CN111808390B - Hydroxyapatite nanowire/polytetrafluoroethylene composite and preparation method thereof - Google Patents
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Abstract
The invention discloses a hydroxyapatite nanowire/polytetrafluoroethylene composite and a preparation method thereof. Firstly, polytetrafluoroethylene powder is uniformly dispersed in ethanol, then calcium ions and hydrogen phosphate ions are added into suspension, hydroxyapatite (HAP) nanowires are synthesized through hydrothermal reaction in an alkaline environment and in the presence of polytetrafluoroethylene, the prepared suspension is filtered, washed, dried and formed through cold pressing and sintering after hydrothermal treatment, and in-situ filling of the HAP nanowires in PTFE is realized through the processes. The method provided by the invention realizes high dispersion of the HAP nanowires in the PTFE matrix, and improves the mechanical, thermal and tribological properties of the PTFE matrix.
Description
Technical Field
The invention relates to a high polymer material and a preparation method thereof, in particular to a hydroxyapatite nanowire/polytetrafluoroethylene composite and a preparation method thereof.
Background
Polytetrafluoroethylene (PTFE) is an engineering material with wide application, has good high-temperature and low-temperature resistance, electrical insulation, chemical stability, non-adhesion, weather resistance, corrosion resistance and self-lubrication, is fluoroplastic with excellent comprehensive performance, enjoys the name of 'plastic king', and is widely used in the fields of aerospace, chemical engineering, machinery, textile and the like.
Although the PTFE has excellent performance, the PTFE has large forming and processing difficulty and low mechanical strength and hardness. Creep and cold flow often occur under long-term compression. The structure of PTFE also causes the product to have larger abrasion in the using process, the service life has certain limitation, and meanwhile, the production cost is high. Therefore, in order to meet the use requirements of PTFE in various fields and expand the application range of PTFE, the modification of PTFE to improve the related properties is urgent. Poor resistance to fretting is an important limiting factor in the useful life of PTFE, and suitable fillers for modified PTFE include inorganic materials, organic materials, rubbers, and thermoplastic elastomers. Wherein the inorganic material comprises silicon dioxide, carbon fiber, glass fiber, hydroxyapatite and the like. The wear resistance of the composite material prepared by filling the PTFE with graphene is improved, and the graphene is used for supporting load and forming a lubricating film in the composite material (functional material, 2014, 2 months). The carbon fiber has higher hardness and strength, can improve the strength and modulus of the composite material when being filled into PTFE, forms a smoother transfer film in the friction process, and effectively reduces the friction coefficient and the wear rate of the composite material (Composites Part B: engineering, 2016, 4 months). The organic material includes polyimide, polyphenylene sulfide, polyparahydroxybenzoate, polyphenyl ester, etc. The friction and wear resistance of the composite material can be effectively improved by filling the polyphenyl ester and the polyamide into the PTFE (Current Applied Physics, 11 months 2009).
The composite of hydroxyapatite nanowires (HAP nanowires) and PTFE is prepared by mechanical mixing, and because the hydroxyapatite nanowires have high surface energy and are easy to agglomerate, the hydroxyapatite nanowires are difficult to disperse well in a matrix, and the performance of the composite material is seriously affected.
Disclosure of Invention
The purpose of the invention is as follows: the invention aims to provide a hydroxyapatite nanowire/polytetrafluoroethylene composite which enables nano-filler to be uniformly dispersed through in-situ filling and has excellent tribological properties, and a preparation method thereof.
The technical scheme is as follows: the invention provides a hydroxyapatite nanowire/polytetrafluoroethylene composite, wherein a matrix of the composite is polytetrafluoroethylene, and a filler is hydroxyapatite nanowires. The polytetrafluoroethylene powder preferably has an average particle diameter of 25 μm and an apparent density of 0.35g/mL. The diameter of the hydroxyapatite nano-wire is preferably 50-500nm, the length-diameter ratio is preferably 10-100, and the mass content is preferably 0.25-2.0%.
The hydroxyapatite nanowire/polytetrafluoroethylene composite is prepared by in-situ hydrothermal synthesis.
Further, firstly, polytetrafluoroethylene powder is uniformly dispersed in ethanol, then calcium ions and hydrogen phosphate ions are added into suspension, hydroxyapatite (HAP) nanowires are synthesized through hydrothermal reaction in an alkaline environment and in the presence of polytetrafluoroethylene, and after hydrothermal treatment, the prepared suspension is filtered, washed, dried and formed through cold pressing-sintering.
Further, the hydrogen phosphate ion is monobasic or dibasic phosphate.
Further, the preparation method of the hydroxyapatite nanowire/polytetrafluoroethylene composite comprises the following steps:
(1) Respectively preparing NaOH aqueous solution and CaCl 2 Aqueous solution, naH 2 PO 4 The concentration of the prepared NaOH aqueous solution is preferably 0.625-2.5mol/L, caCl 2 The concentration of the aqueous solution is preferably 0.05-0.2mol/L, naH 2 PO 4 The concentration of the aqueous solution is preferably 0.05 to 0.2mol/L.
(2) Respectively adding NaOH aqueous solution and CaCl under the condition of continuous stirring 2 Aqueous solution, naH 2 PO 4 The aqueous solution is sequentially and slowly added into the mixed solution of oleic acid and ethanol in a dropwise manner, and the volume ratio of the oleic acid to the ethanol is preferably 3: 10. The ethanol is used as a solvent, can effectively infiltrate the surface of the PTFE after being mixed with water, and can disperse PTFE with strong hydrophobicity in a solution, so that the solution fully enters microscopic pores of a PTFE base material, and the dispersion of HAP nanowires on the surface of the PTFE is favorably improved. And oleic acid is used as a template agent to increase the viscosity of the solution, thereby being beneficial to dispersing PTFE in the solution and strengthening the dispersion effect.
(3) Under the condition of continuous stirring, adding an ethanol solution dispersed with polytetrafluoroethylene powder into the mixed solution to prepare polytetrafluoroethylene suspension, carrying out high-temperature reaction on the system, and naturally cooling to room temperature;
(4) And adding ethanol into the reaction solution cooled to room temperature to reduce the viscosity of the system, filtering, washing a filter cake by deionized water and ethanol, and drying to obtain the hydroxyapatite nanowire/polytetrafluoroethylene composite powder. The viscosity of the reaction product cooled to room temperature is higher, and the viscosity of the system is reduced by adding ethanol, so that the liquid is easier to filter. As oleic acid is attached to the surface of PTFE, the reaction product is repeatedly mixed, pulped and filtered for more than 3 times by using deionized water and ethanol respectively.
(5) The composite powder is subjected to cold pressing and then sintering molding to prepare a hydroxyapatite nanowire/polytetrafluoroethylene composite sample wafer, wherein the sintering conditions are preferably as follows: heating the sample to 375 ℃, keeping the temperature for 1.5h, then cooling to 325 ℃, keeping the temperature for 0.5h, and finally naturally cooling to room temperature. The sintering temperature of PTFE is 360-380 ℃, the melting point is about 325 ℃, and when the temperature exceeds the melting point, the PTFE has obvious thermal expansion, so the PTFE is kept at the temperature of 325 ℃ for half an hour, and the deformation and the cracking caused by the uneven expansion are reduced. The cold pressing conditions are preferably: the pressure is 20-25MPa, and the action time is 1h. And after cold pressing, the steel plate is placed at room temperature for 12 hours to eliminate internal stress. The higher pressure makes the PTFE powder easier to form, and the longer action time is favorable for removing air in the powder to the maximum extent.
The excellent physical and chemical properties of the nano filler can be fully exerted by filling the nano particles into the PTFE matrix, and the nano filler can generate stronger interaction and better interface combination with the matrix material. The nano particles are filled into the PTFE by using an in-situ filling method, so that the particle size advantage of the nano filler can be effectively exerted, the filler can be highly dispersed in the matrix material, and the filler and the matrix material have better compatibility.
The hydroxyapatite has good biocompatibility, bioactivity and osteoinductivity. Nano-sized hydroxyapatite exhibits more properties than micro-sized hydroxyapatite, including quantum size effects, small size effects, surface effects, and macroscopic quantum tunneling effects. In addition, the nano hydroxyapatite has more excellent mechanical property and biological activity and larger specific surface area. The nano-hydroxyapatite with one-dimensional morphology has the characteristics of micron and nano-scale, has high crystallinity and length-diameter ratio, and is easy to disperse in a solution or a matrix phase.
In the method of the invention, the PTFE matrix is uniformly dispersed in the reaction system by using oleic acid as a soft template agent and ethanol as a dispersing agent, and calcium ions (such as Ca) are generated in the 180 ℃ alkaline environment 2+ ) And hydrogen phosphate ions (e.g., HPO) 4 2- ) Nucleating on the surface of PTFE, selectively growing along the c-axis direction, washing, filtering, drying, cold pressing and sintering to form hydroxyapatite nano-wires on the surface of PTFEIn-situ filling. In the preparation process, the HAP nanowire is hydrothermally synthesized in situ in a liquid phase and is attached to the surface of PTFE, so that the interface combination and interaction of the HAP nanowire and the PTFE can be improved, the dispersion degree of the nano filler in a matrix is improved, and the composite material obtains better wear resistance and biocompatibility.
Has the beneficial effects that: according to the invention, hydroxyapatite nanowires are filled into PTFE in situ through hydrothermal synthesis, and can be effectively dispersed in PTFE, so that a highly dispersed hydroxyapatite nanosheet/PTFE composite material is prepared, and the friction and wear resistance of a matrix is remarkably improved.
Drawings
FIG. 1 is a schematic flow chart of the method of example 1;
fig. 2 is an SEM image of a product of the present invention, wherein a is an SEM image of a HAP nanowire/PTFE composite prepared by in-situ filling of example 2 and having a mass fraction of 0.5%, B is an SEM image of a HAP nanowire/PTFE composite prepared by mechanical mixing of comparative example 2 and having a mass fraction of 0.5%, and C is an SEM image of a HAP nanowire/PTFE composite prepared by in-situ filling of comparative example 3 and having an alcohol-water ratio of 1.25 adjusted.
Detailed Description
Example 1
According to the process shown in fig. 1, the method specifically comprises the following steps: at room temperature, 80mL ethanol and 24mL oleic acid were added to a beaker and stirred until dissolved. Three portions of 40mL deionized water are weighed, and then 1.00g of NaOH and 0.22g of CaCl are weighed 2 、0.24g NaH 2 PO 4 Respectively put into a beaker with 40mL of deionized water, stirred until the deionized water is completely dissolved to obtain NaOH aqueous solution and CaCl 2 Aqueous solution and NaH 2 PO 4 An aqueous solution. And then, slowly dripping the three solutions into a mixed solution of oleic acid and ethanol in turn, and continuously stirring. Adding ethanol solution dispersed with polytetrafluoroethylene powder, and stirring to obtain suspension. Transferring the obtained suspension into a polytetrafluoroethylene-lined stainless steel autoclave, heating to 180 ℃, reacting at constant temperature for 24 hours, and naturally cooling to room temperature. The resulting viscous reaction system was dispersed in 200mL of ethanol to reduce its viscosity. The obtained suspension is filtered and separated, and firstlyThen, the filter cake was mixed with 100mL of absolute ethanol and 100mL of deionized water, slurried, and filtered 3 times each. And finally, transferring the filter cake into a baking oven at 120 ℃ for drying overnight to prepare HAP nanowire/PTFE composite powder with the mass fraction of 0.25%, placing the composite powder into a mould pressing die, and pressurizing for 1 hour at room temperature in a hydraulic forming machine, wherein the pressure is set to be 20-25MPa. And taking out the pressed sample wafer and placing for 12h to release internal stress. And then placing the sample wafer in a muffle furnace for sintering and molding, adjusting the sintering temperature to 375 ℃, keeping the temperature for 1.5h, then naturally cooling to 325 ℃, keeping the temperature for half an hour, finally naturally cooling to room temperature to obtain the HAP nanowire/PTFE compound sample wafer with the mass fraction of 0.25%, and summarizing the performance of the HAP nanowire/PTFE compound sample wafer in Table 1 after testing.
Example 2
According to the process shown in FIG. 1, the method specifically comprises the following steps: at room temperature, 80mL ethanol and 24mL oleic acid were added to a beaker and stirred until dissolved. Three portions of 40mL deionized water are weighed, and then 2.00g of NaOH and 0.44g of CaCl are weighed 2 、0.48g NaH 2 PO 4 Respectively putting the mixture into beakers with 40mL of deionized water, and stirring the mixture until the mixture is completely dissolved to obtain NaOH aqueous solution and CaCl 2 Aqueous solution and NaH 2 PO 4 An aqueous solution. And then, slowly dripping the three solutions into a mixed solution of oleic acid and ethanol in turn, and continuously stirring. Adding ethanol solution dispersed with polytetrafluoroethylene powder, and stirring to obtain suspension. Transferring the obtained suspension into a polytetrafluoroethylene-lined stainless steel autoclave, heating to 180 ℃, reacting at constant temperature for 24 hours, and naturally cooling to room temperature. The resulting viscous reaction system was dispersed in 200mL of ethanol to reduce its viscosity. And carrying out suction filtration and separation on the obtained suspension, mixing the filter cake with 100mL of absolute ethyl alcohol and 100mL of deionized water successively, pulping, and filtering for 3 times respectively. And finally, transferring the filter cake into a baking oven at 120 ℃ for drying overnight to prepare HAP nanowire/PTFE composite powder with the mass fraction of 0.5%, placing the composite powder into a mould pressing die, and pressurizing for 1 hour at room temperature in a hydraulic forming machine, wherein the pressure is set to be 20-25MPa. And taking out the pressed sample wafer and placing for 12h to release internal stress. Then placing the sample wafer in a muffle furnace for sintering and forming, adjusting the sintering temperature to 375 ℃, keeping the temperature for 1.5h, then naturally cooling to 325 ℃, keeping the temperature for half an hourAnd finally, naturally cooling to room temperature to obtain a HAP nanowire/PTFE compound sample wafer with the mass fraction of 0.5%, and testing to summarize the performance of the sample wafer in the table 1.
Example 3
According to the process shown in FIG. 1, the method specifically comprises the following steps: at room temperature, 80mL ethanol and 24mL oleic acid were added to a beaker and stirred until dissolved. Three portions of 40mL deionized water are weighed, and then 4.00g of NaOH and 0.88g of CaCl are weighed 2 、0.96g NaH 2 PO 4 Respectively putting the mixture into beakers with 40mL of deionized water, and stirring the mixture until the mixture is completely dissolved to obtain NaOH aqueous solution and CaCl 2 Aqueous solution and NaH 2 PO 4 An aqueous solution. And then the three solutions are sequentially and slowly dripped into the mixed solution of oleic acid and ethanol and continuously stirred. Adding ethanol solution dispersed with polytetrafluoroethylene powder, and stirring to obtain suspension. Transferring the obtained suspension into a polytetrafluoroethylene-lined stainless steel autoclave, heating to 180 ℃, reacting at constant temperature for 24 hours, and naturally cooling to room temperature. The resulting viscous reaction system was dispersed in 200mL of ethanol to reduce its viscosity. And carrying out suction filtration and separation on the obtained suspension, mixing the filter cake with 100mL of absolute ethyl alcohol and 100mL of deionized water in sequence, pulping, and filtering for 3 times respectively. And finally, transferring the filter cake into an oven at 120 ℃ for drying overnight to prepare HAP nanowire/PTFE compound powder with the mass fraction of 1%, placing the compound powder into a mould pressing die, and pressurizing for 1h at room temperature in a hydraulic forming machine, wherein the pressure is set to be 20-25MPa. And taking out the pressed sample wafer and placing for 12h to release internal stress. And then placing the sample wafer in a muffle furnace for sintering and molding, adjusting the sintering temperature to 375 ℃, keeping the temperature for 1.5h, then naturally cooling to 325 ℃, keeping the temperature for half an hour, finally naturally cooling to room temperature to obtain the HAP nanowire/PTFE compound sample wafer with the mass fraction of 1%, and summarizing the performance of the HAP nanowire/PTFE compound sample wafer in Table 1 after testing.
Example 4
According to the process shown in FIG. 1, the method specifically comprises the following steps: at room temperature, 150mL ethanol and 24mL oleic acid were added to a beaker and stirred until dissolved. Three portions of 40mL deionized water are weighed, and then 2.00g of NaOH and 0.44g of CaCl are weighed 2 、0.48g NaH 2 PO 4 Separately put into a beaker containing 40ml of deionized water and stirredDissolving completely to obtain NaOH aqueous solution and CaCl 2 Aqueous solution and NaH 2 PO 4 An aqueous solution. And then the three solutions are sequentially and slowly dripped into the mixed solution of oleic acid and ethanol and continuously stirred. Adding ethanol solution dispersed with polytetrafluoroethylene powder, and stirring to obtain suspension. Transferring the obtained suspension into a polytetrafluoroethylene-lined stainless steel autoclave, heating to 180 ℃, reacting at constant temperature for 24 hours, and naturally cooling to room temperature. The resulting viscous reaction system was dispersed in 200mL of ethanol to reduce its viscosity. And carrying out suction filtration and separation on the obtained suspension, mixing the filter cake with 100mL of absolute ethyl alcohol and 100mL of deionized water in sequence, pulping, and filtering for 3 times respectively. And finally, transferring the filter cake into a drying oven at 120 ℃ for drying overnight to prepare HAP nanowire/PTFE compound powder with the mass fraction of 0.5%, placing the compound powder into a mould pressing die, and pressurizing for 1 hour at room temperature in a hydraulic forming machine, wherein the pressure is set to be 20-25MPa. And taking out the pressed sample wafer and placing for 12h to release internal stress. And then placing the sample wafer in a muffle furnace for sintering and molding, adjusting the sintering temperature to 375 ℃, keeping the temperature for 1.5h, then naturally cooling to 325 ℃, keeping the temperature for half an hour, finally naturally cooling to room temperature to obtain the HAP nanowire/PTFE compound sample wafer with the mass fraction of 0.5%, and summarizing the performance of the HAP nanowire/PTFE compound sample wafer in Table 1 after testing.
Comparative example 1:
putting pure PTFE powder into a die, and pressurizing for 1 hour at room temperature in a hydraulic forming machine, wherein the pressure is set to be 20-25MPa. And taking out the pressed sample wafer and placing for 12h to release internal stress. And then placing the sample wafer in a muffle furnace for sintering and molding, adjusting the sintering temperature to 375 ℃, keeping the temperature for 1.5h, then naturally cooling to 325 ℃, keeping the temperature for half an hour, finally naturally cooling to room temperature to obtain a pure PTFE sample wafer, and testing the performance of the pure PTFE sample wafer to be summarized in Table 1.
Comparative example 2:
24mL of oleic acid is weighed and added into 40mL of ethanol, and the mixture is stirred uniformly to obtain a mixed solution. Three portions of 40mL deionized water are weighed, and then 2.00g of NaOH and 0.44g of CaCl are weighed 2 、0.48g NaH 2 PO 4 Respectively putting the mixture into beakers with 40mL of deionized water, and stirring the mixture until the mixture is completely dissolved to obtain NaOH aqueous solution and CaCl 2 Aqueous solution and NaH 2 PO 4 An aqueous solution. And then the three solutions are sequentially and slowly dripped into the mixed solution of oleic acid and ethanol and continuously stirred. Transferring the obtained white suspension into a polytetrafluoroethylene-lined stainless steel autoclave, heating to 180 ℃, reacting at constant temperature for 24 hours, and naturally cooling to room temperature. The resulting viscous reaction system was dispersed in 50mL of ethanol to reduce its viscosity. And carrying out suction filtration and separation on the obtained suspension, mixing the filter cake with 50mL of absolute ethyl alcohol and 100mL of deionized water in sequence, pulping, and filtering for 3 times respectively. And finally, transferring the filter cake into an oven at 120 ℃ to dry overnight to obtain white powder, namely the HAP nanowire. HAP nanowires with diameter of 100-300nm and length-diameter ratio of 50-150 prepared in laboratory were mixed with PTFE powder at mass ratio of 0.5: 100, and mixed for 3 times (10 s each time) with a high speed stirrer rotating at 29000 r/min. The HAP nanowire/PTFE composite powder with the mass fraction of 0.5 percent, which is obtained by the mechanical mixing method, is placed in a die, and 1h is pressurized in a hydraulic forming machine at room temperature, wherein the pressure is set to be 20-25MPa. And taking out the pressed sample wafer and placing for 12h to release internal stress. And then placing the sample wafer in a muffle furnace for sintering and molding, adjusting the sintering temperature to 375 ℃, keeping the temperature for 1.5h, then naturally cooling to 325 ℃, keeping the temperature for half an hour, finally naturally cooling to room temperature to obtain the HAP nanowire/PTFE compound sample wafer with the mass fraction of 0.5% prepared by mechanical mixing, and summarizing the performance of the sample wafer in Table 1 after testing.
Table 1 is a table comparing the basic performance parameters of the composites obtained in examples 1-4 and comparative examples 1-2
As shown in fig. 2A, which is an SEM image of the hydroxyapatite nanowire/polytetrafluoroethylene nanocomposite prepared in example 2, the HAP nanowires prepared by in-situ filling are uniformly dispersed in the composite material, have uniform size, and have good interface bonding with the matrix; fig. 2B is an SEM image of the HAP nanowire/PTFE nanocomposite prepared by the mechanical mixing method in comparative example 2, which shows that the aggregation of HAP nanowires is significant, the nanowires have non-uniform sizes, and fragments are attached to the PTFE surface; fig. 2C is an SEM image of the hydroxyapatite nanowire/PTFE composite prepared in comparative example 3, in which the aspect ratio of the synthesized HAP nanowire is reduced by increasing the content of ethanol in the reaction condition, and the size is uniform and well dispersed on the PTFE surface.
In the present invention, HAP nanowires are in-situ filled into PTFE by a hydrothermal synthesis method, as can be seen from table 1, the stiffness, glass transition temperature and hydrophobicity of HAP nanowire/PTFE composites prepared by in-situ filling are significantly improved compared to pure PTFE and HAP nanowire/PTFE composites prepared by mechanical mixing. More importantly, the HAP nanowire/PTFE composites prepared by in situ filling of the present invention exhibit significantly reduced coefficient of friction and volumetric wear rates.
In conclusion, the HAP nanowires in the HAP nanowire/PTFE nano composite prepared by the method are uniform in size and highly dispersed, and the HAP nanowires are well combined with PTFE interfaces, so that the tribological performance of PTFE can be remarkably improved, and the HAP nanowires are superior to samples prepared by a conventional mechanical mixing method.
Claims (2)
1. A hydroxyapatite nanowire/polytetrafluoroethylene composite is characterized in that: the composite matrix is polytetrafluoroethylene, the filler is hydroxyapatite nano-wires,
the compound is prepared by in-situ hydrothermal synthesis;
(1) Respectively preparing NaOH aqueous solution and CaCl 2 Aqueous solution, naH 2 PO 4 Water solution, mixed solution of oleic acid and ethanol;
(2) Respectively adding NaOH aqueous solution and CaCl under the condition of continuous stirring 2 Aqueous solution, naH 2 PO 4 Sequentially and slowly dripping the aqueous solution into the mixed solution of oleic acid and ethanol;
(3) Under the condition of continuous stirring, adding an ethanol solution dispersed with polytetrafluoroethylene powder into the mixed solution to prepare polytetrafluoroethylene suspension, carrying out a heating hydrothermal reaction on the system, and naturally cooling to room temperature;
(4) Adding ethanol into the reaction solution cooled to room temperature to reduce the system viscosity, filtering, washing a filter cake by deionized water and ethanol, and drying to obtain hydroxyapatite nanowire/polytetrafluoroethylene composite powder;
(5) The composite powder is cold pressed and then sintered and molded to prepare a hydroxyapatite nanowire/polytetrafluoroethylene composite sample wafer,
the hydroxyapatite nano wire accounts for 0.5 percent of the mass fraction of the hydroxyapatite nano wire/polytetrafluoroethylene composite powder, the diameter is 100-300nm, and the length-diameter ratio is 50-150.
2. The method for preparing a hydroxyapatite nanowire/polytetrafluoroethylene composite according to claim 1, characterized in that: the method comprises the following steps:
(1) Respectively preparing NaOH aqueous solution and CaCl 2 Aqueous solution, naH 2 PO 4 Water solution, mixed solution of oleic acid and ethanol;
(2) Respectively adding NaOH aqueous solution and CaCl under the condition of continuous stirring 2 Aqueous solution, naH 2 PO 4 Sequentially and slowly dripping the aqueous solution into the mixed solution of oleic acid and ethanol;
(3) Under the condition of continuous stirring, adding an ethanol solution dispersed with polytetrafluoroethylene powder into the mixed solution to prepare polytetrafluoroethylene suspension, carrying out a heating hydrothermal reaction on the system, and naturally cooling to room temperature;
(4) Adding ethanol into the reaction solution cooled to room temperature to reduce the system viscosity, filtering, washing a filter cake by deionized water and ethanol, and drying to obtain hydroxyapatite nanowire/polytetrafluoroethylene composite powder;
(5) And (3) cold pressing the composite powder, and then sintering and molding to obtain a hydroxyapatite nanowire/polytetrafluoroethylene composite sample wafer.
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