CN107137772B - Preparation method of carbon nano tube reinforced hydroxyapatite composite material - Google Patents
Preparation method of carbon nano tube reinforced hydroxyapatite composite material Download PDFInfo
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Abstract
The invention discloses a preparation method of a carbon nano tube reinforced hydroxyapatite composite material, relates to a composition taking phosphate as a base material, and particularly relates to a preparation method of a carbon nano tube reinforced hydroxyapatite composite material, which is characterized in that a carbon nano tube is prepared by a chemical vapor deposition method and is subjected to functional treatment, a collagen layer is coated on the surface of the carbon nano tube subjected to the functional treatment in situ by adopting a method of combining a magnetic liquid phase stirring method and a hydrogel method, and then the collagen-coated carbon nano tube reinforced hydroxyapatite composite material is prepared by a dry state press forming method. The method overcomes the defects of low interface bonding strength of the carbon nano tube reinforced hydroxyapatite composite material and poor dispersibility of the carbon nano tube in the prior art, which leads to low comprehensive mechanical property of the composite material; the composite material has poor biocompatibility and even has toxicity, and the composite material has risks when being used as a biomedical material; poor repair of bone cell migration, growth and differentiation; and the defect of poor using effect as a biomedical material.
Description
Technical Field
The technical scheme of the invention relates to a composition taking phosphate as a base material, in particular to a preparation method of a carbon nano tube reinforced hydroxyapatite composite material.
Background
Hydroxyapatite, which accounts for about 70% of inorganic components in hard tissues of human body and has a structure very similar to that of bone tissues of human body, has been widely used in the biomedical field, particularly as a carrier of drugs and genes and a bone tissue repair material, in view of its non-toxic and non-carcinogenic effects and its excellent characteristics of bioactivity, biodegradability, osteoconductivity, biocompatibility and non-immunogenicity. However, pure hydroxyapatite has poor mechanical properties and reliability, cannot be directly implanted into a human body as a load-bearing bone, and restricts the wide application of the pure hydroxyapatite in the biomedical field. Therefore, in order to meet the requirements of biological application of hydroxyapatite as a hard tissue implant, research on the reinforcement and toughening of hydroxyapatite has become a crucial link in promoting the wide application of hydroxyapatite in the biomedical field.
In the development work on hydroxyapatite reinforcement and toughening, various reinforcement phases have been tried, such as titanium and its alloys, alumina, zirconia, silicon carbide, polyethylene and carbon nanotube reinforcement phases. The carbon nano tube has the advantages of light weight, large length-diameter ratio, excellent mechanical property, extremely high specific surface area and good electrical, thermal and magnetic properties, and is considered as an ideal reinforcing phase for reinforcing the hydroxyapatite composite material. In recent years, there have been some reports on the prior art of carbon nanotube-hydroxyapatite composite materials: CN104998301A reports a preparation method of a carbon nanotube-reinforced mesoporous hydroxyapatite composite material, in which carbon nanotube-hydroxyapatite composite powder is prepared by an in-situ synthesis method, and then mesoporous hydroxyapatite is coated on the surface of a carbon nanotube in situ by using a uniform precipitation method and a hydrogel method, thereby preparing a carbon nanotube-reinforced mesoporous hydroxyapatite composite material; CN102976743A reports a method for preparing a carbon nanotube-reinforced hydroxyapatite composite material, which is a method for synthesizing carbon nanotubes in hydroxyapatite powder, and performing surface modification on the carbon nanotubes by using hydroxyapatite to prepare a carbon nanotube-reinforced hydroxyapatite composite material; CN201510125744 discloses a dual in-situ synthesis for preparing carbon nanotube reinforced hydroxyapatite composite materialThe method comprises the steps of synthesizing a hydroxyapatite layer on the surface of the carbon nano tube in situ by a sol-gel process on the basis of preparing the carbon nano tube-hydroxyapatite in situ composite powder, and further preparing the carbon nano tube reinforced hydroxyapatite composite material; CN105523536A reports a method for preparing a carbon nanotube-hydroxyapatite composite material, which comprises subjecting a multi-walled carbon nanotube to surface oxidation treatment, dispersing the multi-walled carbon nanotube in an aqueous solution, and preparing a carbon nanotube-hydroxyapatite composite powder by an in-situ composite method to prepare the carbon nanotube-hydroxyapatite composite material; in addition, CN103100308A discloses a method for preparing a gelatin film and a gelatin single-walled carbon nanotube composite film, which uses Cu (OH)2The nanowires are used as sacrificial layers, gelatin is deposited on Cu (OH) by a filtration method2And (3) performing cross-linking on the nanowires to obtain a gelatin film, and depositing gelatin on the single-walled carbon nanotube substrate by a filtration method to perform cross-linking to obtain the gelatin single-walled carbon nanotube composite film. In the prior art, the carbon nano tube reinforced hydroxyapatite composite material has low interface bonding strength and poor dispersibility of the carbon nano tube, so that the composite material has low comprehensive mechanical property; the composite material has poor biocompatibility and even has toxicity, and the composite material has risks when being used as a biomedical material; poor repair of bone cell migration, growth and differentiation; and the defect of poor using effect as a biomedical material. Therefore, there is still a need to further develop a new preparation method of the carbon nanotube-hydroxyapatite composite material, improve the performance thereof, and solve the urgent problem faced by the application thereof in the biomedical field.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: the preparation method is characterized by preparing the carbon nano tube by using a chemical vapor deposition method, performing functionalization treatment on the carbon nano tube, coating a collagen layer on the surface of the carbon nano tube subjected to the functionalization treatment in situ by adopting a method of combining a magnetic liquid phase stirring method and a hydrogel method, and preparing the collagen-coated carbon nano tube reinforced hydroxyapatite composite material by using a dry-state pressing forming method. The method overcomes the defects of low interface bonding strength of the carbon nano tube reinforced hydroxyapatite composite material and poor dispersibility of the carbon nano tube in the prior art, which leads to low comprehensive mechanical property of the composite material; the composite material has poor biocompatibility and even has toxicity, and the composite material has risks when being used as a biomedical material; poor repair of bone cell migration, growth and differentiation; and the defect of poor using effect as a biomedical material.
The technical scheme adopted by the invention for solving the technical problem is as follows: a preparation method of a carbon nano tube reinforced hydroxyapatite composite material is a preparation method which prepares a carbon nano tube by a chemical vapor deposition method, carries out functionalization treatment on the carbon nano tube, coats a collagen layer on the surface of the carbon nano tube which is subjected to functionalization treatment in situ by a method of combining a magnetic liquid phase stirring method and a hydrogel method, and then prepares the collagen-coated carbon nano tube reinforced hydroxyapatite composite material by a dry state pressing forming method, and comprises the following specific steps:
step one, preparing carbon nano tube-hydroxyapatite composite powder:
weighing ferric chloride hexahydrate and hydroxyapatite particles with the particle size of 10-60 nm according to the mass ratio of 0.55-1.75: 1, adding the weighed hydroxyapatite particles into deionized water under the condition of stirring by using a mechanical stirrer at the rotating speed of 100-400 r/min until hydroxyapatite suspension with the molar concentration of 0.01-0.3 mol/L is formed, then adding the weighed ferric chloride hexahydrate into the hydroxyapatite suspension, stirring for 2-4 h, uniformly soaking ferric chloride in hydroxyapatite to obtain suspension I, adding 25 mass percent of ammonia water into the suspension I to 20-100: 1, adding 25 mass percent of ammonia water into the suspension I, continuously stirring for 1-4 h to obtain suspension II, placing the formed suspension II into an ultrasonic dispersion instrument, and performing ultrasonic dispersion for 40-60 min at the frequency of 20-40 kHz to enable the ferric chloride and the ammonia water to fully react to generate Fe (OH) )3Colloid, and then aging for 10-20 h at room temperature to obtain Fe (OH)3Filtering the binary colloid mixture of hydroxyapatite with microporous membrane, washing with deionized water for 2-4 times, and drying in an electrothermal drying oven at 60-100 deg.CDrying for 5-10 h, and drying the Fe (OH) solution3Putting the hydroxyapatite binary colloid mixture into a ball milling tank, ball milling for 1-5 h by adopting a planetary ball mill at the rotating speed of 800-1400 r/min, and carrying out ball milling on the Fe (OH) after ball milling treatment3The hydroxyapatite binary colloid mixture is spread in a quartz ark which is arranged in a constant temperature area of a tube furnace, introducing helium or argon into the tubular furnace at a flow rate of 100-200 mL/min, heating to 400-800 ℃, then closing helium or argon, simultaneously introducing carbon monoxide into the tubular furnace at the flow rate of 50-150 mL/min, heating to 700-1000 ℃, preserving heat for 0.5-1.5 h, heating again to 800-1200 ℃, continuously introducing mixed gas with the volume ratio of helium or argon to carbon monoxide of 10-50: 1 into the tubular furnace at the flow rate of 100-400 mL/min, preserving the heat for 0.5-1.5 h, then closing the carbon monoxide gas, adjusting the flow rate of the helium or argon to 60-200 mL/min, simultaneously stopping heating the tubular furnace to naturally cool the tubular furnace to the room temperature, thus preparing the carbon nano tube-hydroxyapatite composite powder with the mass percentage of the carbon nano tube of 1.4-37.9%;
step two, preparing the carbon nano tube subjected to functional treatment:
placing 0.05-0.55 g of the carbon nanotube-hydroxyapatite composite powder prepared in the first step into 10-50 mL of absolute ethyl alcohol, stirring for 1-10 h at the rotating speed of 300-600 r/min by using a mechanical stirrer, adding 20-60 mL of potassium permanganate solution with the mass percentage concentration of 3% and 2-20 mL of nitric acid with the mass percentage concentration of 45%, filtering the obtained liquid by using a microporous filter membrane, and drying the obtained filtrate for 1-9 h in a vacuum drying oven with the temperature of 40-90 ℃ and the vacuum degree of-0.1-0.05 MPa to prepare the carbon nanotube-hydroxyapatite composite powder subjected to functional treatment;
step three, preparing the collagen-coated carbon nanotube-hydroxyapatite composite powder:
the preparation method of the collagen-coated carbon nano tube-hydroxyapatite composite powder by combining a magnetic liquid phase stirring method and a hydrogel method comprises the following specific operation methods: adding 1-5 g of the carbon nano tube-hydroxyapatite composite powder subjected to the functionalization treatment prepared in the second step into 10-100 mL of deionized water or absolute ethyl alcohol to obtain A, adding 0.5-2.5 g of collagen into 10-100 mL of acetic acid, heating to 40-90 ℃, stirring for 1-4 h on a magnetic stirrer at a rotating speed of 100-600 r/min to obtain B, dropwise adding the B into the A at a speed of 1-20 mL/min, regulating the pH value of the mixed solution to 9-15 by using urea or ammonia water, continuously stirring for 4-9 h by using the magnetic stirrer after dropwise adding the B to obtain a mixed solution C, aging the obtained mixed solution C in a drying box at 40-90 ℃ for 1-4 h, heating to 100-200 ℃ for drying, regulating the temperature of the drying box to 90-180 ℃ until the gel is dried into a fluffy block body, the collagen-coated carbon nano tube-hydroxyapatite composite powder is prepared, wherein the mass percentage of the carbon nano tube is 0.7-34.6%, and the mass percentage of the collagen is 0.2-16.8%;
fourthly, preparing the collagen-coated carbon nano tube reinforced hydroxyapatite composite material:
and (2) using a dry-state pressing forming method, using an inner pipe and an outer pipe with an exhaust function as a graphite pressing die, placing the collagen-coated carbon nano tube-hydroxyapatite composite powder prepared in the third step into the pressing die, sliding by using a piston, the inner pipe and the outer pipe, applying a pressure of 10-100 MPa to the collagen-coated carbon nano tube-hydroxyapatite composite powder in an annular space between the inner pipe and the outer pipe, axially compressing and maintaining the pressure for 1-3 min, raising the temperature of the die to a sintering temperature of 400-650 ℃ at a temperature rise speed of 40-190 ℃/min by controlling a current in a discharge plasma sintering process, and maintaining the sintering temperature for 1-20 min to prepare the collagen-coated carbon nano tube reinforced hydroxyapatite composite material.
The raw materials of the preparation method of the carbon nanotube reinforced hydroxyapatite composite material are all obtained commercially, and the used equipment and process are all well known to those skilled in the art.
The invention has the following beneficial effects:
compared with the prior art, the method has the following prominent substantive characteristics:
(1) in the use of biomedical materials, it is required as a hard tissue implantThe hydroxyapatite composite material has good biocompatibility, biological adhesion performance and plasticity, and is required to meet the use requirement of hard tissue implants. In the design and implementation processes of the invention, in order to endow the carbon nano tube with good biocompatibility for the reinforced hydroxyapatite composite material, and simultaneously solve the problems that the carbon nano tube is easy to agglomerate and the carbon nano tube is toxic, the invention innovatively provides a novel preparation process method for preparing the collagen-coated carbon nano tube reinforced hydroxyapatite composite material by coating a collagen layer on the surface of the carbon nano tube subjected to the functionalization in situ by adopting a method of combining a magnetic liquid phase stirring method and a hydrogel method and further preparing the collagen-coated carbon nano tube reinforced hydroxyapatite composite material by a dry state press forming method. By functional treatment of-CO2Introducing H and-OH functional groups onto carbon nanotube, and combining magnetic liquid phase stirring method with hydrogel method to make-NH of collagen2-CO of functional groups with carbon nanotubes2And combining the H functional groups to prepare collagen-coated carbon nanotube-hydroxyapatite composite powder, and further preparing the collagen-coated carbon nanotube reinforced hydroxyapatite composite material by using the collagen-coated carbon nanotube-hydroxyapatite composite powder as a raw material. The collagen coated on the surface of the carbon nano tube is the most important water-insoluble fibrin outside the cell and is a skeleton forming extracellular matrix, so the collagen-coated carbon nano tube reinforced hydroxyapatite composite material prepared by the method has excellent biocompatibility, good biological adhesion performance and plasticity and no toxic or side effect on a human body.
(2) As the reinforcing phase of the hydroxyapatite composite material, the reinforcing phase is required to have good dispersion performance, thereby ensuring that the reinforcing phase plays good roles of reinforcing and toughening in a hydroxyapatite composite material matrix and avoiding the defect that reinforcing phase aggregates become the composite material matrix. In the design process of the invention, the problem of dispersion of the collagen-coated carbon nanotube reinforcing phase in the hydroxyapatite matrix is fully considered, and in the design and implementation processes, the surface of the carbon nanotube is modified by a surface carboxylation process, so that the carbon nanotube has good dispersibility in a solvent, and the agglomeration phenomenon of the carbon nanotube is avoided; meanwhile, through in-situ synthesis and in-situ collagen modification of the carbon nano tubes in the hydroxyapatite matrix, agglomeration of the carbon nano tube reinforced phase caused by an external method is avoided, dispersion distribution of the collagen-coated carbon nano tube reinforced phase in the hydroxyapatite matrix and formation of good interface combination of the reinforced phase and the matrix are realized, and good reinforcing and toughening effects of the carbon nano tubes are fully exerted. Therefore, the collagen-coated carbon nanotube reinforced hydroxyapatite composite material prepared by the method has excellent mechanical properties.
(3) In the preparation process of the carbon nanotube reinforced hydroxyapatite composite material, in order to improve the dispersibility and biocompatibility of the carbon nanotube reinforced phase, a surface modification layer needs to be prepared on the carbon nanotube, and the interface between the surface modification layer and the carbon nanotube is combined, so that the reinforcing effect of the carbon nanotube in the composite material is directly influenced. In order to overcome the defects that the interface bonding between the carbon nano tube and the surface modification layer thereof is poor and easy to peel off in the prior art, so that the reinforcing and toughening effects of the carbon nano tube in the hydroxyapatite composite material are poor, in the design process of the invention, the improvement of the interface bonding effect of the carbon nano tube-collagen is taken as one of key technologies, and the method of functionalization treatment is innovatively provided for leading-CO to be used2Introducing H and-OH functional groups onto carbon nanotube, and combining magnetic liquid phase stirring method with hydrogel method to make-NH of collagen2-CO of functional groups with carbon nanotubes2The combination of H functional groups not only obviously increases the area of the combination interface of collagen and the carbon nano tube, but also forms extremely strong chemical bond combination with the carbon nano tube, obviously improves the interface combination force of the carbon nano tube and the collagen, and improves the reinforcing and toughening capability of the carbon nano tube in the hydroxyapatite composite material through the excellent interface combination state. Therefore, the collagen-coated carbon nanotube reinforced hydroxyapatite composite material prepared by the method has excellent mechanical properties.
(4) In the design process of the invention, in order to solve the defects that the biocompatibility of the carbon nano tube reinforced hydroxyapatite composite material is poor and the repairing effect of migration, growth and differentiation of bone cells of the composite material after being implanted into a human body is poor in the prior art, a novel process method adopting the carbon nano tube coated by collagen as a hydroxyapatite composite material reinforcing phase is creatively provided. Collagen is one of the main components of the tissue structure of vertebrates, accounts for about 25 to 33 percent of the total amount of protein in a human body, is widely present in tissue organs such as skin, bones, cartilages and the like of the human body, maintains the shape and the structure of the skin and the tissue organs, and plays a role in repairing each damaged tissue; meanwhile, the collagen has good biological compatibility, can greatly promote the formation of new cells and the adhesion among the cells, and has the function of stopping bleeding. Therefore, the invention adopts the innovation of the process method, uses the carbon nano tube coated by the collagen as the reinforcing phase of the hydroxyapatite composite material, and the prepared carbon nano tube coated by the collagen enhances the hydroxyapatite composite material to realize good biocompatibility, obviously improves the repairing effect of migration, growth and differentiation of bone cells, can improve the cell adhesion, has the function of hemostasis, can supplement collagen required by a human body in the process of artificial bone degradation, and has obvious using effect as a biomedical material.
Compared with the prior art, the method provided by the invention has the following remarkable improvements:
(1) in the prior art, CN103100308A uses a cross-linking agent glutaraldehyde to combine gelatin and carbon nanotubes together in the process of preparing a gelatin film and a gelatin single-walled carbon nanotube composite film, and the cross-linking agent glutaraldehyde has certain toxicity and can cause bronchitis and pulmonary edema, so that the problems of poor biocompatibility and toxicity and use risk exist when the cross-linking agent glutaraldehyde is used as a composite material for enhancing phase; the cross-linking agent can cross-link linear molecules, and van der Waals' force action among the molecules can cause the agglomeration phenomenon of the carbon nano-tube, thus causing the problems that the carbon nano-tube is difficult to disperse in the hydroxyapatite composite material and the reinforcing and toughening effects are poor; the cross-linking agent is characterized in that collagen and carbon nanotubes are cross-linked into a net structure by bridging among linear molecules of gelatin and carbon nanotubes, the gelatin is attached to the surfaces of the carbon nanotubes in a physical adsorption mode, and the interface bonding force between the gelatin and the carbon nanotubes is very small, so that the gelatin and the carbon nanotubes are easy to peel off when the gelatin is used as a reinforcing phase of a composite material, the mechanical property of the hydroxyapatite composite material is poor, and the toxicity caused by the carbon nanotubes after the gelatin is peeled off can occur. The collagen-coated carbon nanotube reinforced hydroxyapatite composite material prepared by the method completely overcomes the defects of the prior art CN 103100308A.
(2) In the prior art, CN104998301A and CN105523536A use hydroxyapatite-coated carbon nanotubes as a reinforcing phase of a hydroxyapatite composite material, and since hydroxyapatite does not have the ability to promote the formation of new cells and further promote cell adhesion, the prepared hydroxyapatite composite material has poor repairing effects such as biocompatibility, migration, growth, differentiation of osteocytes, and the like, and has poor using effect as a biomedical material; although the mesoporous hydroxyapatite structure coated on the surface of the carbon nano tube is beneficial to the climbing growth of cells, the mesoporous structure can be a microcrack source in the hydroxyapatite composite material, so that the problem that the composite material is poor in bending strength and fracture toughness is caused. The collagen-coated carbon nanotube reinforced hydroxyapatite composite material prepared by the method completely overcomes the defects of CN104998301A and CN105523536A in the prior art.
(3) The prior art CN102976743A and CN201510125744 have the following fundamental defects: (a) the hydroxyapatite-modified carbon nanotube is characterized in that nano hydroxyapatite particles are attached to the surface of the carbon nanotube in a physical adsorption mode. As is well known, the physical adsorption acting force between the carbon nanotube and the nano-hydroxyapatite particle belongs to the category of van der waals force, so that the interface bonding force between the carbon nanotube and the nano-hydroxyapatite particle is very small, and the effects of transferring load and inhibiting crack propagation are difficult to achieve; the composite material pressed into blocks subsequently still maintains the original physical bonding state, so that the fracture toughness of the composite material is only 1.4-3.6 MPa-m1/2And 2.9 to 6.7 MPa.m1/2The fracture toughness required by human skeleton is 12 MPa.m1/2The mechanical properties of the composite material are difficult to meet the use requirements of the hard tissue implant due to a large difference; (b) the hydroxyapatite is used for modifying the carbon nano tube, and the hydroxyapatite does not have the capability of promoting the formation of new cells and further promoting cell adhesion, so that the prepared hydroxyapatite composite material has poor repairing effects on biocompatibility, migration, growth, differentiation and the like of osteocytes, and can be used as a material for repairing the cellsThe use effect of the biomedical materials is poor; (c) in addition, the catalyst adopted in CN102976743A is a harmful heavy metal element nickel, which inevitably remains in the composite material, and during the use of the composite material, the existence of the element can cause chronic adverse effects on the human immune system, hematopoietic system, reproductive system, skin, etc., so that the prepared composite material has safety risk when used as a biomaterial. The collagen-coated carbon nanotube reinforced hydroxyapatite composite material prepared by the method completely overcomes the defects of CN102976743A and CN201510125744 in the prior art.
(4) The carbon nano tube-reinforced hydroxyapatite composite material prepared by the method takes the carbon nano tube coated by the collagen as a reinforced phase-reinforced hydroxyapatite composite material, and the collagen-coated carbon nano tube is innovatively adopted, so that the composite material has excellent biocompatibility, the repairing effects of migration, growth and differentiation of bone cells are obviously improved, the composite material has good biological adhesion performance and plasticity, has no toxic or side effect on a human body, has a hemostatic function, and can supplement collagen required by the human body in the artificial bone degradation process; through the innovation of the process method, the chemical combination of the collagen-carbon nanotube interface and the good dispersion of the carbon nanotube are realized, so that the composite material has excellent mechanical properties;
(5) the preparation method of the collagen-coated carbon nano tube reinforced hydroxyapatite composite material by the dry state press forming method adopts mouse osteoblasts MC3T3-E1 to carry out in-vitro cytotoxicity experiments, and the invention uses the chemical vapor deposition method to prepare the carbon nano tubes, adopts the method of combining the magnetic liquid phase stirring method and the hydrogel method to coat the collagen layer on the surface of the carbon nano tubes which are subjected to the functionalization treatment in situ, and further uses the dry state press forming method to prepare the collagen-coated carbon nano tube reinforced hydroxyapatite composite material which has no cytotoxicity and has similar biocompatibility with pure hydroxyapatite; after the cells are infected and cultured for 72h, the cell morphology still keeps fusiform or triangularThe growth state of the cells is good; the cell proliferation rate was 96% after 24h of culture, 90% after 48h of culture, and 85% after 72h of culture. Mechanical property tests show that the bending strength of the collagen-coated carbon nano tube reinforced hydroxyapatite composite material reaches 164-366 MPa, and the fracture toughness reaches 3.6-8.4 MPa.m1/2The composite material has fracture toughness similar to that of human skeleton, excellent comprehensive mechanical performance and obviously superior performance to that of hydroxyapatite-base composite material prepared in available technology.
Drawings
The invention is further illustrated with reference to the following figures and examples.
Fig. 1 is an X-ray diffraction pattern of the collagen-coated carbon nanotube-hydroxyapatite composite powder prepared in example 1 of the present invention.
Fig. 2 is a scanning electron microscope photograph of the collagen-coated carbon nanotube-hydroxyapatite composite powder prepared in example 1 of the present invention.
Fig. 3 is a low power transmission electron microscope photograph of the collagen-coated carbon nanotube-hydroxyapatite composite powder prepared in example 1 of the present invention.
Fig. 4 is a high power transmission electron microscope photograph of the collagen-coated carbon nanotube-hydroxyapatite composite powder prepared in example 1 of the present invention.
Fig. 5 is a scanning electron microscope photograph of a tensile cross section of the collagen-coated carbon nanotube-reinforced hydroxyapatite composite material prepared in example 1 of the present invention.
Detailed Description
Example 1
Step one, preparing carbon nano tube-hydroxyapatite composite powder:
weighing ferric chloride hexahydrate and hydroxyapatite particles with the particle size of 10nm according to the mass ratio of 0.55: 1, adding the weighed hydroxyapatite particles into deionized water under the condition of stirring by using a mechanical stirrer at the rotating speed of 100r/min until hydroxyapatite suspension with the molar concentration of 0.01mol/L is formed, then adding the weighed ferric chloride hexahydrate into the hydroxyapatite suspension, and stirring2h, uniformly soaking ferric chloride in hydroxyapatite to obtain a suspension I, adding 25 mass percent of ammonia water into the suspension I according to the volume ratio of 100: 1 to 25 mass percent of ammonia water, continuously stirring for 1h to obtain a suspension II, placing the formed suspension II in an ultrasonic disperser, and performing ultrasonic dispersion at the frequency of 20kHz for 40min to ensure that the ferric chloride and the ammonia water fully react to generate Fe (OH)3Colloid, then aged at room temperature for 10h to give Fe (OH)3-filtering the binary colloid mixture of hydroxyapatite with microporous membrane, washing with deionized water for 2 times, oven drying at 60 deg.C for 5 hr, and drying with dried Fe (OH)3Putting the hydroxyapatite binary colloid mixture into a ball milling tank, ball milling for 1h at the rotating speed of 800r/min by adopting a planetary ball mill, and carrying out ball milling treatment on Fe (OH)3-the hydroxyapatite binary colloid mixture is flatly laid in a quartz boat placed in a constant temperature area of a tubular furnace, helium or argon is introduced into the tubular furnace at a flow rate of 100mL/min and heated to 400 ℃, then the helium or argon is closed, simultaneously carbon monoxide is introduced into the tubular furnace at a flow rate of 50mL/min and heated to 700 ℃, the temperature is maintained for 0.5h, after the temperature is raised to 800 ℃ again, a mixed gas with a volume ratio of helium or argon to carbon monoxide of 50: 1 is continuously introduced into the tubular furnace at a flow rate of 100mL/min and the temperature is maintained for 0.5h, then carbon monoxide gas is closed and the flow rate of helium or argon is adjusted to 60mL/min, and meanwhile, the heating of the tubular furnace is stopped to naturally cool the tubular furnace to room temperature, so that the carbon nanotube-hydroxyapatite composite powder with the carbon nanotube mass percentage content of 1.4% is prepared;
step two, preparing the carbon nano tube subjected to functional treatment:
placing 0.05g of the carbon nanotube-hydroxyapatite composite powder prepared in the first step into 10mL of absolute ethyl alcohol, stirring for 1h by using a mechanical stirrer at the rotating speed of 300r/min, adding 20mL of a potassium permanganate solution with the mass percentage concentration of 3% and 2mL of nitric acid with the mass percentage concentration of 45% into the mechanical stirrer to oxidize and functionalize the carbon nanotube and simultaneously retain the hydroxyapatite, filtering the obtained liquid by using a microporous filter membrane, and drying the obtained filter in a vacuum drying oven with the temperature of 40 ℃ and the vacuum degree of-0.05 MPa for 1h to prepare the functionalized carbon nanotube-hydroxyapatite composite powder;
step three, preparing the collagen-coated carbon nanotube-hydroxyapatite composite powder:
the preparation method of the collagen-coated carbon nano tube-hydroxyapatite composite powder by combining a magnetic liquid phase stirring method and a hydrogel method comprises the following specific operation methods: adding 1g of the carbon nano tube-hydroxyapatite composite powder which is prepared in the second step and is subjected to functional treatment into 10mL of deionized water or absolute ethyl alcohol to obtain A, adding 2.5g of collagen into 100mL of acetic acid, heating the mixture to 40 ℃, stirring the mixture for 1h on a magnetic stirrer at the rotating speed of 100r/min to obtain B, dripping the B into the A at the speed of 1mL/min, regulating the pH value of the mixed solution to 9 by using urea or ammonia water during the dripping process, continuing stirring the mixture for 4h by using the magnetic stirrer after the dripping of the B is finished to obtain a mixed solution C, aging the obtained mixed solution C in a drying oven for 1h at 40 ℃, heating the mixed solution C to 100 ℃ for drying, regulating the temperature of the drying oven to 90 ℃ when the mixed solution C becomes gel, and drying the gel into a fluffy block body to obtain the carbon nano tube-hydroxyapatite composite powder coated with the collagen, wherein the mass percent of the carbon nano tube is 0.7 percent, and the mass percent of the collagen is 16.8 percent;
FIG. 1 is an X-ray diffraction pattern of a collagen-coated carbon nanotube-hydroxyapatite composite powder prepared in this example, showing X-ray diffraction patterns of a carbon nanotube (shown by ● in the figure), hydroxyapatite (shown by ■ in the figure) and collagen (shown by XX in the figure), respectively, in the collagen-coated carbon nanotube-hydroxyapatite composite powder, it can be seen that hydroxyapatite (shown by ■ in the figure) in the collagen-coated carbon nanotube-hydroxyapatite composite powder shows distinct characteristic peaks near positions at diffraction angles of 10.8 °, 26.2 °, 37.8 °, 45.1 °, 53.8 °, etc., a carbon nanotube (shown by ● in the figure) shows characteristic peaks at positions at diffraction angles of 26.2 ° and 53.8 °, indicating that the carbon nanotube is successfully synthesized in the composite powder, a collagen (shown by ● in the figure) shows characteristic peaks at positions at diffraction angles of 7.2 ° and 22.3 °, a diffraction peak without an iron catalyst in the X-ray diffraction pattern, which is due to a low iron catalyst content, and a collagen-coated carbon nanotube is obtained by a magnetic stirring method using a collagen-coated carbon nanotube powder.
Fig. 2 is a scanning electron microscope photograph of the collagen-coated carbon nanotube-hydroxyapatite composite powder prepared in this example. As can be seen from this figure, -NH is formed on collagen2Functional groups and-CO introduced onto carbon nanotubes2The H functional group is chemically combined, so that collagen is uniformly coated on the surface of the carbon nano tube; the carbon nano tubes are uniformly dispersed and completely and tightly coated by the collagen, and the phenomenon of bare carbon nano tubes does not occur, which indicates that the collagen successfully coats the carbon nano tubes; meanwhile, the carbon nano tubes coated by the collagen are uniformly dispersed in the hydroxyapatite matrix powder, and the phenomena of agglomeration and winding are not generated, so that the subsequent preparation of the hydroxyapatite-based composite material is facilitated to exert the reinforcing and toughening effects of the carbon nano tubes and form good interface combination of a matrix-reinforcing phase, and the composite material is ensured to have excellent comprehensive mechanical properties.
Fig. 3 is a low power transmission electron microscope photograph of the collagen-coated carbon nanotube-hydroxyapatite composite powder prepared in this example. According to the figure, the carbon nano tube is completely coated by the collagen layer, the collagen in the coating layer is a thin layer which is uniformly distributed, the thickness is 6-9 nm, and the hollow carbon nano tube can be densely coated, so that the composite material is endowed with good biocompatibility; meanwhile, the hydroxyapatite particles and the carbon nano tubes are tightly connected together to form good combination.
Fig. 4 is a high power transmission electron microscope photograph of the collagen-coated carbon nanotube-hydroxyapatite composite powder prepared in this example. As can be seen from the figure, the material coating the wall of the carbon nanotube is collagen, the collagen is distributed uniformly and has uniform thickness, and the thickness is between 6 and 9 nm; the carbon nano tube still keeps good structural integrity, and graphite stripes in the tube wall are clearly visible; the interface between the carbon nano tube and the collagen is tightly combined, and the good reinforcing and toughening effects of the collagen-coated carbon nano tube can be fully exerted.
Fourthly, preparing the collagen-coated carbon nano tube reinforced hydroxyapatite composite material:
and (2) using a dry-state pressing forming method, using an inner pipe and an outer pipe with an exhaust function as graphite pressing dies, placing the collagen-coated carbon nano tube-hydroxyapatite composite powder prepared in the third step into the dies, sliding by using a piston, the inner pipe and the outer pipe, applying a pressure of 10MPa to the collagen-coated carbon nano tube-hydroxyapatite composite powder in an annular space between the inner pipe and the outer pipe, axially compressing and maintaining the pressure for 1min, raising the temperature of the dies to a sintering temperature of 400 ℃ at a heating rate of 40 ℃/min by controlling current in a discharge plasma sintering process, and maintaining the sintering temperature for 1min to prepare the collagen-coated carbon nano tube reinforced hydroxyapatite composite material.
Fig. 5 is a scanning electron microscope photograph of a tensile cross section of the collagen-coated carbon nanotube reinforced hydroxyapatite composite material prepared in this example. As can be seen from the figure, the prepared composite material has compact structure, and no obvious pore or crack exists in the matrix; a large amount of fine dimples appear in the tensile fracture, which shows that the composite material shows a plastic fracture trend; the collagen-coated carbon nano tube embedded in the hydroxyapatite matrix and the holes left after the collagen-coated carbon nano tube is pulled out can be seen on the fracture surface, which shows that the collagen-coated carbon nano tube reinforcing phase has good wettability, strong interface binding force and tight combination with the hydroxyapatite matrix, and the collagen-coated carbon nano tube reinforcing phase can play a role in bridging force transfer among hydroxyapatite crystal grains in the stretching process, thereby playing the effects of load sharing and interface strengthening, and obviously improving the mechanical property of the prepared collagen-coated carbon nano tube reinforced hydroxyapatite composite material.
Example 2
Step one, preparing carbon nano tube-hydroxyapatite composite powder:
weighing ferric chloride hexahydrate and hydroxyapatite particles with the particle size of 40nm according to the mass ratio of 1.2: 1, stirring the mixture by using a mechanical stirrer at the rotating speed of 250r/min,adding weighed hydroxyapatite particles into deionized water to form a hydroxyapatite suspension with the molar concentration of 0.15mol/L, then adding weighed ferric chloride hexahydrate into the hydroxyapatite suspension, stirring for 3 hours to ensure that the ferric chloride is uniformly soaked in the hydroxyapatite to obtain a suspension I, adding 25 mass percent of ammonia water into the suspension I to obtain a suspension II according to the volume ratio of 60: 1, continuously stirring for 2.5 hours to obtain a suspension II, placing the suspension II into an ultrasonic disperser, and performing ultrasonic dispersion for 50 minutes at the frequency of 30kHz to ensure that the ferric chloride and the ammonia water fully react to generate Fe (OH)3Colloid, then aged at room temperature for 15h to give Fe (OH)3-filtering the binary colloid mixture of hydroxyapatite with microporous membrane, washing with deionized water for 3 times, oven drying at 80 deg.C for 7 hr, and drying with Fe (OH)3Putting the hydroxyapatite binary colloid mixture into a ball milling tank, ball milling for 3h at the rotating speed of 1000r/min by adopting a planetary ball mill, and carrying out ball milling treatment on Fe (OH)3-the hydroxyapatite binary colloid mixture is flatly laid in a quartz boat placed in a constant temperature area of a tubular furnace, helium or argon is introduced into the tubular furnace at a flow rate of 150mL/min and heated to 600 ℃, then the helium or argon is closed, simultaneously carbon monoxide is introduced into the tubular furnace at a flow rate of 100mL/min and heated to 850 ℃, the temperature is maintained for 1h, after the temperature is raised to 1000 ℃, mixed gas with a volume ratio of helium or argon to carbon monoxide being 30: 1 is continuously introduced into the tubular furnace at a flow rate of 300mL/min and maintained for 1h, then carbon monoxide gas is closed, the flow rate of helium or argon is adjusted to 100mL/min, and the heating of the tubular furnace is stopped at the same time to naturally cool the tubular furnace to room temperature, so that carbon nanotube-hydroxyapatite composite powder with a carbon nanotube mass percentage content of 23.7% is prepared;
step two, preparing the carbon nano tube subjected to functional treatment:
placing 0.3g of the carbon nanotube-hydroxyapatite composite powder prepared in the first step into 30mL of absolute ethyl alcohol, stirring for 5 hours by using a mechanical stirrer at the rotating speed of 450r/min, adding 40mL of potassium permanganate solution with the mass percentage concentration of 3% and 10mL of nitric acid with the mass percentage concentration of 45% into the mixture to oxidize and functionalize the carbon nanotube and simultaneously retain the hydroxyapatite, filtering the obtained liquid by using a microporous filter membrane, and drying the obtained filter in a vacuum drying oven with the temperature of 60 ℃ and the vacuum degree of-0.08 MPa for 5 hours to prepare the functionalized carbon nanotube-hydroxyapatite composite powder;
step three, preparing the collagen-coated carbon nanotube-hydroxyapatite composite powder:
the preparation method of the collagen-coated carbon nano tube-hydroxyapatite composite powder by combining a magnetic liquid phase stirring method and a hydrogel method comprises the following specific operation methods: adding 3g of the carbon nano tube-hydroxyapatite composite powder which is prepared in the second step and is subjected to functional treatment into 50mL of deionized water or absolute ethyl alcohol to obtain A, adding 1.5g of collagen into 50mL of acetic acid, heating the mixture to 65 ℃, stirring the mixture for 2.5 hours on a magnetic stirrer at the rotating speed of 300r/min to obtain B, dripping the B into the A at the speed of 10mL/min, regulating the pH value of the mixed solution to be 12 by using urea or ammonia water during the dripping process, continuing stirring the mixture for 6 hours by using the magnetic stirrer after the dripping of the B is finished to obtain a mixed solution C, aging the obtained mixed solution C in a drying box at the temperature of 65 ℃ for 2.5 hours, heating the mixed solution C to 150 ℃ for drying, regulating the temperature of the drying box to 130 ℃ when the mixed solution C becomes gel until the gel is dried to be a block body, thus obtaining the carbon nano tube-hydroxyapatite composite powder coated by the collagen, wherein the mass percent of the carbon nano tube is 17.4 percent, and the mass percent of the collagen is 8.3 percent;
fourthly, preparing the collagen-coated carbon nano tube reinforced hydroxyapatite composite material:
and (2) using a dry-state pressing forming method, using an inner pipe and an outer pipe with an exhaust function as graphite pressing dies, placing the collagen-coated carbon nano tube-hydroxyapatite composite powder prepared in the third step into the dies, sliding by using a piston, the inner pipe and the outer pipe, applying 50MPa pressure to the collagen-coated carbon nano tube-hydroxyapatite composite powder in an annular space between the inner pipe and the outer pipe, axially compressing and maintaining the pressure for 2min, raising the temperature of the dies to 500 ℃ at a heating rate of 110 ℃/min by controlling current in a discharge plasma sintering process, and maintaining the sintering temperature for 10min to prepare the collagen-coated carbon nano tube reinforced hydroxyapatite composite material.
Example 3
Step one, preparing carbon nano tube-hydroxyapatite composite powder:
weighing ferric chloride hexahydrate and hydroxyapatite particles with the particle size of 60nm according to the mass ratio of 1.75: 1, adding the weighed hydroxyapatite particles into deionized water under the condition of stirring by using a mechanical stirrer at the rotating speed of 400r/min until a hydroxyapatite suspension with the molar concentration of 0.3mol/L is formed, then adding the weighed ferric chloride hexahydrate into the hydroxyapatite suspension, stirring for 4 hours to ensure that the ferric chloride is uniformly immersed into the hydroxyapatite to obtain suspension I, wherein the volume ratio of the suspension I to 25 percent (mass percentage) of ammonia water is 20 to 1, adding 25 percent (mass percentage) of ammonia water into the suspension I, continuously stirring for 4 hours to obtain a suspension II, placing the formed suspension II into an ultrasonic dispersion instrument, dispersing the mixture by ultrasonic wave at the frequency of 40kHz for 60min to ensure that the ferric chloride and the ammonia water fully react to generate Fe (OH).3Colloid, then aged at room temperature for 20h to give Fe (OH)3-filtering the binary colloid mixture of hydroxyapatite with microporous membrane, washing with deionized water for 4 times, oven drying at 100 deg.C for 10 hr, and drying with Fe (OH)3Putting the hydroxyapatite binary colloid mixture into a ball milling tank, ball milling for 5 hours at the rotating speed of 1400r/min by adopting a planetary ball mill, and carrying out ball milling treatment on the Fe (OH)3-the hydroxyapatite binary colloid mixture is flatly paved in a quartz boat which is arranged in a constant temperature area of a tube furnace, helium or argon is introduced into the tube furnace at the flow rate of 200mL/min and the temperature is raised to 800 ℃, then the helium or the argon is closed, simultaneously carbon monoxide is introduced into the tube furnace at the flow rate of 150mL/min and the temperature is raised to 1000 ℃, the temperature is maintained for 1.5h, after the temperature is raised to 1200 ℃ again, mixed gas with the volume ratio of helium or argon to carbon monoxide being 10: 1 is continuously introduced into the tube furnace at the flow rate of 400mL/min and the temperature is maintained for 1.5h, then carbon monoxide gas is closed and the flow rate of helium or argon is adjusted to 200mL/min, and simultaneously the heating of the tube furnace is stopped to naturally cool the tube furnace to 200mL/At room temperature, the carbon nano tube-hydroxyapatite composite powder with the mass percentage of the carbon nano tube of 37.9 percent is prepared;
step two, preparing the carbon nano tube subjected to functional treatment:
placing 0.55g of the carbon nanotube-hydroxyapatite composite powder prepared in the first step into 50mL of absolute ethyl alcohol, stirring for 10 hours by using a mechanical stirrer at the rotating speed of 600r/min, adding 60mL of potassium permanganate solution with the mass percentage concentration of 3% and 20mL of nitric acid with the mass percentage concentration of 45% into the mixture to oxidize and functionalize the carbon nanotube and simultaneously retain the hydroxyapatite, filtering the obtained liquid by using a microporous filter membrane, and drying the obtained filter in a vacuum drying oven with the temperature of 90 ℃ and the vacuum degree of-0.1 MPa for 9 hours to prepare the functionalized carbon nanotube-hydroxyapatite composite powder;
step three, preparing the collagen-coated carbon nanotube-hydroxyapatite composite powder:
the preparation method of the collagen-coated carbon nano tube-hydroxyapatite composite powder by combining a magnetic liquid phase stirring method and a hydrogel method comprises the following specific operation methods: adding 5g of the carbon nano tube-hydroxyapatite composite powder which is prepared in the second step and is subjected to functionalization treatment into 100mL of deionized water or absolute ethyl alcohol to obtain A, adding 0.5g of collagen into 10mL of acetic acid, heating the mixture to 90 ℃, stirring the mixture for 4 hours on a magnetic stirrer at the rotating speed of 600r/min to obtain B, dripping the B into the A at the speed of 20mL/min, regulating the pH value of the mixed solution to be 15 by using urea or ammonia water during the dripping process, continuing stirring the mixture for 9 hours by using the magnetic stirrer after the dripping of the B is finished to obtain a mixed solution C, aging the obtained mixed solution C in a drying box for 4 hours at 90 ℃, heating the mixed solution C to 200 ℃ for drying, regulating the temperature of the drying box to 180 ℃ when the mixed solution C becomes gel, and drying the gel into a fluffy block body to obtain the carbon nano tube-hydroxyapatite composite powder coated with the collagen, wherein the mass percent of the carbon nano tube is 34.6 percent, and the mass percent of the collagen is 0.2 percent;
fourthly, preparing the collagen-coated carbon nano tube reinforced hydroxyapatite composite material:
and (2) using a dry-state pressing forming method, using an inner pipe and an outer pipe with an exhaust function as graphite pressing dies, placing the collagen-coated carbon nano tube-hydroxyapatite composite powder prepared in the third step into the dies, sliding by using a piston, the inner pipe and the outer pipe, applying 100MPa pressure to the collagen-coated carbon nano tube-hydroxyapatite composite powder in an annular space between the inner pipe and the outer pipe, axially compressing and maintaining the pressure for 3min, raising the temperature of the dies to 650 ℃ at a temperature rise speed of 190 ℃/min by controlling current in a discharge plasma sintering process, and maintaining the sintering temperature for 20min to prepare the collagen-coated carbon nano tube reinforced hydroxyapatite composite material.
In the above examples, the raw materials are commercially available and the equipment and processes used are well known to those skilled in the art.
Claims (2)
1. The preparation method of the carbon nano tube reinforced hydroxyapatite composite material is characterized by comprising the following steps: the preparation method is a preparation method for preparing the carbon nano tube by using a chemical vapor deposition method, performing functionalization treatment on the carbon nano tube, coating a collagen layer on the surface of the carbon nano tube subjected to functionalization treatment in situ by adopting a method combining a magnetic liquid phase stirring method and a hydrogel method, and further preparing the collagen-coated carbon nano tube reinforced hydroxyapatite composite material by using a dry state press forming method, and comprises the following specific steps:
step one, preparing carbon nano tube-hydroxyapatite composite powder:
weighing ferric chloride hexahydrate and hydroxyapatite particles with the particle size of 10-60 nm according to the mass ratio of 0.55-1.75: 1, adding the weighed hydroxyapatite particles into deionized water under the condition of stirring by using a mechanical stirrer at the rotating speed of 100-400 r/min until hydroxyapatite suspension with the molar concentration of 0.01-0.3 mol/L is formed, then adding the weighed ferric chloride hexahydrate into the hydroxyapatite suspension, stirring for 2-4 h to ensure that ferric chloride is uniformly soaked in hydroxyapatite to obtain suspension I, adding 25 mass percent of ammonia water into the suspension I according to the volume ratio of 20-100: 1, adding 25 mass percent of ammonia water into the suspension I, and continuously stirringStirring for 1-4 h to obtain a suspension II, placing the suspension II in an ultrasonic disperser, performing ultrasonic dispersion at the frequency of 20-40 kHz for 40-60 min to ensure that ferric chloride and ammonia water fully react to generate Fe (OH)3Colloid, and then aging for 10-20 h at room temperature to obtain Fe (OH)3Filtering the binary colloid mixture of hydroxyapatite with a microporous filter membrane, washing with deionized water for 2-4 times, drying in an electrothermal drying oven at 60-100 deg.C for 5-10 h, and drying with Fe (OH)3Putting the hydroxyapatite binary colloid mixture into a ball milling tank, ball milling for 1-5 h by adopting a planetary ball mill at the rotating speed of 800-1400 r/min, and carrying out ball milling on the Fe (OH) after ball milling treatment3The hydroxyapatite binary colloid mixture is spread in a quartz ark which is arranged in a constant temperature area of a tube furnace, introducing helium or argon into the tubular furnace at a flow rate of 100-200 mL/min, heating to 400-800 ℃, then closing helium or argon, simultaneously introducing carbon monoxide into the tubular furnace at the flow rate of 50-150 mL/min, heating to 700-1000 ℃, preserving heat for 0.5-1.5 h, heating again to 800-1200 ℃, continuously introducing mixed gas with the volume ratio of helium or argon to carbon monoxide of 10-50: 1 into the tubular furnace at the flow rate of 100-400 mL/min, preserving the heat for 0.5-1.5 h, then closing the carbon monoxide gas, adjusting the flow rate of the helium or argon to 60-200 mL/min, simultaneously stopping heating the tubular furnace to naturally cool the tubular furnace to the room temperature, thus preparing the carbon nano tube-hydroxyapatite composite powder with the mass percentage of the carbon nano tube of 1.4-37.9%;
step two, preparing the carbon nano tube subjected to functional treatment:
placing 0.05-0.55 g of the carbon nanotube-hydroxyapatite composite powder prepared in the first step into 10-50 mL of absolute ethyl alcohol, stirring for 1-10 h at the rotating speed of 300-600 r/min by using a mechanical stirrer, adding 20-60 mL of potassium permanganate solution with the mass percentage concentration of 3% and 2-20 mL of nitric acid with the mass percentage concentration of 45%, filtering the obtained liquid by using a microporous filter membrane, and drying the obtained filtrate for 1-9 h in a vacuum drying oven with the temperature of 40-90 ℃ and the vacuum degree of-0.1-0.05 MPa to prepare the carbon nanotube-hydroxyapatite composite powder subjected to functional treatment;
step three, preparing the collagen-coated carbon nanotube-hydroxyapatite composite powder:
the preparation method of the collagen-coated carbon nano tube-hydroxyapatite composite powder by combining a magnetic liquid phase stirring method and a hydrogel method comprises the following specific operation methods: adding 1-5 g of the carbon nano tube-hydroxyapatite composite powder subjected to the functionalization treatment prepared in the second step into 10-100 mL of deionized water or absolute ethyl alcohol to obtain A, adding 0.5-2.5 g of collagen into 10-100 mL of acetic acid, heating to 40-90 ℃, stirring for 1-4 h on a magnetic stirrer at a rotating speed of 100-600 r/min to obtain B, dropwise adding the B into the A at a speed of 1-20 mL/min, regulating the pH value of the mixed solution to 9-15 by using urea or ammonia water, continuously stirring for 4-9 h by using the magnetic stirrer after dropwise adding the B to obtain a mixed solution C, aging the obtained mixed solution C in a drying box at 40-90 ℃ for 1-4 h, heating to 100-200 ℃ for drying, regulating the temperature of the drying box to 90-180 ℃ until the gel is dried into a fluffy block body, the collagen-coated carbon nano tube-hydroxyapatite composite powder is prepared, wherein the mass percentage of the carbon nano tube is 0.7-34.6%, and the mass percentage of the collagen is 0.2-16.8%;
fourthly, preparing the collagen-coated carbon nano tube reinforced hydroxyapatite composite material:
and (2) using a dry-state pressing forming method, using an inner pipe and an outer pipe with an exhaust function as a graphite pressing die, placing the collagen-coated carbon nano tube-hydroxyapatite composite powder prepared in the third step into the pressing die, sliding by using a piston, the inner pipe and the outer pipe, applying a pressure of 10-100 MPa to the collagen-coated carbon nano tube-hydroxyapatite composite powder in an annular space between the inner pipe and the outer pipe, axially compressing and maintaining the pressure for 1-3 min, raising the temperature of the die to a sintering temperature of 400-650 ℃ at a temperature rise speed of 40-190 ℃/min by controlling a current in a discharge plasma sintering process, and maintaining the sintering temperature for 1-20 min to prepare the collagen-coated carbon nano tube reinforced hydroxyapatite composite material.
2. The carbon nano-meter of claim 1The preparation method of the tube reinforced hydroxyapatite composite material is characterized by comprising the following steps: the prepared collagen-coated carbon nano tube reinforced hydroxyapatite composite material forms-NH on collagen2Functional groups and-CO introduced onto carbon nanotubes2The H functional group is chemically combined, so that collagen is uniformly coated on the surface of the carbon nano tube; the carbon nano tubes are uniformly dispersed and completely and tightly coated by the collagen, the collagen in the coating layer is a uniformly distributed thin layer, the thickness of the collagen is 6-9 nm, the carbon nano tubes are not exposed, and the collagen-coated carbon nano tubes are uniformly dispersed in the hydroxyapatite matrix powder and are not agglomerated or wound.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102976743A (en) * | 2012-12-19 | 2013-03-20 | 河北工业大学 | Preparation method of carbon nanotube reinforced hydroxyapatite composite material |
| CN103100308A (en) * | 2013-01-17 | 2013-05-15 | 浙江大学 | Preparation method of gelatin thin film and composite thin film for single-walled gelatin carbon nanometer tube |
| KR20140095118A (en) * | 2013-01-15 | 2014-08-01 | 단국대학교 천안캠퍼스 산학협력단 | Nanocomposite scaffolds having 3D porous structure for bone reconstruction |
| CN104998301A (en) * | 2015-08-12 | 2015-10-28 | 河北工业大学 | Preparation method of carbon nano tube reinforced mesoporous hydroxyapatite composite material |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| KR20140095118A (en) * | 2013-01-15 | 2014-08-01 | 단국대학교 천안캠퍼스 산학협력단 | Nanocomposite scaffolds having 3D porous structure for bone reconstruction |
| CN103100308A (en) * | 2013-01-17 | 2013-05-15 | 浙江大学 | Preparation method of gelatin thin film and composite thin film for single-walled gelatin carbon nanometer tube |
| CN104998301A (en) * | 2015-08-12 | 2015-10-28 | 河北工业大学 | Preparation method of carbon nano tube reinforced mesoporous hydroxyapatite composite material |
Non-Patent Citations (2)
| Title |
|---|
| 《Carbon nanotube-hydroxyapatite nanocomposite:A novel platform forglucose/O2 biofuel cell》;Zhao H Y，et al;《Biosens and Bioelectronics》;20090228;第25卷(第2期);第463-468页 * |
| 《碳纳米管／羟基磷灰石复合材料的制备及表征》;纪美茹等;《复合材料学报》;20120630;第29卷(第3期);第85-89页 * |
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