CN108675281B - Carbon nanotube-based composite material with both conductivity and magnetism and preparation method thereof - Google Patents

Carbon nanotube-based composite material with both conductivity and magnetism and preparation method thereof Download PDF

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CN108675281B
CN108675281B CN201810295504.9A CN201810295504A CN108675281B CN 108675281 B CN108675281 B CN 108675281B CN 201810295504 A CN201810295504 A CN 201810295504A CN 108675281 B CN108675281 B CN 108675281B
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卢晓英
唐荣平
李冕
魏立恒
卢怡
翁杰
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Southwest Jiaotong University
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Abstract

The invention discloses a carbon nanotube-based composite material with both conductivity and magnetism and a preparation method thereof. The method comprises the following steps: (1) dropwise adding a solution containing ferric salt into a magnesium oxide solution, performing ultrasonic treatment, and then heating and evaporating to dryness to obtain a solid mixture; wherein the molar ratio of magnesium oxide to iron element is 1-2: 0.5-1; (2) adding water to dissolve the solid mixture, and carrying out hydrothermal treatment at 160-200 ℃ for 2-4 h to obtain an Fe/MgO precursor; (3) preparing a carbon nanotube-based framework by using a Fe/MgO precursor as a raw material through a vapor deposition method; (4) and placing the prepared carbon nanotube-based framework in an in-vitro mineralization liquid, and soaking for 2-7 days under the stimulation condition to obtain the carbon nanotube-based composite material with both conductivity and magnetism. The carbon nanotube-based composite material prepared by the method has excellent conductivity and magnetism, and has great potential application value in the fields of bone repair and the like.

Description

Carbon nanotube-based composite material with both conductivity and magnetism and preparation method thereof
Technical Field
The invention belongs to the technical field of biological application materials, and particularly relates to a carbon nanotube-based composite material with both conductivity and magnetism and a preparation method thereof.
Background
Hydroxyapatite is a calcium phosphate bioceramic widely existing in tooth and bone tissues of animals, has chemical components and crystal structures similar to inorganic substances in natural bones of human bodies, and thus has excellent biocompatibility and bioactivity. The hydroxyapatite is nontoxic, harmless and degradable to organisms, can enhance the healing of bones, is chemically combined with natural bones, can be well used as a filling material for bone defects, provides a support for the formation of new bones, and plays a good bone conduction role. The hydroxyapatite material has unique performance and obvious effect in the application fields of bone tissue engineering repair, medicine carrying, environmental decontamination and the like. However, hydroxyapatite has the disadvantages of brittleness, low wear resistance, poor toughness and the like, and the hydroxyapatite itself has no magnetism and electric conductivity, so that the disadvantages limit the application of the hydroxyapatite in biomedicine.
The magnetic material has good prospect in the aspects of biology and medicine due to the unique property, the magnetic material can carry medicine to kill tumor tissues or tumor cells in a targeted way, and the magnetic heat therapy can convert the energy of an external magnetic field into heat energy so as to kill the cells in a tumor area. At present, electrical stimulation bone repair has good application in clinic, electrical stimulation has a long history in the field of bone treatment, electrical stimulation has a remarkable effect in recovery after femoral head necrosis, lumbar intervertebral disc fusion and the like, and preparation of a bone repair material with conductivity is particularly important. However, most of the materials now have only a single property, and cannot use both the electrical stimulation and the magnetic therapy. Therefore, the material with good magnetism, conductivity and biocompatibility has great potential application value.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a carbon nanotube-based composite material with both conductivity and magnetism and a preparation method thereof.
In order to achieve the purpose, the technical scheme adopted by the invention for solving the technical problems is as follows:
1. a preparation method of a carbon nanotube-based composite material with both conductivity and magnetism comprises the following steps:
(1) dropwise adding a solution containing ferric salt into a magnesium oxide solution, performing ultrasonic treatment, and then heating and evaporating to dryness to obtain a solid mixture; wherein the molar ratio of magnesium oxide to iron element is 1-2: 0.5-1;
(2) adding water to dissolve the solid mixture, and carrying out hydrothermal treatment at 160-200 ℃ for 2-4 h to obtain an Fe/MgO precursor;
(3) preparing a carbon nanotube-based framework by using a Fe/MgO precursor as a raw material through a vapor deposition method;
(4) placing the prepared carbon nanotube-based framework in an in-vitro mineralization liquid, and soaking for 2-7 days under the stimulation condition to obtain a carbon nanotube-based composite material with both conductivity and magnetism; wherein the weight ratio of the carbon nanotube-based skeleton to the in-vitro mineralized liquid is 0.5-2: 100.
Further, in the step (1), the ferric salt is soluble salt, specifically FeSO4、Fe2(SO4)3、Fe(NO3)3、Fe(NO3)2、FeCl3、FeCl2Or FeCO3。
Further, the molar ratio of magnesium oxide to iron element in the step (1) is 2: 1.
Further, the specific process of vapor deposition in step (3) is as follows:
argon as shielding gas, C2H2Taking gas as a carbon source, heating to 500-800 ℃ at the speed of 10 ℃/min, and then depositing for 30-120 min; wherein, argon and C2H2The flow rate ratio of (A) is 8-10: 1.
Furthermore, the electric conductivity of the carbon nanotube-based skeleton in the step (3) is 3-26S/cm, and the magnetic saturation intensity is 30-40 emu/g.
Further, in the step (4), the in vitro mineralized liquid is biomimetic mineralized liquid (SBF), accelerated mineralized liquid (ACS) or saturated mineralized liquid (SCS).
Further, the stimulation condition in the step (4) is current stimulation, static magnetic field stimulation, electromagnetic field stimulation, dual stimulation of current and electromagnetic field or dual stimulation of current and static magnetic field.
The carbon nanotube-based composite material with both conductivity and magnetism is prepared by the method.
Furthermore, the electric conductivity of the carbon nanotube-based composite material is 1-30S/cm, and the magnetic saturation intensity is 25-30 emu/g.
The invention has the beneficial effects that:
1. the invention takes Fe/MgO precursor as raw material, takes acetylene as carbon source, and can prepare the carbon nano tube-based framework with certain magnetism and conductivity by catalytically cracking the acetylene in the vapor deposition process, so that one of the main components of the prepared carbon nano tube-based composite material is CNTs, and the CNTs with excellent mechanical property are introduced, thereby greatly improving the overall mechanical property of the biological composite materialEnergy is saved; meanwhile, in the vapor deposition process, due to the presence of metal particles as a catalyst, magnetic Fe is generated by the reaction of acetylene and Fe/MgO precursor3C, and Fe3C, depositing on the carbon nanotube-based framework to ensure that the carbon nanotube-based composite material contains magnetic metal particles; further imparting conductivity and magnetism to the entire carbon nanotube-based composite material.
2. Through stimulation of external conditions, the conductivity of the carbon nanotube-based composite material can be effectively improved under the coordination of the original performance of the carbon nanotube-based composite material.
3. In the process of putting the carbon nano tube-based skeleton into in-vitro mineralization liquid for mineralization, the carbon nano tube-based skeleton is taken as a template, calcium phosphate is deposited on the carbon nano tube-based skeleton to generate Ca10(PO4)6(OH)2One of the main components of the prepared carbon nanotube-based composite material is Ca10(PO4)6(OH)2And also Ca10(PO4)6(OH)2Is the main inorganic component in natural bone, so the prepared carbon nanotube-based composite material has good biocompatibility and osteogenic activity.
4. The electromagnetic response performance of the composite material is adjusted by adjusting the stimulation mode and the stimulation duration of the external electric/magnetic field, so that the composite material is more beneficial to the treatment and repair of bones.
5. The method has the advantages of simple process, environmental protection, safety, no toxicity, simple process and strong operability, is suitable for industrial production, and has great potential application value in the field of orthopedic disease treatment such as tissue engineering, biosensing, drug controlled release, bone defect and the like.
Drawings
FIG. 1 is an XRD spectrum of a carbon nanotube-based composite material prepared in examples 1 to 5 of the present invention and a comparative example;
FIG. 2 is an SEM image of carbon nanotube-based composite materials prepared in examples 1 to 5 of the present invention and a comparative example;
FIG. 3 is a hysteresis loop test chart of carbon nanotube-based composites prepared in examples 1 to 5 of the present invention and comparative example;
fig. 4 is a graph showing the electrical conductivity of the carbon nanotube-based composite materials prepared in examples 1 to 5 of the present invention and comparative example.
Detailed Description
The following description of the embodiments of the present invention is provided to facilitate the understanding of the present invention by those skilled in the art, but it should be understood that the present invention is not limited to the scope of the embodiments, and it will be apparent to those skilled in the art that various changes may be made without departing from the spirit and scope of the invention as defined and defined in the appended claims, and all matters produced by the invention using the inventive concept are protected.
Example 1
A preparation method of a carbon nanotube-based composite material with both conductivity and magnetism comprises the following steps:
(1) 4.11g MgO and 12.3g Fe (NO)3)3·9H2O is respectively added into 100mL deionized water for ultrasonic dispersion for 30min to prepare MgO dispersion liquid and Fe (NO)3)3A solution;
(2) mixing Fe (NO)3)3Dropwise adding the solution into the MgO dispersion liquid, performing ultrasonic treatment for 30min, heating to 100 ℃ to boil the solution, and continuing heating until the solution is evaporated to dryness to obtain a yellow solid mixture;
(3) adding the solid mixture into 200mL of deionized water, ultrasonically dissolving for 1h, transferring into a 250mL reaction kettle, heating at 180 ℃ for 2h, naturally cooling to room temperature, taking out a reaction product in the reaction kettle, performing suction filtration and washing, drying at 60 ℃ for 24h, and grinding to obtain a Fe/MgO precursor;
(4) taking 0.5g of Fe/MgO precursor, flatly paving the Fe/MgO precursor in a quartz boat, placing the quartz boat in a tube furnace, then introducing 25sccm of argon into the tube furnace, and simultaneously heating the tube furnace to 600 ℃ at the speed of 10 ℃/min;
(5) after the temperature reached 600 ℃ it was maintained for 2h and then 225sccm of argon and 25sccm of C were introduced simultaneously2H2After 30min of deposition, stopping introducing C2H2Continuously introducing 25sccm of argon gas, naturally cooling to room temperature, and stopping introducing the argon gas to prepare the carbon nanotube-based framework with conductivity and magnetism;
(6) 0.1g of the carbon nanotube-based framework is placed in 100mL of accelerated mineralization liquid (ACS) to be soaked for 2 days, and is stimulated by a static magnetic field of 2.8mT for 5 hours every day, so that the carbon nanotube-based composite material with both conductivity and magnetism is prepared.
Example 2
A preparation method of a carbon nanotube-based composite material with both conductivity and magnetism comprises the following steps:
(1) 4.11g MgO and 12.3g Fe (NO)3)3·9H2O is respectively added into 100mL deionized water for ultrasonic dispersion for 30min to prepare MgO dispersion liquid and Fe (NO)3)3A solution;
(2) mixing Fe (NO)3)3Dropwise adding the solution into the MgO dispersion liquid, performing ultrasonic treatment for 30min, heating to 100 ℃ to boil the solution, and continuing heating until the solution is evaporated to dryness to obtain a yellow solid mixture;
(3) adding the solid mixture into 200mL of deionized water, ultrasonically dissolving for 1h, transferring into a 250mL reaction kettle, heating at 180 ℃ for 2h, naturally cooling to room temperature, taking out a reaction product in the reaction kettle, performing suction filtration and washing, drying at 60 ℃ for 24h, and grinding to obtain a Fe/MgO precursor;
(4) taking 0.5g of Fe/MgO precursor, flatly paving the Fe/MgO precursor in a quartz boat, placing the quartz boat in a tube furnace, then introducing 25sccm of argon into the tube furnace, and simultaneously heating the tube furnace to 600 ℃ at the speed of 10 ℃/min;
(5) after the temperature reached 600 ℃ it was maintained for 2h and then 225sccm of argon and 25sccm of C were introduced simultaneously2H2After 30min of deposition, stopping introducing C2H2Continuously introducing 25sccm of argon gas, naturally cooling to room temperature, and stopping introducing the argon gas to prepare the carbon nanotube-based framework with conductivity and magnetism;
(6) 0.1g of carbon nanotube-based framework is placed in 100mL of accelerated mineralization liquid (ACS) to be soaked for 2 days, and is stimulated by an electromagnetic field of 2.8mT for 5 hours every day, so that the carbon nanotube-based composite material with both conductivity and magnetism is prepared.
Example 3
A preparation method of a carbon nanotube-based composite material with both conductivity and magnetism comprises the following steps:
(1) 4.11g MgO and 12.3g Fe (NO)3)3·9H2O is respectively added into 100mL deionized water for ultrasonic dispersion for 30min to prepare MgO dispersion liquid and Fe (NO)3)3A solution;
(2) mixing Fe (NO)3)3Dropwise adding the solution into the MgO dispersion liquid, performing ultrasonic treatment for 30min, heating to 100 ℃ to boil the solution, and continuing heating until the solution is evaporated to dryness to obtain a yellow solid mixture;
(3) adding the solid mixture into 200mL of deionized water, ultrasonically dissolving for 1h, transferring into a 250mL reaction kettle, heating at 180 ℃ for 2h, naturally cooling to room temperature, taking out a reaction product in the reaction kettle, performing suction filtration and washing, drying at 60 ℃ for 24h, and grinding to obtain a Fe/MgO precursor;
(4) taking 0.5g of Fe/MgO precursor, flatly paving the Fe/MgO precursor in a quartz boat, placing the quartz boat in a tube furnace, then introducing 25sccm of argon into the tube furnace, and simultaneously heating the tube furnace to 600 ℃ at the speed of 10 ℃/min;
(5) after the temperature reached 600 ℃ it was maintained for 2h and then 225sccm of argon and 25sccm of C were introduced simultaneously2H2After 30min of deposition, stopping introducing C2H2Continuously introducing 25sccm of argon gas, naturally cooling to room temperature, and stopping introducing the argon gas to prepare the carbon nanotube-based framework with conductivity and magnetism;
(6) and (3) placing 0.1g of the carbon nanotube-based framework in 100mL of accelerated mineralization liquid (ACS), soaking for 2 days, stimulating by using 100mA direct current for 5 hours every day, and preparing the carbon nanotube-based composite material with both conductivity and magnetism.
Example 4
A preparation method of a carbon nanotube-based composite material with both conductivity and magnetism comprises the following steps:
(1) 4.11g MgO and 12.3g Fe (NO)3)3·9H2O is respectively added into 100mL deionized water for ultrasonic dispersion for 30min to prepare MgO dispersion liquid and Fe (NO)3)3A solution;
(2) mixing Fe (NO)3)3Dropwise adding the solution into the MgO dispersion liquid, performing ultrasonic treatment for 30min, heating to 100 ℃ to boil the solution, and continuing heating until the solution is evaporated to dryness to obtain a yellow solid mixture;
(3) adding the solid mixture into 200mL of deionized water, ultrasonically dissolving for 1h, transferring into a 250mL reaction kettle, heating at 180 ℃ for 2h, naturally cooling to room temperature, taking out a reaction product in the reaction kettle, performing suction filtration and washing, drying at 60 ℃ for 24h, and grinding to obtain a Fe/MgO precursor;
(4) taking 0.5g of Fe/MgO precursor, flatly paving the Fe/MgO precursor in a quartz boat, placing the quartz boat in a tube furnace, then introducing 25sccm of argon into the tube furnace, and simultaneously heating the tube furnace to 600 ℃ at the speed of 10 ℃/min;
(5) after the temperature reached 600 ℃ it was maintained for 2h and then 225sccm of argon and 25sccm of C were introduced simultaneously2H2After 30min of deposition, stopping introducing C2H2Continuously introducing 25sccm of argon gas, naturally cooling to room temperature, and stopping introducing the argon gas to prepare the carbon nanotube-based framework with conductivity and magnetism;
(6) 0.1g of carbon nanotube-based framework is placed in 100mL of accelerated mineralization liquid (ACS) to be soaked for 2 days, and is stimulated by 100mA direct current and 2.8mT electromagnetic field together for 5h every day to prepare the carbon nanotube-based composite material with both conductivity and magnetism.
Example 5
A preparation method of a carbon nanotube-based composite material with both conductivity and magnetism comprises the following steps:
(1) 4.11g MgO and 12.3g Fe (NO)3)3·9H2O is respectively added into 100mL of deionized water for ultrasonic dispersion of 30min, preparing to obtain MgO dispersion and Fe (NO)3)3A solution;
(2) mixing Fe (NO)3)3Dropwise adding the solution into the MgO dispersion liquid, performing ultrasonic treatment for 30min, heating to 100 ℃ to boil the solution, and continuing heating until the solution is evaporated to dryness to obtain a yellow solid mixture;
(3) adding the solid mixture into 200mL of deionized water, ultrasonically dissolving for 1h, transferring into a 250mL reaction kettle, heating at 180 ℃ for 2h, naturally cooling to room temperature, taking out a reaction product in the reaction kettle, performing suction filtration and washing, drying at 60 ℃ for 24h, and grinding to obtain a Fe/MgO precursor;
(4) taking 0.5g of Fe/MgO precursor, flatly paving the Fe/MgO precursor in a quartz boat, placing the quartz boat in a tube furnace, then introducing 25sccm of argon into the tube furnace, and simultaneously heating the tube furnace to 600 ℃ at the speed of 10 ℃/min;
(5) after the temperature reached 600 ℃ it was maintained for 2h and then 225sccm of argon and 25sccm of C were introduced simultaneously2H2After 30min of deposition, stopping introducing C2H2Continuously introducing 25sccm of argon gas, naturally cooling to room temperature, and stopping introducing the argon gas to prepare the carbon nanotube-based framework with conductivity and magnetism;
(6) and (3) placing 0.1g of the carbon nanotube-based framework in 100mL of accelerated mineralization liquid (ACS), and soaking for 2 days to prepare the carbon nanotube-based composite material with both conductivity and magnetism.
Example 6
A preparation method of a carbon nanotube-based composite material with both conductivity and magnetism comprises the following steps:
(1) 4.11g of MgO and 12.3g of FeCl3Respectively adding into 100mL deionized water, and ultrasonically dispersing for 30min to obtain MgO dispersion and Fe (NO)3)3A solution;
(2) mixing Fe (NO)3)3Dropwise adding the solution into the MgO dispersion liquid, performing ultrasonic treatment for 30min, heating to 100 ℃ to boil the solution, and continuing heating until the solution is evaporated to dryness to obtain a yellow solid mixture;
(3) adding the solid mixture into 200mL of deionized water, ultrasonically dissolving for 1h, transferring into a 250mL reaction kettle, heating at 180 ℃ for 2h, naturally cooling to room temperature, taking out a reaction product in the reaction kettle, performing suction filtration and washing, drying at 60 ℃ for 24h, and grinding to obtain a Fe/MgO precursor;
(4) taking 0.5g of Fe/MgO precursor, flatly paving the Fe/MgO precursor in a quartz boat, placing the quartz boat in a tube furnace, then introducing 25sccm of argon into the tube furnace, and simultaneously heating the tube furnace to 600 ℃ at the speed of 10 ℃/min;
(5) after the temperature reached 600 ℃ it was maintained for 2h and then 225sccm of argon and 25sccm of C were introduced simultaneously2H2After 30min of deposition, stopping introducing C2H2Continuously introducing 25sccm of argon gas, naturally cooling to room temperature, and stopping introducing the argon gas to prepare the carbon nanotube-based framework with conductivity and magnetism;
(6) 0.1g of the carbon nanotube-based framework is placed in 100mL of accelerated mineralization liquid (ACS) to be soaked for 2 days, and is stimulated by a static magnetic field of 2.8mT for 5 hours every day, so that the carbon nanotube-based composite material with both conductivity and magnetism is prepared.
Example 7
A preparation method of a carbon nanotube-based composite material with both conductivity and magnetism comprises the following steps:
(1) 4.11g MgO and 12.3g Fe (NO)3)3·9H2O is respectively added into 100mL deionized water for ultrasonic dispersion for 30min to prepare MgO dispersion liquid and Fe (NO)3)3A solution;
(2) mixing Fe (NO)3)3Dropwise adding the solution into the MgO dispersion liquid, performing ultrasonic treatment for 30min, heating to 100 ℃ to boil the solution, and continuing heating until the solution is evaporated to dryness to obtain a yellow solid mixture;
(3) adding the solid mixture into 200mL of deionized water, ultrasonically dissolving for 1h, transferring into a 250mL reaction kettle, heating at 160 ℃ for 2h, naturally cooling to room temperature, taking out a reaction product in the reaction kettle, performing suction filtration and washing, drying at 60 ℃ for 24h, and grinding to obtain a Fe/MgO precursor;
(4) taking 0.5g of Fe/MgO precursor, flatly paving the Fe/MgO precursor in a quartz boat, placing the quartz boat in a tube furnace, then introducing 25sccm of argon into the tube furnace, and simultaneously heating the tube furnace to 600 ℃ at the speed of 10 ℃/min;
(5) after the temperature reached 600 ℃ it was maintained for 2h and then 225sccm of argon and 25sccm of C were introduced simultaneously2H2After 30min of deposition, stopping introducing C2H2Continuously introducing 25sccm of argon gas, naturally cooling to room temperature, and stopping introducing the argon gas to prepare the carbon nanotube-based framework with conductivity and magnetism;
(6) 0.1g of the carbon nanotube-based framework is placed in 100mL of accelerated mineralization liquid (ACS) to be soaked for 2 days, and is stimulated by a static magnetic field of 2.8mT for 5 hours every day, so that the carbon nanotube-based composite material with both conductivity and magnetism is prepared.
Example 8
A preparation method of a carbon nanotube-based composite material with both conductivity and magnetism comprises the following steps:
(1) 4.11g MgO and 12.3g Fe (NO)3)3·9H2O is respectively added into 100mL deionized water for ultrasonic dispersion for 30min to prepare MgO dispersion liquid and Fe (NO)3)3A solution;
(2) mixing Fe (NO)3)3Dropwise adding the solution into the MgO dispersion liquid, performing ultrasonic treatment for 30min, heating to 100 ℃ to boil the solution, and continuing heating until the solution is evaporated to dryness to obtain a yellow solid mixture;
(3) adding the solid mixture into 200mL of deionized water, ultrasonically dissolving for 1h, transferring into a 250mL reaction kettle, heating at 200 ℃ for 2h, naturally cooling to room temperature, taking out a reaction product in the reaction kettle, performing suction filtration and washing, drying at 60 ℃ for 24h, and grinding to obtain a Fe/MgO precursor;
(4) taking 0.5g of Fe/MgO precursor, flatly paving the Fe/MgO precursor in a quartz boat, placing the quartz boat in a tube furnace, then introducing 25sccm of argon into the tube furnace, and simultaneously heating the tube furnace to 600 ℃ at the speed of 10 ℃/min;
(5) after the temperature reached 600 ℃ it was maintained for 2h and then 225sccm of argon and 25sccm of C were introduced simultaneously2H2After 30min of deposition, stopping introducing C2H2Continuously introducing 25sccm of argon gas, naturally cooling to room temperature, and stopping introducing the argon gas to prepare the carbon nanotube-based framework with conductivity and magnetism;
(6) 0.1g of the carbon nanotube-based framework is placed in 100mL of accelerated mineralization liquid (ACS) to be soaked for 2 days, and is stimulated by a static magnetic field of 2.8mT for 5 hours every day, so that the carbon nanotube-based composite material with both conductivity and magnetism is prepared.
Example 9
A preparation method of a carbon nanotube-based composite material with both conductivity and magnetism comprises the following steps:
(1) 4.11g MgO and 12.3g Fe (NO)3)3·9H2O is respectively added into 100mL deionized water for ultrasonic dispersion for 30min to prepare MgO dispersion liquid and Fe (NO)3)3A solution;
(2) mixing Fe (NO)3)3Dropwise adding the solution into the MgO dispersion liquid, performing ultrasonic treatment for 30min, heating to 100 ℃ to boil the solution, and continuing heating until the solution is evaporated to dryness to obtain a yellow solid mixture;
(3) adding the solid mixture into 200mL of deionized water, ultrasonically dissolving for 1h, transferring into a 250mL reaction kettle, heating at 180 ℃ for 3h, naturally cooling to room temperature, taking out a reaction product in the reaction kettle, performing suction filtration and washing, drying at 60 ℃ for 24h, and grinding to obtain a Fe/MgO precursor;
(4) taking 0.5g of Fe/MgO precursor, flatly paving the Fe/MgO precursor in a quartz boat, placing the quartz boat in a tube furnace, then introducing 25sccm of argon into the tube furnace, and simultaneously heating the tube furnace to 600 ℃ at the speed of 10 ℃/min;
(5) after the temperature reached 600 ℃ it was maintained for 2h and then 225sccm of argon and 25sccm of C were introduced simultaneously2H2After 30min of deposition, stopping introducing C2H2Then, continuously introducing 25sccm argon gas to naturally cool the mixture to room temperature,then stopping introducing the argon gas, and preparing the carbon nanotube-based framework with conductivity and magnetism;
(6) 0.1g of the carbon nanotube-based framework is placed in 100mL of accelerated mineralization liquid (ACS) to be soaked for 2 days, and is stimulated by a static magnetic field of 2.8mT for 5 hours every day, so that the carbon nanotube-based composite material with both conductivity and magnetism is prepared.
Example 10
A preparation method of a carbon nanotube-based composite material with both conductivity and magnetism comprises the following steps:
(1) 4.11g MgO and 12.3g Fe (NO)3)3·9H2O is respectively added into 100mL deionized water for ultrasonic dispersion for 30min to prepare MgO dispersion liquid and Fe (NO)3)3A solution;
(2) mixing Fe (NO)3)3Dropwise adding the solution into the MgO dispersion liquid, performing ultrasonic treatment for 30min, heating to 100 ℃ to boil the solution, and continuing heating until the solution is evaporated to dryness to obtain a yellow solid mixture;
(3) adding the solid mixture into 200mL of deionized water, ultrasonically dissolving for 1h, transferring into a 250mL reaction kettle, heating at 180 ℃ for 1h, naturally cooling to room temperature, taking out a reaction product in the reaction kettle, performing suction filtration and washing, drying at 60 ℃ for 24h, and grinding to obtain a Fe/MgO precursor;
(4) taking 0.5g of Fe/MgO precursor, flatly paving the Fe/MgO precursor in a quartz boat, placing the quartz boat in a tube furnace, then introducing 25sccm of argon into the tube furnace, and simultaneously heating the tube furnace to 600 ℃ at the speed of 10 ℃/min;
(5) after the temperature reached 600 ℃ it was maintained for 2h and then 225sccm of argon and 25sccm of C were introduced simultaneously2H2After 30min of deposition, stopping introducing C2H2Continuously introducing 25sccm of argon gas, naturally cooling to room temperature, and stopping introducing the argon gas to prepare the carbon nanotube-based framework with conductivity and magnetism;
(6) 0.1g of the carbon nanotube-based framework is placed in 100mL of accelerated mineralization liquid (ACS) to be soaked for 2 days, and is stimulated by a static magnetic field of 2.8mT for 5 hours every day, so that the carbon nanotube-based composite material with both conductivity and magnetism is prepared.
Comparative example
In comparison with example 1, the mineralization treatment described in step (6) was absent, and the rest of the procedure was the same as in example 1.
Examples of the experiments
The products from examples 1 to 5 and comparative example were subjected to the following performance tests:
x-ray diffraction analysis
Putting the product in a vacuum drying oven at 60 ℃ for drying, and then analyzing the product by using an X-ray diffractometer (XRD), wherein the determination parameters are as follows: the results are shown in fig. 1 for a copper target with a scan speed of 10 °/min and a diffraction angle in the range of 2 θ of 20 to 70 °, where a is comparative example, b is example 5, c is example 3, d is example 2, e is example 1, and f is example 4.
2. Analysis by scanning Electron microscope
The microscopic morphology of the product sections was observed by Scanning Electron Microscopy (SEM) and the results are shown in FIG. 2, where a is comparative example, b is example 5, c is example 3, d is example 2, e is example 1, and f is example 4.
3. Magnetic property test
Weighing the powder of the product, packaging in a raw material tape to obtain a small ball for testing, wherein the mass of the product is detected to be 10-20mg, the testing temperature is 300K, and the applied magnetic field strength is-6 × 105～6×105A/m, the results are shown in FIG. 3; wherein a is a comparative example, b is an embodiment 5, c is an embodiment 3, d is an embodiment 2, e is an embodiment 1, and f is an embodiment 4.
4. Electrical Performance testing
And testing the conductivity of the product by adopting four probes to represent the electrical property of the product. The prepared product was pressed with a mold into 0.3mm circular pieces with a diameter of 10mm and the test results are shown in FIG. 4 at room temperature, wherein unmineralized as comparative example and no stimulation are shown in example 5, DC is 100mA direct current stimulation (example 3), EMF is 2.8mT electromagnetic field stimulation (example 2), SMF is 2.8mT static magnetic field stimulation (example 1), DC and EMF are 100mA current stimulation and 2.8mT electromagnetic field stimulation dual stimulation (example 4).
From the experimental results of fig. 1 to 4, it is clear that: the carbon nanotube-based composite material with both conductivity and magnetism prepared by the invention mainly contains Ca10(PO4)6(OH)2、CNTs、Fe3C and MgO, wherein CNTs constructs a conductive network in the composite material to enable the composite material to have conductivity, and Fe3The C has magnetism, so that the composite material has magnetism and reaches 25-30 emu/g.
Under different stimulation conditions, the magnetic property and the conductivity of the product obtained in the embodiment 1-5 are different, which shows that the external stimulation mode has great influence on the conductivity of the product and has certain influence on the magnetic property. The conductivity of the product prepared in example 4 is higher than that of the comparative example, and the conductivity of the products prepared in examples 1-3 and example 5 is lower than that of the comparative example (refer to FIG. 4); indicating that the product prepared by the method described in example 4 has the best conductivity.
The maximum saturation intensities of the examples 1-5 and the comparative example are 26.40emu/g, 27.84emu/g, 26.97emu/g, 26.78emu/g, 29.17emu/g and 31.35emu/g in sequence. Therefore, the magnetic saturation intensities of the examples 1 to 5 are all lower than those of the comparative examples, and the difference values are all 0 to 4emu/g (refer to fig. 3), which shows that the external stimulation mode has a certain influence on the magnetic performance, but the influence degree is not large and is within an acceptable range.
In conclusion, the carbon nanotube-based composite material with both conductivity and magnetism, which is prepared by the invention, not only has good conductivity and magnetism, but also has good biocompatibility and mechanical properties, and has great potential application value in the fields of bone repair and the like.

Claims (8)

1. A preparation method of a carbon nanotube-based composite material with both conductivity and magnetism is characterized by comprising the following steps:
(1) dropwise adding a solution containing ferric salt into a magnesium oxide solution, performing ultrasonic treatment, and then heating and evaporating to dryness to obtain a solid mixture; wherein the molar ratio of magnesium oxide to iron element is 1-2: 0.5-1;
(2) adding water to dissolve the solid mixture, and carrying out hydrothermal treatment at 160-200 ℃ for 2-4 h to obtain an Fe/MgO precursor;
(3) preparing a carbon nanotube-based framework by using a Fe/MgO precursor as a raw material through a vapor deposition method;
(4) placing the prepared carbon nanotube-based framework in an in-vitro mineralization liquid, and soaking for 2-7 days under the conditions of double stimulation of current and electromagnetic field to obtain a carbon nanotube-based composite material with both conductivity and magnetism; wherein the weight ratio of the carbon nanotube-based skeleton to the in-vitro mineralized liquid is 0.5-2: 100.
2. The method for preparing the carbon nanotube-based composite material having both conductivity and magnetism according to claim 1, wherein the iron salt in the step (1) is a soluble salt; the soluble salt is FeSO4、Fe2(SO4)3、Fe(NO3)3、Fe(NO3)2、FeCl3Or FeCl2。
3. The method for preparing a carbon nanotube-based composite material having both conductivity and magnetism according to claim 1, wherein the molar ratio of magnesium oxide to iron in step (1) is 2: 1.
4. The method for preparing a carbon nanotube-based composite material having both conductivity and magnetism according to claim 1, wherein the vapor deposition in the step (3) comprises:
argon as shielding gas, C2H2Taking gas as a carbon source, heating to 500-800 ℃ at the speed of 10 ℃/min, and then depositing for 30-120 min; wherein, argon and C2H2The flow rate ratio of (A) is 8-10: 1.
5. The method for preparing a carbon nanotube-based composite material having both conductivity and magnetism according to claim 1, wherein in the step (3), the carbon nanotube-based skeleton has a conductivity of 3 to 26S/cm and a magnetic saturation intensity of 30 to 40 emu/g.
6. The method for preparing a carbon nanotube-based composite material having both conductivity and magnetism according to claim 1, wherein the in vitro mineralization liquid in the step (4) is a biomimetic mineralization liquid, an accelerated mineralization liquid or a saturated mineralization liquid.
7. The carbon nanotube-based composite material having both conductivity and magnetism, which is prepared by the method of any one of claims 1 to 6.
8. The carbon nanotube-based composite material according to claim 7, wherein the carbon nanotube-based composite material has an electrical conductivity of 1 to 30S/cm and a magnetic saturation intensity of 25 to 30 emu/g.
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