CN112457000B - (Si-N) @ C-Ca-P-C biomedical bone replacement composite material and preparation method thereof - Google Patents
(Si-N) @ C-Ca-P-C biomedical bone replacement composite material and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a (Si-N) @ C-Ca-P-C biomedical bone replacement composite material and a preparation method thereof. The (Si-N) @ C-Ca-P-C biomedical bone replacement composite material prepared by the invention has the advantages that the molecules are connected by chemical bonds in the ultra-high temperature synthesis process, the Si-N line has high strength in a chemical combination mode, the Si-N line is subjected to surface strengthening by the double-layer C wrapping layer, the wheat-ear-shaped Ca-P further plays a role in point strengthening, the pores of the material are obviously reduced by the densification of C, and the density of the material is improved. By combining the factors, the maximum value of the compressive strength of the (Si-N) @ C-Ca-P-C biomedical bone replacement composite material prepared by the invention reaches 85.4MPa, and is improved by 83.7 percent compared with the maximum value of the compressive strength of the background technology.
Description
Technical Field
The invention belongs to a biological material and a preparation method thereof, and relates to a (Si-N) @ C-Ca-P-C biomedical bone replacement composite material and a preparation method thereof.
Background
With the aggravation of the aging problem of the society, the skeletal lesion and the skeletal injury of the old people become important problems influencing the life quality of the old people, and the skeletal replacement by adopting the artificially synthesized biological material is an effective method for solving the skeletal lesion and the skeletal injury. In the research process of artificially synthesizing the biological material, researchers pay attention to the biocompatibility of the material on one hand, so that the biological material is not subjected to rejection reaction with the human body after being implanted into the human body, and the effective combination of the biological material and the human skeleton can be promoted. On the other hand, since the bone is a load-bearing part of the human body, the strength of the biomaterial needs to be increased, and particularly, the bone is more commonly subjected to compressive load, and therefore, researchers have been devoted to improving the compressive strength of the biomedical bone replacement material.
Document 1 "Limin, Zpachian, Tangan, etc. HA/TiO with porous structure 2 Research on preparation process of biological material in mining and metallurgy engineering, 2012,32(4):106- 2 Biomedical bone replacement material, the compressive strength of which was found to be 4.0 MPa.
Document 2 "da, quay, et al. foam carbon material and its use in bioengineering materials world complex medicine 2015,10(04): 343-. The use of carbon foam as a biomedical bone replacement material is reported to have a compressive strength of 20.0 MPa.
Document 3, "zhangqiang, pericircuit, wanfen, yangjun, xiaoling, preparation of Si-HA nanopowder by ultrasonic copolymerization method and mechanical properties of bone cement thereof, material report, 2010,24(22): 42-45" reports that a silicon-containing hydroxyapatite biomedical bone replacement material is prepared by compounding silicon-containing hydroxyapatite nanopowder with citric acid and acrylic acid, and the compressive strength of the material reaches 46.5 MPa.
All the studies have prepared the biomaterial applied to bone replacement, but the prepared bone replacement material has the highest compression strength of only 46.5MPa, and has the problem of insufficient compression strength.
Disclosure of Invention
Technical problem to be solved
In order to avoid the defects of the prior art, the invention provides a (Si-N) @ C-Ca-P-C biomedical bone replacement composite material and a preparation method thereof, and solves the problem of insufficient compressive strength of the bone replacement material.
Technical scheme
A (Si-N) @ C-Ca-P-C biomedical bone replacement composite material is characterized by comprising Si-N lines, wheat-ear-shaped Ca-P and C materials; taking a Si-N line as a central nuclear layer structure, wrapping two layers of C materials outside the nuclear layer structure, and wrapping the C material with ear-shaped Ca-P outside the wrapping layer; the molecules are connected by chemical bonds; the pores in all structures were filled with C.
A preparation method of the (Si-N) @ C-Ca-P-C biomedical bone replacement composite material is characterized by comprising the following steps:
step 1: adding polysilazane and ferrocene into xylene, uniformly stirring, standing in the air for natural curing, and then grinding the cured material into powder;
the powder was laid flat between two pieces of U-shaped carbon paper and subsequently placed in a high temperature furnace for heat treatment: firstly, introducing nitrogen with the flow rate of 4-10L/min, then heating to 200-300 ℃ at the speed of 5-10 ℃/min, keeping the temperature for 1-3 hours, then heating to 1300-1450 ℃ at the speed of 8-10 ℃/min, keeping the temperature for 2-5 hours, naturally cooling the system to the room temperature, and taking out the material deposited on the surface of the U-shaped carbon paper as a Si-N line;
the mass ratio of the polysilazane to the ferrocene is 7:1-9: 1;
the mass ratio of the polysilazane to the xylene is 1:40-1: 60;
step 2: putting the Si-N wire into a high temperature furnace, introducing nitrogen with the flow rate of 5-10L/min, heating to 700-800 ℃ at the speed of 8-10 ℃/min, introducing natural gas with the flow rate of 0.5-0.8L/min after reaching the temperature, adjusting the flow rate of the nitrogen to 2.0-2.5L/min, and reacting for 1-3 hours; then heating to 1000-1200 ℃ at the speed of 5-8 ℃/min, adjusting the flow rate of the natural gas to 0.2-0.4L/min after the temperature is reached, keeping the flow rate of nitrogen unchanged, and depositing for 1-3 hours to obtain a carbon wrapping layer on the outer layer of the Si-N line;
and step 3: placing in carbon spraying instrument under pressure of 5 × 10 -2 -6×10 -2 Pa, spraying carbon for 10-30 seconds under the condition that the current is 3-5mA, and obtaining the material (Si-N) @ C of a second carbon wrapping layer on the outer layer of the carbon wrapping layer;
and 4, step 4: immersing the Si-N wire with the carbon wrapping layer in a mixed solution of calcium nitrate and ammonium dihydrogen phosphate, putting the immersed Si-N wire and the mixed solution in a high-pressure kettle together, and treating the immersed Si-N wire and the mixed solution for 10 to 30 minutes at the temperature of 100-120 ℃;
the molar ratio of the calcium nitrate to the ammonium dihydrogen phosphate in the mixed solution of the calcium nitrate and the ammonium dihydrogen phosphate is 1.6-1.8;
and 5: taking a graphite sheet as an anode, taking the material treated in the step 4 as a cathode, applying a voltage of 2-5V, a pulse width of 50-80ms, a pulse interval of 100-150ms, a reaction time of 1-10 minutes and a reaction temperature of 40-60 ℃ to obtain a material which takes a Si-N line as a core and is wrapped by two layers of C and wheat-ear-shaped Ca-P;
step 6: and (5) placing the material obtained in the step (5) in a chemical vapor deposition furnace, heating to 950-.
The mixed solution of the calcium nitrate and the ammonium dihydrogen phosphate is as follows: dissolving ammonium dihydrogen phosphate in hydrogen peroxide to prepare a solution with the concentration of 100-150mmol/L, and dissolving calcium nitrate in water to prepare a mixed solution of the solution with the concentration of 100-150 mmol/L.
Advantageous effects
The invention provides a (Si-N) @ C-Ca-P-C biomedical bone replacement composite material and a preparation method thereof. The (Si-N) @ C-Ca-P-C biomedical bone replacement composite material prepared by the invention has the advantages that the molecules are connected by chemical bonds in the ultra-high temperature synthesis process, the Si-N line has high strength in a chemical combination mode, the Si-N line is subjected to surface strengthening by the double-layer C wrapping layer, the wheat-ear-shaped Ca-P further plays a role in point strengthening, the pores of the material are obviously reduced by the densification of C, and the density of the material is improved. By combining the factors, the maximum value of the compressive strength of the (Si-N) @ C-Ca-P-C biomedical bone replacement composite material prepared by the invention reaches 85.4MPa, and is improved by 83.7 percent compared with the maximum value of the compressive strength of the background technology.
Drawings
FIG. 1 is a scanning electron micrograph of sample C prepared in example 3
FIG. 2 is a scanning electron micrograph of sample F prepared in example 3
FIG. 3 is a scanning electron micrograph of (Si-N) @ C-Ca-P-C biomedical bone replacement composite of example 3 preparation
Detailed Description
The invention will now be further described with reference to the following examples and drawings:
the (Si-N) @ C-Ca-P-C biomedical bone replacement composite material takes a Si-N line as a central nuclear layer structure, two layers of C materials are wrapped outside the nuclear layer structure, and the outer layer of the C wrapping layer is the spike-shaped Ca-P; the molecules are connected by chemical bonds; the pores in all structures were filled with C.
The preparation method comprises the following steps:
(1) adding polysilazane and ferrocene into xylene, wherein the mass ratio of polysilazane to ferrocene is 7:1-9:1, the mass ratio of polysilazane to xylene is 1:40-1:60, uniformly stirring, standing in air for natural curing, grinding the cured material into powder, paving the powder at the bottom of U-shaped carbon paper, covering with another piece of U-shaped carbon paper, then placing into a high-temperature furnace for heat treatment, firstly introducing nitrogen with the flow rate of 4-10L/min, then heating to 200-300 ℃ at the speed of 5-10 ℃/min, keeping at the temperature for 1-3 hours, then heating to 1300-1450 ℃ at the speed of 8-10 ℃/min, keeping at the temperature for 2-5 hours, naturally cooling the system to room temperature, taking out a sample deposited on the surface of the upper layer of U-shaped carbon paper, obtaining a Si-N line marked as A;
(2) putting the A into a high-temperature furnace, introducing nitrogen with the flow rate of 5-10L/min, heating to 700-800 ℃ at the speed of 8-10 ℃/min, after reaching the temperature, introducing natural gas with the flow rate of 0.5-0.8L/min, adjusting the flow rate of the nitrogen to 2.0-2.5L/min, reacting for 1-3 hours, heating to 1000-1200 ℃ at the speed of 5-8 ℃/min, after reaching the temperature, adjusting the flow rate of the natural gas to 0.2-0.4L/min, keeping the flow rate of the nitrogen unchanged, and depositing for 1-3 hours to obtain a carbon coating B on the outer layer of the Si-N line;
(3) sample B was placed in a carbon-spraying apparatus at a pressure of 5X 10 -2 -6×10 -2 Pa, spraying carbon for 10-30 seconds under the condition of 3-5mA current, and marking the obtained material (Si-N) @ C of the second carbon wrapping layer as C;
(4) dissolving ammonium dihydrogen phosphate in hydrogen peroxide to prepare a solution with the concentration of 100-150mmol/L, dissolving calcium nitrate in water to prepare a solution with the concentration of 100-150mmol/L, and uniformly mixing the hydrogen peroxide solution of ammonium dihydrogen phosphate and the aqueous solution of calcium nitrate according to the molar ratio of 1.6-1.8 of calcium nitrate and ammonium dihydrogen phosphate to obtain a solution D;
(5) putting the sample C and the solution D together in an autoclave, completely immersing the sample C in the solution D, and treating for 10-30 minutes at the temperature of 100-120 ℃, wherein the obtained sample is marked as E;
(6) taking a graphite sheet as an anode and a sample E as a cathode, applying a voltage of 2-5V, a pulse width of 50-80ms, a pulse interval of 100-150ms, a reaction time of 1-10 minutes, a reaction temperature of 40-60 ℃, and marking the obtained sample as F;
(7) and (F) is placed in a chemical vapor deposition furnace, the temperature is raised to 950-1100 ℃ at the speed of 3-10 ℃/min, then natural gas with the flow rate of 0.5-0.8L/min and argon with the flow rate of 2.1-2.4L/min are introduced, the deposition time is 20-60 hours, and the (Si-N) @ C-Ca-P-C biomedical bone replacement composite material can be obtained after the deposition is finished.
Example 1:
(1) adding polysilazane and ferrocene into xylene, wherein the mass ratio of polysilazane to ferrocene is 7:1, the mass ratio of polysilazane to xylene is 1:40, uniformly stirring, standing in air for natural solidification, grinding the solidified material into powder, paving the powder at the bottom of U-shaped carbon paper, covering the powder with another U-shaped carbon paper, then placing the U-shaped carbon paper into a high-temperature furnace for heat treatment, firstly introducing nitrogen with the flow rate of 4L/min, then heating to 200 ℃ at the speed of 5 ℃/min, keeping the temperature for 1 hour, then heating to 1300 ℃ at the speed of 8 ℃/min, keeping the temperature for 2 hours, naturally cooling the system to room temperature, and taking out a sample deposited on the surface of the upper layer of U-shaped carbon paper, and marking the sample as A;
(2) putting the A into a high-temperature furnace, introducing nitrogen with the flow rate of 5L/min, heating to 700 ℃ at the speed of 8 ℃/min, introducing natural gas with the flow rate of 0.5L/min after the temperature is reached, adjusting the flow rate of the nitrogen to 2.0L/min, reacting for 1 hour, heating to 1000 ℃ at the speed of 5 ℃/min, adjusting the flow rate of the natural gas to 0.2L/min after the temperature is reached, keeping the flow rate of the nitrogen unchanged, and keeping the deposition time to 1 hour, wherein the obtained sample is marked as B;
(3) sample B was placed in a carbon-spraying apparatus at a pressure of 5X 10 -2 Pa, spraying carbon for 10 seconds under the condition of current of 3mA, and marking an obtained sample as C;
(4) dissolving ammonium dihydrogen phosphate in hydrogen peroxide to prepare a solution with the concentration of 100mmol/L, dissolving calcium nitrate in water to prepare a solution with the concentration of 100mmol/L, and uniformly mixing the hydrogen peroxide solution of the ammonium dihydrogen phosphate and the aqueous solution of the calcium nitrate according to the molar ratio of the calcium nitrate to the ammonium dihydrogen phosphate of 1.6 to obtain a solution D;
(5) putting the sample C and the solution D together in an autoclave, completely immersing the sample C in the solution D, and treating for 10 minutes at the temperature of 100 ℃, wherein the obtained sample is marked as E;
(6) taking a graphite sheet as an anode and a sample E as a cathode, applying a voltage of 2V, wherein the pulse width is 50ms, the pulse interval is 100ms, the reaction time is 1 minute, the reaction temperature is 40 ℃, and the obtained sample is marked as F;
(7) and (2) placing the F into a chemical vapor deposition furnace, heating to 950 ℃ at the speed of 3 ℃/min, then introducing natural gas with the flow rate of 0.5L/min and argon with the flow rate of 2.1L/min, and depositing for 20 hours to obtain the (Si-N) @ C-Ca-P-C biomedical bone replacement composite material after the deposition is completed.
The compression strength of the (Si-N) @ C-Ca-P-C biomedical bone replacement composite material obtained in the example was 78.4 MPa.
Example 2 of embodiment
(1) Adding polysilazane and ferrocene into xylene, wherein the mass ratio of polysilazane to ferrocene is 9:1, the mass ratio of polysilazane to xylene is 1:60, uniformly stirring, standing in air for natural solidification, grinding the solidified material into powder, paving the powder at the bottom of U-shaped carbon paper, covering the powder with another U-shaped carbon paper, then placing the U-shaped carbon paper into a high-temperature furnace for heat treatment, firstly introducing nitrogen with the flow rate of 10L/min, then heating to 300 ℃ at the speed of 10 ℃/min, keeping the temperature for 3 hours, then heating to 1450 ℃ at the speed of 10 ℃/min, keeping the temperature for 5 hours, naturally cooling the system to room temperature, and taking out a sample deposited on the surface of the upper layer of U-shaped carbon paper, and marking the sample as A;
(2) putting the A into a high-temperature furnace, introducing nitrogen with the flow rate of 10L/min, heating to 800 ℃ at the speed of 10 ℃/min, introducing natural gas with the flow rate of 0.8L/min after the temperature is reached, adjusting the flow rate of the nitrogen to be 2.5L/min, reacting for 3 hours, heating to 1200 ℃ at the speed of 8 ℃/min, adjusting the flow rate of the natural gas to be 0.4L/min after the temperature is reached, keeping the flow rate of the nitrogen unchanged, and keeping the deposition time to be 3 hours, wherein the obtained sample is marked as B;
(3) sample B was placed in a carbon-spraying apparatus at a pressure of 6X 10 -2 Pa, spraying carbon for 30 seconds under the condition of 5mA current, and marking an obtained sample as C;
(4) dissolving ammonium dihydrogen phosphate in hydrogen peroxide to prepare a solution with the concentration of 150mmol/L, dissolving calcium nitrate in water to prepare a solution with the concentration of 150mmol/L, and uniformly mixing the hydrogen peroxide solution of ammonium dihydrogen phosphate and the aqueous solution of calcium nitrate according to the molar ratio of calcium nitrate to ammonium dihydrogen phosphate of 1.8 to obtain a solution D;
(5) putting the sample C and the solution D together in an autoclave, completely immersing the sample C in the solution D, and treating for 30 minutes at the temperature of 120 ℃, wherein the obtained sample is marked as E;
(6) taking a graphite sheet as an anode and a sample E as a cathode, applying a voltage of 5V, wherein the pulse width is 80ms, the pulse interval is 150ms, the reaction time is 10 minutes, the reaction temperature is 60 ℃, and the obtained sample is marked as F;
(7) and (2) placing the F into a chemical vapor deposition furnace, heating to 1100 ℃ at the speed of 10 ℃/min, then introducing natural gas with the flow rate of 0.8L/min and argon with the flow rate of 2.4L/min, depositing for 60 hours, and obtaining the (Si-N) @ C-Ca-P-C biomedical bone replacement composite material after the deposition is finished.
The compression strength of the (Si-N) @ C-Ca-P-C biomedical bone replacement composite material obtained in the example was 80.6 MPa.
EXAMPLE 3
(1) Adding polysilazane and ferrocene into xylene, wherein the mass ratio of polysilazane to ferrocene is 8:1, the mass ratio of polysilazane to xylene is 1:50, uniformly stirring, standing in air for natural solidification, grinding the solidified material into powder, paving the powder at the bottom of U-shaped carbon paper, covering the powder with another U-shaped carbon paper, then placing the U-shaped carbon paper into a high-temperature furnace for heat treatment, firstly introducing nitrogen with the flow rate of 8L/min, then heating to 250 ℃ at the speed of 8 ℃/min, keeping the temperature for 2 hours, then heating to 1400 ℃ at the speed of 9 ℃/min, keeping the temperature for 3 hours, naturally cooling the system to room temperature, and taking out a sample deposited on the surface of the upper layer of U-shaped carbon paper, and marking the sample as A;
(2) putting the A into a high-temperature furnace, introducing nitrogen with the flow rate of 8L/min, heating to 750 ℃ at the speed of 9 ℃/min, introducing natural gas with the flow rate of 0.7L/min after the temperature is reached, adjusting the flow rate of the nitrogen to 2.3L/min, reacting for 2 hours, heating to 1100 ℃ at the speed of 6 ℃/min, adjusting the flow rate of the natural gas to 0.3L/min after the temperature is reached, keeping the flow rate of the nitrogen unchanged, and keeping the deposition time to 2 hours, wherein the obtained sample is marked as B;
(3) sample B was placed in a carbon-spraying apparatus at a pressure of 5.5X 10 -2 Pa, spraying carbon for 20 seconds under the condition of current of 4mA, and marking an obtained sample as C;
(4) dissolving ammonium dihydrogen phosphate in hydrogen peroxide to prepare a solution with the concentration of 120mmol/L, dissolving calcium nitrate in water to prepare a solution with the concentration of 120mmol/L, and uniformly mixing the hydrogen peroxide solution of ammonium dihydrogen phosphate and the aqueous solution of calcium nitrate according to the molar ratio of 1.7 of calcium nitrate to ammonium dihydrogen phosphate to obtain a solution D;
(5) putting the sample C and the solution D together in an autoclave, completely immersing the sample C in the solution D, and treating at the temperature of 110 ℃ for 20 minutes, wherein the obtained sample is marked as E;
(6) taking a graphite sheet as an anode and a sample E as a cathode, applying a voltage of 3V, wherein the pulse width is 60ms, the pulse interval is 120ms, the reaction time is 5 minutes, the reaction temperature is 50 ℃, and the obtained sample is marked as F;
(7) and (2) placing the F into a chemical vapor deposition furnace, heating to 1000 ℃ at the speed of 5 ℃/min, then introducing natural gas with the flow rate of 0.7L/min and argon with the flow rate of 2.3L/min, depositing for 40 hours, and finishing deposition to obtain the (Si-N) @ C-Ca-P-C biomedical bone replacement composite material.
The compression strength of the (Si-N) @ C-Ca-P-C biomedical bone replacement composite material obtained in this example was 85.4 MPa.
EXAMPLE 4
(1) Adding polysilazane and ferrocene into xylene, wherein the mass ratio of polysilazane to ferrocene is 7:1, the mass ratio of polysilazane to xylene is 1:45, uniformly stirring, standing in air for natural solidification, grinding the solidified material into powder, paving the powder at the bottom of U-shaped carbon paper, covering the powder with another U-shaped carbon paper, then placing the U-shaped carbon paper into a high-temperature furnace for heat treatment, firstly introducing nitrogen with the flow rate of 10L/min, then heating to 300 ℃ at the speed of 5 ℃/min, keeping the temperature for 2 hours, then heating to 1400 ℃ at the speed of 10 ℃/min, keeping the temperature for 4 hours, naturally cooling the system to room temperature, and taking out a sample deposited on the surface of the upper layer of U-shaped carbon paper, and marking the sample as A;
(2) putting the A into a high-temperature furnace, introducing nitrogen with the flow rate of 10L/min, heating to 700 ℃ at the speed of 10 ℃/min, introducing natural gas with the flow rate of 0.5L/min after the temperature is reached, adjusting the flow rate of the nitrogen to 2.0L/min, reacting for 2 hours, heating to 1100 ℃ at the speed of 8 ℃/min, adjusting the flow rate of the natural gas to 0.2L/min after the temperature is reached, keeping the flow rate of the nitrogen unchanged, and keeping the deposition time to 3 hours, wherein the obtained sample is marked as B;
(3) sample B was placed in a carbon-spraying apparatus at a pressure of 5X 10 -2 Pa, spraying carbon for 10 seconds under the condition of 5mA current, and marking an obtained sample as C;
(4) dissolving ammonium dihydrogen phosphate in hydrogen peroxide to prepare a solution with the concentration of 140mmol/L, dissolving calcium nitrate in water to prepare a solution with the concentration of 100mmol/L, and uniformly mixing the hydrogen peroxide solution of ammonium dihydrogen phosphate and the aqueous solution of calcium nitrate according to the molar ratio of 1.67 of calcium nitrate to ammonium dihydrogen phosphate to obtain a solution D;
(5) putting the sample C and the solution D together in an autoclave, completely immersing the sample C in the solution D, and treating for 10 minutes at the temperature of 110 ℃, wherein the obtained sample is marked as E;
(6) taking a graphite sheet as an anode and a sample E as a cathode, applying a voltage of 5V, a pulse width of 60ms, a pulse interval of 100ms, a reaction time of 7 minutes, a reaction temperature of 40 ℃, and marking the obtained sample as F;
(7) and (2) placing the F into a chemical vapor deposition furnace, heating to 1050 ℃ at the speed of 10 ℃/min, then introducing natural gas with the flow rate of 0.5L/min and argon with the flow rate of 2.4L/min, depositing for 30 hours, and obtaining the (Si-N) @ C-Ca-P-C biomedical bone replacement composite material after the deposition is finished.
The compression strength of the (Si-N) @ C-Ca-P-C biomedical bone replacement composite material obtained in this example was 81.8 MPa.
Claims (2)
1. A (Si-N) @ C-Ca-P-C biomedical bone replacement composite material is characterized by comprising Si-N lines, wheat-ear-shaped Ca-P and C materials; taking a Si-N line as a central nuclear layer structure, wrapping two layers of C materials outside the nuclear layer structure, and wrapping the C material with ear-shaped Ca-P outside the wrapping layer; the molecules are connected by chemical bonds; the preparation method of the composite material comprises the following steps:
step 1: adding polysilazane and ferrocene into xylene, uniformly stirring, standing in the air for natural curing, and then grinding the cured material into powder;
the powder was laid flat between two pieces of U-shaped carbon paper and subsequently placed in a high temperature furnace for heat treatment: firstly, introducing nitrogen with the flow rate of 4-10L/min, then heating to 200-300 ℃ at the speed of 5-10 ℃/min, keeping the temperature for 1-3 hours, then heating to 1300-1450 ℃ at the speed of 8-10 ℃/min, keeping the temperature for 2-5 hours, naturally cooling the system to the room temperature, and taking out the material deposited on the surface of the U-shaped carbon paper as a Si-N line;
the mass ratio of the polysilazane to the ferrocene is 7:1-9: 1;
the mass ratio of the polysilazane to the xylene is 1:40-1: 60;
step 2: putting the Si-N wire into a high temperature furnace, introducing nitrogen with the flow rate of 5-10L/min, heating to 700-800 ℃ at the speed of 8-10 ℃/min, introducing natural gas with the flow rate of 0.5-0.8L/min after reaching the temperature, adjusting the flow rate of the nitrogen to 2.0-2.5L/min, and reacting for 1-3 hours; then heating to 1000-1200 ℃ at the speed of 5-8 ℃/min, adjusting the flow rate of the natural gas to 0.2-0.4L/min after the temperature is reached, keeping the flow rate of nitrogen unchanged, and depositing for 1-3 hours to obtain a carbon wrapping layer on the outer layer of the Si-N line;
and step 3: placing in carbon spraying instrument under pressure of 5 × 10 -2 -6×10 -2 Pa, spraying carbon for 10-30 seconds under the condition of 3-5mA current, and obtaining the material (Si-N) @ C of a second carbon wrapping layer on the outer layer of the carbon wrapping layer;
and 4, step 4: immersing the Si-N wire with the carbon wrapping layer in a mixed solution of calcium nitrate and ammonium dihydrogen phosphate, putting the immersed Si-N wire and the mixed solution in a high-pressure kettle together, and treating the immersed Si-N wire and the mixed solution for 10 to 30 minutes at the temperature of 100-120 ℃;
the molar ratio of the calcium nitrate to the ammonium dihydrogen phosphate in the mixed solution of the calcium nitrate and the ammonium dihydrogen phosphate is 1.6-1.8;
and 5: taking a graphite sheet as an anode, taking the material treated in the step 4 as a cathode, applying a voltage of 2-5V, a pulse width of 50-80ms, a pulse interval of 100-150ms, a reaction time of 1-10 minutes and a reaction temperature of 40-60 ℃ to obtain a material which takes a Si-N line as a core and is wrapped by two layers of C and wheat-ear-shaped Ca-P;
step 6: and (5) placing the material obtained in the step (5) in a chemical vapor deposition furnace, heating to 950-.
2. The method of claim 1, wherein: the mixed solution of the calcium nitrate and the ammonium dihydrogen phosphate is as follows: dissolving ammonium dihydrogen phosphate in hydrogen peroxide to prepare a solution with the concentration of 100-150mmol/L, and dissolving calcium nitrate in water to prepare a mixed solution of the solution with the concentration of 100-150 mmol/L.
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