所 | Degradable anti-infection and anti-calculus Fe-Cu series alloy suitable for urinary implant material |
| US20210187157A1 (en) * | 2019-12-19 | 2021-06-24 | Industrial Technology Research Institute | Biodegradable iron-based alloy composition, medical implant applying the same, and manufacturing method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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-
2021
- 2021-09-10 CN CN202111064408.1A patent/CN113755738A/en active Pending
-
2022
- 2022-06-28 WO PCT/CN2022/101949 patent/WO2023035731A1/en unknown
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102776435A (en) * | 2011-05-13 | 2012-11-14 | 中国科学院金属研究所 | Degradable Fe-Mn-C ternary iron alloy material and its application |
| CN104694848A (en) * | 2015-01-28 | 2015-06-10 | 燕山大学 | Biodegradable quaternary iron-based alloy material and preparation method thereof |
| CN109811265A (en) * | 2017-11-22 | 2019-05-28 | 中国科学院金属研究所 | A kind of Fe-Mn-Cu-C system alloy and its medical application |
| CN111235476A (en) * | 2018-11-29 | 2020-06-05 | 中国科学院金属研究所 | Degradable anti-infection and anti-calculus Fe-Cu series alloy suitable for urinary implant material |
| CN110477982A (en) * | 2019-07-24 | 2019-11-22 | 中国科学院金属研究所 | Anti- calculus anastomosis staple of degradable antibacterial suitable for urinary system and preparation method thereof |
| US20210187157A1 (en) * | 2019-12-19 | 2021-06-24 | Industrial Technology Research Institute | Biodegradable iron-based alloy composition, medical implant applying the same, and manufacturing method thereof |
| CN111187965A (en) * | 2019-12-31 | 2020-05-22 | 中南大学湘雅二医院 | FeMn biodegradable alloy and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| 刘艳肖: "粉末冶金高锰无磁钢材料制备与性能的研究", 《中国优秀硕士学位论文全文数据库 工程科技I辑》 * |
| 朱权利: "粉末冶金高锰无磁钢Fe-25Mn-xCu-C的组织与性能研究", 《粉末冶金工业》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2023035731A1 (en) * | 2021-09-10 | 2023-03-16 | 广东粤海华金科技股份有限公司 | Degradable iron-based alloy material, preparation method therefor and application thereof |
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