CN109082569B - Preparation method of nano silicon dioxide/ferroferric oxide magnetic contrast particle enhanced biological magnesium-based composite material - Google Patents
Preparation method of nano silicon dioxide/ferroferric oxide magnetic contrast particle enhanced biological magnesium-based composite material Download PDFInfo
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Abstract
A preparation method of a nano silicon dioxide/ferroferric oxide magnetic contrast particle enhanced biological magnesium-based composite material relates to a preparation method of a magnesium-based composite material. The invention aims to solve the technical problems of poor target positioning capability and low forming capability of the existing biomedical magnesium-based composite material. The invention comprises the following steps: firstly, preparing a nano magnetic contrast particle combination; and secondly, carrying out ultrasonic coupling stirring self-regulation treatment and carrying out stepped variable-temperature infiltration hot-press molding. The invention is beneficial to improving the interfacial activity of the nano silicon dioxide hollow microspheres and the ferroferric oxide magnetic particles through high-temperature mechanical ball milling, can reduce magnesium liquid inclusion, improve the uniformity of the structure, enhance the targeting positioning capability, further improve the infiltration capability through graded temperature-variable hot pressing, reduce casting defects and refine crystal grains through the ultrasonic coupled stirring self-regulation treatment and the graded temperature-variable infiltration hot pressing molding, and can obviously improve the obdurability of the magnesium-based composite material.
Description
Technical Field
The invention relates to a preparation method of a biological magnesium-based composite material.
Background
The metal stent has remarkable curative effect after being applied to clinical treatment, but is easy to cause thrombosis, high in restenosis rate, and causes the problems of vessel wall injury and the like. The magnesium-based alloy is degradable, has better vascular supporting force, and effectively reduces stent restenosis, thereby gaining wide attention. However, the traditional magnesium-based alloy cannot realize effective diagnosis and real-time monitoring of living tissue diseases, and has low strength and poor plasticity.
Aiming at the problems, the mesoporous nano biomaterial has adjustable nano-scale pore diameter, high specific surface area and pore volume, rich chemical functional groups and good biocompatibility and degradability, can be used as contrast particles to replace gas microbubble contrast agents which are easy to dissolve and break in blood and difficult to control the particle size, and is expected to play an important role in the diagnosis and treatment of serious human diseases in the future. The mesoporous silica hollow nano material has good biocompatibility and mechanical stability, has a huge cavity nano structure, a high specific surface area and a large pore volume, can generate a strong echo signal in an imaging mode, and can load an object molecule. The magnetic ferroferric oxide nano material is used as a special nano material, has the basic characteristics of a common nano material, and also has special superparamagnetism and enzyme-like activity.
Disclosure of Invention
The invention provides a preparation method of a nano silicon dioxide/ferroferric oxide magnetic contrast particle reinforced biological magnesium-based composite material, aiming at solving the technical problems of poor target positioning capability and low forming capability of the existing biomedical magnesium-based composite material.
The preparation method of the nano silicon dioxide/ferroferric oxide magnetic contrast particle reinforced biological magnesium-based composite material is carried out according to the following steps:
firstly, preparing a nano silicon dioxide/ferroferric oxide magnetic contrast particle combination: carrying out high-temperature ball milling and mixing on the nano-silica hollow microspheres and the ferroferric oxide magnetic nanoparticles at the temperature of 250-400 ℃, then carrying out hot pressing, and naturally cooling to room temperature to obtain a nano-silica/ferroferric oxide magnetic contrast particle combination;
the mass ratio of the nano silicon dioxide hollow microspheres to the ferroferric oxide magnetic nanoparticles is 1 (1.8-3);
the ball milling time of the high-temperature ball milling and mixing is 0.5 h-1.5 h, and the ball milling speed is 250 r/min-400 r/min;
the hot pressing temperature is 250-400 ℃, the pressure is 150-250 MPa, and the pressure maintaining time is 3 min;
secondly, heating the nano silicon dioxide/ferroferric oxide magnetic contrast particle combination obtained in the first step to 150-250 ℃, adding the combination into semi-solid magnesium slurry, heating to 680-760 ℃ to obtain a liquid magnesium-based composite material melt, adding pure magnesium with the temperature of 100 ℃ into the liquid magnesium-based composite material melt under the conditions that the temperature is 680-760 ℃, the ultrasonic power is 600-1800W and the mechanical stirring speed is 500-1700 rpm to obtain an adjusted liquid magnesium alloy, and then stirring and ultrasonically treating for 15-30 min under the conditions that the temperature is 680-760 ℃, the ultrasonic power is 600-1800W and the mechanical stirring speed is 500-1700 rpm; then heating to 780 ℃, and then placing the mixture into a mold with the temperature of 550-650 ℃ for carrying out stepped variable-temperature infiltration hot-press molding to obtain the nano silicon dioxide/ferroferric oxide magnetic contrast particle reinforced biological magnesium-based composite material;
the mass of the nano silicon dioxide/ferroferric oxide magnetic contrast particle combination in the adjusted liquid magnesium alloy is 1-15%;
the semi-solid magnesium slurry consists of 8% of Zn, 4% of Sr and 88% of Mg according to mass fraction;
the three elements of Zn, Sr and Mg in the adjusted liquid magnesium alloy are composed of the following components in percentage by mass: 2% Zn, 1% Sr and 97% Mg;
the method for the step variable temperature infiltration hot press molding comprises the following steps: maintaining the pressure for 1-2 min at 550-650 ℃ and 300-500 MPa for the first-stage hot pressing; and then, maintaining the pressure for 5-8 min at the temperature of 400-550 ℃ and the pressure of 450-700 MPa to perform second-stage hot pressing, wherein the temperature of the second-stage hot pressing is lower than that of the first-stage hot pressing.
The temperature of the semi-solid magnesium slurry is 620-640 ℃.
According to the invention, through high-temperature mechanical ball milling, the interface activity of the nano silicon dioxide hollow microspheres and the ferroferric oxide magnetic particles is favorably improved, the ultrasonic coupling stirring self-regulation treatment can reduce magnesium liquid inclusion, improve the tissue uniformity and enhance the targeting positioning capability, the stepped variable-temperature hot pressing can further improve the infiltration capability, reduce casting defects and refine crystal grains, and the obdurability of the nano silicon dioxide/ferroferric oxide magnetic contrast particle enhanced biological magnesium-based composite material can be obviously improved under the effects of the ultrasonic coupling stirring self-regulation treatment and the stepped variable-temperature infiltration hot pressing.
The Mg-Zn-Sr alloy is used as a biological magnesium alloy of a degradable cardiovascular stent, has low strength and poor plasticity, and cannot detect the condition of the cardiovascular stent in real time through in-vitro equipment; the semi-solid magnesium slurry has high alloy content, is easy to realize semi-solid state, reduces impurities, but has more second phases due to over high alloy elements and has high degradation speed in the alloy body, so that the corrosion resistance of the alloy can be improved after pure magnesium is added to dilute the alloy.
The invention combines the specific application and the using environment of the human body implant material, selects raw materials from the idea of the bionic principle, comprehensively considers the factors of the components and the tissue structure of the material on the mechanical property and the corrosion resistance of the material and the like, adopts the nano silicon dioxide/ferroferric oxide magnetic contrast particles as the reinforcement to prepare the biological magnesium-based composite material, has the advantages of targeted positioning, convenience for medical diagnosis, small addition amount and large performance improvement amplitude, and obtains the biological magnesium-based composite material with synchronously improved obdurability.
The invention has the beneficial effects that:
according to the invention, the nano silicon dioxide/ferroferric oxide magnetic contrast particle combination is prepared through high-temperature mechanical ball milling and hot pressing in the first step, and the nano silicon dioxide/ferroferric oxide magnetic contrast particle combination with higher interfacial activity, which is prepared by the method, can be obviously improved in the combination degree with a biological magnesium alloy matrix; the second step of ultrasonic coupling stirring self-regulation treatment can reduce magnesium liquid inclusion, improve tissue uniformity, enhance targeting positioning capability, further improve infiltration capability by graded temperature-changing hot pressing, reduce casting defects and refine crystal grains, and can enable the strength and toughness of the nano silicon dioxide/ferroferric oxide magnetic contrast particle enhanced biological magnesium-based composite material to be remarkably improved under the effects of ultrasonic coupling stirring self-regulation treatment and graded temperature-changing infiltration hot-press molding, the tensile strength reaches more than 380MPa, the yield strength reaches more than 350MPa, and the elongation reaches more than 9%.
Drawings
FIG. 1 is a schematic view of an apparatus for hot pressing in step one and step two of the embodiment;
FIG. 2 is a schematic view of an apparatus for hot press forming by infiltration at a variable temperature in a step II according to an embodiment;
FIG. 3 is an optical microstructure of a nano-silica/ferroferric oxide magnetic contrast particle enhanced biological Mg-based composite prepared in the first experiment;
FIG. 4 is an optical microstructure of a nano-silica/ferroferric oxide magnetic contrast particle enhanced biological magnesium-based composite prepared by experiment four;
FIG. 5 is a graph of engineering stress versus engineering strain;
FIG. 6 is a graph of engineering stress versus engineering strain;
fig. 7 is a graph of engineering stress versus engineering strain.
Detailed Description
The first embodiment is as follows: the embodiment is a preparation method of a nano silicon dioxide/ferroferric oxide magnetic contrast particle reinforced biological magnesium-based composite material, which is specifically carried out according to the following steps:
firstly, preparing a nano silicon dioxide/ferroferric oxide magnetic contrast particle combination: carrying out high-temperature ball milling and mixing on the nano-silica hollow microspheres and the ferroferric oxide magnetic nanoparticles at the temperature of 250-400 ℃, then carrying out hot pressing, and naturally cooling to room temperature to obtain a nano-silica/ferroferric oxide magnetic contrast particle combination;
the mass ratio of the nano silicon dioxide hollow microspheres to the ferroferric oxide magnetic nanoparticles is 1 (1.8-3);
the ball milling time of the high-temperature ball milling and mixing is 0.5 h-1.5 h, and the ball milling speed is 250 r/min-400 r/min;
the hot pressing temperature is 250-400 ℃, the pressure is 150-250 MPa, and the pressure maintaining time is 3 min;
secondly, heating the nano silicon dioxide/ferroferric oxide magnetic contrast particle combination obtained in the first step to 150-250 ℃, adding the combination into semi-solid magnesium slurry, heating to 680-760 ℃ to obtain a liquid magnesium-based composite material melt, adding pure magnesium with the temperature of 100 ℃ into the liquid magnesium-based composite material melt under the conditions that the temperature is 680-760 ℃, the ultrasonic power is 600-1800W and the mechanical stirring speed is 500-1700 rpm to obtain an adjusted liquid magnesium alloy, and then stirring and ultrasonically treating for 15-30 min under the conditions that the temperature is 680-760 ℃, the ultrasonic power is 600-1800W and the mechanical stirring speed is 500-1700 rpm; then heating to 780 ℃, and then placing the mixture into a mold with the temperature of 550-650 ℃ for carrying out stepped variable-temperature infiltration hot-press molding to obtain the nano silicon dioxide/ferroferric oxide magnetic contrast particle reinforced biological magnesium-based composite material;
the mass of the nano silicon dioxide/ferroferric oxide magnetic contrast particle combination in the adjusted liquid magnesium alloy is 1-15%;
the semi-solid magnesium slurry consists of 8% of Zn, 4% of Sr and 88% of Mg according to mass fraction;
the three elements of Zn, Sr and Mg in the adjusted liquid magnesium alloy are composed of the following components in percentage by mass: 2% Zn, 1% Sr and 97% Mg;
the method for the step variable temperature infiltration hot press molding comprises the following steps: maintaining the pressure for 1-2 min at 550-650 ℃ and 300-500 MPa for the first-stage hot pressing; and then, maintaining the pressure for 5-8 min at the temperature of 400-550 ℃ and the pressure of 450-700 MPa to perform second-stage hot pressing, wherein the temperature of the second-stage hot pressing is lower than that of the first-stage hot pressing.
The device for hot pressing in the first step and the step-by-step variable temperature infiltration hot press molding in the second step in the first embodiment is shown in fig. 1, and comprises an ultrasonic horn 1, a press head 2, an upper cushion block 3, a lower cushion block 4 and a furnace body 5; the upper end face of an ultrasonic amplitude transformer 1 is fixed with a press head 2, an upper cushion block 3 is horizontally arranged in a furnace body 5, the lower end face of the ultrasonic amplitude transformer 1 is tightly contacted with the upper end face of the upper cushion block 3, the ultrasonic amplitude transformer 1 penetrates through the upper end face of the furnace body 5, the side wall of the ultrasonic amplitude transformer 1 is sealed with the upper end face of the furnace body 5, the side wall of the ultrasonic amplitude transformer 1 is in sliding connection with the upper end face of the furnace body 5, a lower cushion block 4 is fixed on the inner bottom face of the furnace body 5, and a heating source 5-1 is fixed on the side wall of the furnace body 5; the use method of the device is as follows: taking the ultrasonic amplitude transformer 1 and the upper cushion block 3 out of the furnace body 5, adding the material to be processed into the furnace body 5 (namely the mould in the step two), then an upper cushion block 3 is horizontally placed on the material to be processed, an ultrasonic amplitude transformer 1 is placed in the upper cushion block 3, the lower end face of the ultrasonic amplitude transformer 1 is tightly contacted with the upper end face of the upper cushion block 3, a heating source 5-1 is started for heating, the pressure is applied to the ultrasonic amplitude transformer 1 by a pressure head 2 of a press machine, so that the upper cushion block 3 carries out hot pressing on the material to be processed, after the first-stage hot pressing is finished, the heating source 5-1 is closed, then when the temperature is reduced to the second-stage hot pressing temperature, the second-stage hot pressing is carried out, the ultrasonic amplitude transformer 1 can transmit load to the blank, the upper cushion block 3 is used for transmitting load when the stepped variable-temperature infiltration hot pressing is applied, which moves downward along with the material to be processed, and the lower pad 4 functions to restrict the downward movement of the material to be processed when the ac-ultrasonic coupled thermal compression is applied.
The device for ultrasonic stirring in the second step of the present embodiment is shown in fig. 2, and is composed of a heating source 6, a mechanical stirrer 7, an ultrasonic horn 8 and a furnace body 9; the heating source 6 is fixed on the side wall of the furnace body 9, and the mechanical stirrer 7 and the ultrasonic amplitude transformer 8 respectively penetrate through the upper end face of the furnace body 9 and are fixed with the upper end face of the furnace body 9 in a sealing way; the use method of the device is as follows: pouring the magnesium alloy melt to be processed into a furnace body 9, adding preheated solid pure magnesium, simultaneously starting a heating source 6, a mechanical stirrer 7 and an ultrasonic amplitude transformer 8, and mechanically stirring the magnesium alloy melt under the action of ultrasonic vibration.
The second embodiment is as follows: the first difference between the present embodiment and the specific embodiment is: the particle size of the nano silicon dioxide hollow microsphere in the step one is 40 nm-100 nm, the aperture is 15 nm-35 nm, and the porosity is 85% -100%. The rest is the same as the first embodiment.
The third concrete implementation mode: the present embodiment differs from the first or second embodiment in that: the particle size of the ferroferric oxide magnetic nanoparticles in the step one is 30-100 nm. The others are the same as in the first or second embodiment.
The fourth concrete implementation mode: the difference between this embodiment mode and one of the first to third embodiment modes is: the mass ratio of the nano silicon dioxide hollow microspheres to the ferroferric oxide magnetic nanoparticles is 1: 2. The rest is the same as one of the first to third embodiments.
The fifth concrete implementation mode: the fourth difference between this embodiment and the specific embodiment is that: and in the second step, the nano silicon dioxide/ferroferric oxide magnetic contrast particle combination obtained in the first step is heated to 200 ℃, and then is added into the semi-solid magnesium slurry. The rest is the same as the fourth embodiment.
The invention was verified with the following tests:
test one: the test is a preparation method of a nano silicon dioxide/ferroferric oxide magnetic contrast particle reinforced biological magnesium-based composite material, which is specifically carried out according to the following steps:
firstly, preparing a nano silicon dioxide/ferroferric oxide magnetic contrast particle combination: carrying out high-temperature ball milling and mixing on the nano-silica hollow microspheres and the ferroferric oxide magnetic nanoparticles at the temperature of 300 ℃, then carrying out hot pressing, and naturally cooling to room temperature to obtain a nano-silica/ferroferric oxide magnetic contrast particle combination;
the particle size of the nano silicon dioxide hollow microsphere in the step one is 60 nm-100 nm, the aperture is 20 nm-35 nm, and the porosity is 85% -100%;
the particle size of the ferroferric oxide magnetic nanoparticles in the step one is 60-100 nm;
the mass ratio of the nano silicon dioxide hollow microspheres to the ferroferric oxide magnetic nanoparticles is 1: 1.8;
the ball milling time of the high-temperature ball milling and mixing is 1.5h, and the ball milling speed is 300 r/min;
the hot pressing temperature is 300 ℃, the pressure is 200MPa, and the pressure maintaining time is 3 min;
secondly, heating the nano silicon dioxide/ferroferric oxide magnetic contrast particle combination obtained in the first step to 200 ℃, adding the combination into semi-solid magnesium slurry, heating to 720 ℃ to obtain a liquid magnesium-based composite material melt, adding pure magnesium with the temperature of 100 ℃ into the liquid magnesium-based composite material melt under the conditions of the temperature of 720 ℃, the ultrasonic power of 1000W and the mechanical stirring speed of 1200rpm to obtain an adjusted liquid magnesium alloy, and then stirring and carrying out ultrasonic treatment for 30min under the conditions of the temperature of 720 ℃, the ultrasonic power of 1000W and the mechanical stirring speed of 1200 rpm; then heating to 780 ℃, and then placing the mixture into a mold with the temperature of 600 ℃ for carrying out stepped variable-temperature infiltration hot-press molding to obtain the nano silicon dioxide/ferroferric oxide magnetic contrast particle reinforced biological magnesium-based composite material;
the preparation method of the semi-solid magnesium slurry comprises the following steps: heating the magnesium alloy from room temperature to 760 ℃, and then cooling to 620 ℃ to obtain a semi-solid magnesium alloy melt;
the mass of the nano silicon dioxide/ferroferric oxide magnetic contrast particle combination in the adjusted liquid magnesium alloy is 5%;
the semi-solid magnesium slurry consists of 8% of Zn, 4% of Sr and 88% of Mg according to mass fraction;
the three elements of Zn, Sr and Mg in the adjusted liquid magnesium alloy are composed of the following components in percentage by mass: 2% Zn, 1% Sr and 97% Mg;
the method for the step variable temperature infiltration hot press molding comprises the following steps: maintaining the pressure for 2min at 600 ℃ and 400MPa to perform first-stage hot pressing; and then, maintaining the pressure for 6min at the temperature of 400 ℃ and the pressure of 550MPa for second-stage hot pressing.
And (2) test II: the test is a comparative test, and is different from the test I in the step I: and (3) performing ball milling and mixing on the nano-silica hollow microspheres and the ferroferric oxide magnetic nanoparticles at room temperature, then performing hot pressing, and naturally cooling to room temperature to obtain the nano-silica/ferroferric oxide magnetic contrast particle combination. The rest is the same as test one.
FIG. 3 shows the optical microstructure of the nano-silica/ferroferric oxide magnetic contrast particle reinforced biological magnesium-based composite material prepared in the first experiment, wherein as shown in the figure, the average grain size is about 40 μm, the grain size is obviously refined, the second phase is uniformly distributed, and the toughness can be improved.
The performance of the nano-silica-ferroferric oxide magnetic contrast particle reinforced biological magnesium-based composite material is tested at room temperature, an engineering stress-engineering strain curve is obtained and is shown in figure 5, ● in the figure represents the nano-silica-ferroferric oxide magnetic contrast particle reinforced biological magnesium-based composite material prepared in the second experiment, and xxx in the figure represents the nano-silica-ferroferric oxide magnetic contrast particle reinforced biological magnesium-based composite material prepared in the first experiment, and the graph 5 shows that the tensile strength of the nano-silica-ferroferric oxide magnetic contrast particle reinforced biological magnesium-based composite material prepared in the second experiment after the combination is subjected to mechanical ball milling treatment at room temperature in the first step is 320MPa, the yield strength is 298MPa, and the elongation is 9.2%; the tensile strength of the nano silicon dioxide/ferroferric oxide magnetic contrast particle reinforced biological magnesium-based composite material prepared in the first test is 374MPa, the yield strength is 349MPa, the elongation is 11.3%, and the tensile strength is obviously superior to that of the second test.
And (3) test III: this test differs from the test one in that: the mass ratio of the nano silicon dioxide hollow microspheres to the ferroferric oxide magnetic nanoparticles is 1: 3. The rest is the same as test one.
And (4) testing: the test is a comparative test, and is different from the test III in the step one: and (3) performing ball milling and mixing on the nano-silica hollow microspheres and the ferroferric oxide magnetic nanoparticles at room temperature, then performing hot pressing, and naturally cooling to room temperature to obtain the nano-silica/ferroferric oxide magnetic contrast particle combination. The rest were the same as in test three.
Fig. 4 is an optical microstructure of the nano-silica/ferroferric oxide magnetic contrast particle reinforced biological magnesium-based composite material prepared by the experiment four, and it can be seen from the optical microstructure that the crystal grain size is large, the second phase is distributed along the grain boundary, the plasticity is poor, and the strength is low.
The performance test is performed on the nano-silica/ferroferric oxide magnetic contrast particle reinforced biological magnesium-based composite material at room temperature, an engineering stress-engineering strain curve is obtained and is shown in fig. 6, ◆ in the diagram indicates the nano-silica/ferroferric oxide magnetic contrast particle reinforced biological magnesium-based composite material prepared by the experiment four, ▲ in the diagram indicates the nano-silica/ferroferric oxide magnetic contrast particle reinforced biological magnesium-based composite material prepared by the experiment three, and the tensile strength, the yield strength and the elongation of the nano-silica/ferroferric oxide magnetic contrast particle reinforced biological magnesium-based composite material prepared by the experiment four after the combination is mechanically ball-milled at room temperature in the first step is 313MPa, 291MPa and 8.8%, and the tensile strength, the yield strength and the elongation of the nano-silica/ferroferric oxide magnetic contrast particle reinforced biological magnesium-based composite material prepared by the experiment three are 361MPa, 346MPa and 10.1%.
And (5) testing: this test differs from the test one in that: in the first step, the nano-silica hollow microspheres and the ferroferric oxide magnetic nanoparticles are subjected to high-temperature ball milling and mixing at the temperature of 400 ℃, then hot pressing is carried out, and natural cooling is carried out to the room temperature, so as to obtain the nano-silica/ferroferric oxide magnetic contrast particle combination. The rest is the same as test one.
And (6) test six: the experiment is a comparative experiment, and is different from the experiment III in that in the step I, the nano-silica hollow microspheres and the ferroferric oxide magnetic nanoparticles are subjected to high-temperature ball milling and mixing at the temperature of 400 ℃, then hot pressing is carried out, and the nano-silica/ferroferric oxide magnetic contrast particle combination is obtained after natural cooling to the room temperature. The other three tests were identical.
Test seven: the test is a comparative test, and is different from the test II in the step I: and mechanically ball-milling the nano-silica hollow microspheres and the ferroferric oxide magnetic nanoparticles at room temperature to obtain a nano-silica/ferroferric oxide magnetic contrast particle combination. The other two tests were identical.
The performance test is performed on the nano-silica/ferroferric oxide magnetic contrast particle reinforced biological magnesium-based composite material at room temperature, so that an engineering stress-engineering strain curve is obtained as shown in fig. 7, wherein ▲ represents the nano-silica/ferroferric oxide magnetic contrast particle reinforced biological magnesium-based composite material prepared in the fifth test, ■ represents the nano-silica/ferroferric oxide magnetic contrast particle reinforced biological magnesium-based composite material prepared in the sixth test, ◆ represents the nano-silica/ferroferric oxide magnetic contrast particle reinforced biological magnesium-based composite material prepared in the seventh test, and as can be seen from fig. 7, the tensile strength of the nano-silica/ferroferric oxide magnetic contrast particle reinforced biological magnesium-based composite material prepared in the fifth test is 397Mpa, the yield strength is 354Mpa, and the elongation is 13.8%, the tensile strength of the nano-silica/ferroferric oxide magnetic contrast particle reinforced biological magnesium-based composite material prepared in the sixth test is 355Mpa, the yield strength is 310Mpa, and the elongation is 13.1%.
Claims (6)
1. A preparation method of a nano silicon dioxide/ferroferric oxide magnetic contrast particle reinforced biological magnesium-based composite material is characterized in that the preparation method of the nano silicon dioxide/ferroferric oxide magnetic contrast particle reinforced biological magnesium-based composite material is carried out according to the following steps:
firstly, preparing a nano silicon dioxide/ferroferric oxide magnetic contrast particle combination: carrying out high-temperature ball milling and mixing on the nano-silica hollow microspheres and the ferroferric oxide magnetic nanoparticles at the temperature of 250-400 ℃, then carrying out hot pressing, and naturally cooling to room temperature to obtain a nano-silica/ferroferric oxide magnetic contrast particle combination;
the mass ratio of the nano silicon dioxide hollow microspheres to the ferroferric oxide magnetic nanoparticles is 1 (1.8-3);
the ball milling time of the high-temperature ball milling and mixing is 0.5 h-1.5 h, and the ball milling speed is 250 r/min-400 r/min;
the hot pressing temperature is 250-400 ℃, the pressure is 150-250 MPa, and the pressure maintaining time is 3 min;
secondly, heating the nano silicon dioxide/ferroferric oxide magnetic contrast particle combination obtained in the first step to 150-250 ℃, adding the combination into semi-solid magnesium slurry, heating to 680-760 ℃ to obtain a liquid magnesium-based composite material melt, adding pure magnesium with the temperature of 100 ℃ into the liquid magnesium-based composite material melt under the conditions that the temperature is 680-760 ℃, the ultrasonic power is 600-1800W and the mechanical stirring speed is 500-1700 rpm to obtain an adjusted liquid magnesium alloy, and then stirring and ultrasonically treating for 15-30 min under the conditions that the temperature is 680-760 ℃, the ultrasonic power is 600-1800W and the mechanical stirring speed is 500-1700 rpm; then heating to 780 ℃, and then placing the mixture into a mold with the temperature of 550-650 ℃ for carrying out stepped variable-temperature infiltration hot-press molding to obtain the nano silicon dioxide/ferroferric oxide magnetic contrast particle reinforced biological magnesium-based composite material;
the mass fraction of the nano silicon dioxide/ferroferric oxide magnetic contrast particle combination in the adjusted liquid magnesium alloy is 1-15%;
the semi-solid magnesium slurry consists of 8% of Zn, 4% of Sr and 88% of Mg according to mass fraction;
the three elements of Zn, Sr and Mg in the adjusted liquid magnesium alloy are composed of the following components in percentage by mass: 2% Zn, 1% Sr and 97% Mg;
the method for the step variable temperature infiltration hot press molding comprises the following steps: maintaining the pressure for 1-2 min at 550-650 ℃ and 300-500 MPa for the first-stage hot pressing; and then, maintaining the pressure for 5-8 min at the temperature of 400-550 ℃ and the pressure of 450-700 MPa to perform second-stage hot pressing, wherein the temperature of the second-stage hot pressing is lower than that of the first-stage hot pressing.
2. The method for preparing a nano-silica/ferroferric oxide magnetic contrast particle reinforced biological magnesium-based composite material according to claim 1, wherein the nano-silica hollow microspheres in the first step have a particle size of 40nm to 100nm, a pore diameter of 15nm to 35nm, and a porosity of 85% to 100%.
3. The preparation method of the nano-silica/ferroferric oxide magnetic contrast particle enhanced biological magnesium-based composite material according to claim 1, wherein the particle size of the ferroferric oxide magnetic nanoparticles in the first step is 30nm to 100 nm.
4. The preparation method of the nano-silica/ferroferric oxide magnetic contrast particle reinforced biological magnesium-based composite material according to claim 1, characterized in that the mass ratio of the nano-silica hollow microspheres to the ferroferric oxide magnetic nanoparticles is 1: 2.
5. The preparation method of the nano-silica/ferroferric oxide magnetic contrast particle enhanced biological magnesium-based composite material according to claim 1, characterized in that in the second step, the nano-silica/ferroferric oxide magnetic contrast particle combination obtained in the first step is heated to 200 ℃ and then added into the semi-solid magnesium slurry.
6. The preparation method of the nano-silica/ferroferric oxide magnetic contrast particle reinforced biological magnesium-based composite material according to claim 1, which is characterized in that the preparation method of the semi-solid magnesium slurry in the step two comprises the following steps: and heating the magnesium alloy from room temperature to 760 ℃, and then cooling to 620 ℃ to obtain the semi-solid magnesium alloy melt.
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