CN110339402B - Alpha-phase nano-alumina reinforced polyetheretherketone biological composite material and preparation method thereof - Google Patents
Alpha-phase nano-alumina reinforced polyetheretherketone biological composite material and preparation method thereof Download PDFInfo
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Abstract
The application relates to an alpha-phase nano-alumina reinforced polyetheretherketone biological composite material and a preparation method thereof. The polyether-ether-ketone resin is used as a matrix, the alpha-phase nano alumina is used as a mechanical strength enhancing phase, the silane coupling agent KH560 is used as an interface compatilizer, the polytetrafluoroethylene is used as a lubricant, the hydroxyapatite is used as a biological activity enhancing phase, and the dispersion degree of particles with enhanced phase in the matrix is obviously improved by utilizing various modes such as magnetic mechanical stirring, ultrasonic blending, graded grinding ball blending, injection molding and the like, so that the polyether-ether-ketone biological composite material with high temperature resistance, high strength, high stability and excellent biocompatibility is finally prepared.
Description
Technical Field
The invention relates to the technical field of composite materials, in particular to an alpha-phase nano-alumina reinforced polyetheretherketone biological composite material and a preparation method thereof.
Background
Orthopedic implants are very common in clinic and are mainly applied to irreparable bone loss conditions caused by trauma, disease, aging, congenital abnormality, surgical resection and the like. At present, metal materials such as stainless steel, titanium and alloys thereof are common orthopedic substitute materials, and the metal materials have good corrosion resistance, mechanical properties and biocompatibility, but have some defects, such as stress shielding effect generated after being implanted into a human body (when two or more materials with different rigidity bear external force together, the material with higher rigidity can bear more load, while the material with lower rigidity only needs to bear lower load, namely stress shielding), and possibly released metal ions can also cause inflammation of surrounding tissues, so that the metal materials can generate artifacts under common medical imaging technologies (CT, MRI and the like), and effective monitoring of bone growth and healing is not facilitated. The radio-opacity, stress shielding effect and metal ion poisoning phenomenon not only hinder bone resorption, but also easily cause operation failure, and the defects seriously affect the application and development of the metal material as a biological material. In order to reduce a series of adverse reactions possibly caused after the orthopedic implant replacement material enters a human body, a novel biological replacement material needs to be searched for to reduce the risk after the orthopedic implant replacement material is implanted into the human body.
As a high performance semi-crystalline thermoplastic engineering polymer plastic, polyetheretherketone is increasingly considered as an effective substitute for metal implants. The elastic modulus (3-4GPa) of the polyether-ether-ketone is closer to that (6-30GPa) of human cortical bone and is far lower than that (more than or equal to 100GPa) of titanium and titanium alloy, so that the risk of poisoning after metal ion release and the risk of bone malabsorption caused by stress shielding effect are basically avoided, and the probability of postoperative adverse reaction is greatly reduced. In addition, polyetheretherketone also has the advantages of good biocompatibility, chemical and thermal stability, natural radiance and the like, and has become the most common biological substitute material. However, since polyetheretherketone has disadvantages such as poor mechanical strength and no bioactivity as compared with a metal material, it is necessary to improve the mechanical strength by various modification methods and further enhance biocompatibility, osteoinductivity, and the like.
Researchers have conducted filling enhancement modification experiments on polyetheretherketone by using nano-scale ceramic materials (such as alumina and zirconia), and have conducted intensive studies on the types, particle sizes, contents, surface modification modes, preparation processes and the like of fillers. Houtianwu et al (CN107541010A) disclose a nano-alumina reinforced polyetheretherketone composite material and a preparation method thereof, wherein the raw materials of the composite material comprise micron or nano-sized alumina, silica and polytetrafluoroethylene particles besides polyetheretherketone, and a process combining an aqueous solution ultrasonic mixing method and hot-press molding is adopted. Due to certain viscoelasticity of the polyether-ether-ketone, demoulding is difficult during hot press molding, and product quality and large-scale industrialization are influenced. Bear Dangsheng et al (CN102058906A) disclose a nanoparticle reinforced polyetheretherketone artificial joint material, which is prepared by screening polyetheretherketone particles with a particle size of less than 100 μm, modifying 10-100nm particles of alumina, zirconia, titania, hydroxyapatite and the like with ethanol and a coupling agent, uniformly mixing the two particles in a solution state by means of mechanical mixing and ultrasonic dispersion, and finally performing hot press molding. The method adopts polyether-ether-ketone particles with larger particle size and reinforcing phase alumina raw materials with smaller size, can not ensure the uniform dispersion of the nano particles, and is easy to agglomerate. Wide et al (CN102643514A) disclose a polyetheretherketone composite material, which comprises micrometer-sized fluorapatite, barium titanate, and polyetheretherketone, and is prepared by directly melting, blending, extruding and molding the raw materials at high temperature, without using coupling agent and lubricant, resulting in interfacial separation between matrix and reinforcing phase, and poor composite effect.
In conclusion, the nanoparticles used in these documents are still easy to agglomerate, and ordinary ultrasonic and mechanical stirring treatment cannot ensure that the nanoparticles are uniformly dispersed in the polyetheretherketone matrix, and the agglomerated nanoparticles can reduce the mechanical strength and consistency of the materials.
Disclosure of Invention
The invention aims to overcome the problems of poor interface compatibility, serious agglomeration effect, unsatisfactory performance and the like of the conventional polyether-ether-ketone composite material, and provides a novel modification and forming method of a polyether-ether-ketone biological composite material. According to the method, a silane coupling agent (KH560), a lubricant (polytetrafluoroethylene) and the like are utilized, and multiple mixing modes such as mechanical stirring, ultrasonic hydrothermal treatment, ball milling, injection molding and the like are assisted, so that the interfacial compatibility between a polyether-ether-ketone matrix and an alpha-phase nano-alumina reinforcing phase is greatly improved, the agglomeration effect is reduced, and the mechanical property of the composite material is improved. In addition, the added hydroxyapatite component with bioactivity improves the biocompatibility of the polyether-ether-ketone matrix. In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
the preparation method of the alpha-phase nano alumina reinforced polyetheretherketone biological composite material comprises the following steps: (a) adding alpha-phase nano alumina into ethanol, stirring uniformly, adding polyether-ether-ketone, polytetrafluoroethylene, a silane coupling agent and hydroxyapatite, and continuously stirring to obtain a suspension; (b) carrying out ultrasonic water bath treatment on the suspension, and then removing the solvent to obtain composite powder; (c) and performing injection molding after ball milling of the composite powder.
Further, in the step (a), before the polyetheretherketone, the alpha-phase nano-alumina, the polytetrafluoroethylene and the hydroxyapatite are used, sufficient water removal (with the water content below 20 ppm) is required, wherein the water removal mode is vacuum drying, the drying temperature is 120 ℃ and 150 ℃, and the drying time is 3-12 h.
Further, the two times of stirring in the step (a) are both 0.5-1.0h, the rotating speed of the stirrer is 500-.
Further, the mass and dosage ratio of the polyetheretherketone, the alpha-phase nano-alumina, the silane coupling agent (KH560), the polytetrafluoroethylene and the hydroxyapatite is 80-100:5-15:1-5:1-5:1-5, and the addition amount of the ethanol is equal to the sum of the mass of the raw materials.
Furthermore, the particle size of the polyetheretherketone in the raw materials is 45-55 μm, the particle size of the alpha-phase nano-alumina is 30-200 nm, the particle size of the polytetrafluoroethylene is 15-20 μm, and the particle size of the hydroxyapatite is 55-65 nm.
Further, in the step (b), the temperature of the ultrasonic water bath is 20-60 ℃, the ultrasonic treatment time is 1-2h, and the ultrasonic frequency is 50-60 KHz.
Further, in the step (b), the solvent in the suspension is removed by drying, wherein the drying temperature is 70-90 ℃, and the drying time is 10-14 h.
Further, in the step (c), 3 kinds of grinding balls (zirconia materials) with different particle diameters are adopted to ball-mill the composite powder, the rotating speed of the ball mill is 350-450r/min, and the ball-milling time is 1-2 h. The diameters of the 3 grinding balls are respectively 3mm, 8mm and 15mm from small to large, the number ratio of the corresponding grinding balls is 1:3:6, and the total weight of the grinding balls is equal to the weight of the added composite powder.
Further, the temperature of each section of the twin-screw extruder used for injection molding in the step (c) is respectively as follows: the first zone is 300-320 ℃, the second zone is 310-330 ℃, the third zone is 320-340 ℃, the fourth zone is 330-350 ℃, the fifth zone is 350-355 ℃, the sixth zone is 355-365 ℃, the length-diameter ratio of the screw is 30-50, and the rotation speed of the screw is 80-100 rpm; the injection molding conditions were: the total pressure is 0.9-1Mpa, the injection pressure is 1.9-1 Mpa, the injection pressure is 2.4-0.5 Mpa, the mold closing time is 2-3s, the injection time is 1-5 s, the injection time is 2-12 s, the temperature of the template area is 220-.
Compared with the prior art, the invention takes the polyether-ether-ketone resin as a matrix, the alpha-phase nano-alumina as a reinforcing phase, the silane coupling agent KH560 as an interface compatilizer and the polytetrafluoroethylene as a lubricant, and utilizes magnetic mechanical stirring, ultrasonic blending and graded grinding ball blending to obviously improve the dispersion degree of the reinforcing phase in the matrix, reduce the agglomeration effect and obviously improve the mechanical property of the composite material. The prepared composite biomaterial not only has good high temperature resistance, high strength and high stability, but also has excellent biocompatibility due to the added hydroxyapatite component, and has good application prospect in the aspect of orthopedics substitute materials.
Drawings
FIG. 1 is an SEM image of a cross section obtained by mechanical strength test of the biocomposite material in example 1;
FIG. 2 is an SEM image of a cross section obtained by mechanical strength test of the biocomposite material in example 2;
FIG. 3 is an SEM image of a cross section obtained by mechanical strength test of the biocomposite material in example 3;
FIG. 4 is an SEM image of a cross section obtained by mechanical strength test of the biocomposite material in example 4;
FIG. 5 is a graph showing the results of cell culture experiments performed on the bio-composite material and the pure PEEK resin extract of examples 1-4.
Detailed Description
In order to make those skilled in the art fully understand the technical solutions and advantages of the present invention, the following embodiments are further described.
Example 1
85g of polyetheretherketone powder having a particle size of 50 μm, 15g of alpha nano-alumina powder having a particle size of 30nm, 1g of polytetrafluoroethylene powder having a particle size of 15 μm, and 5g of hydroxyapatite having a particle size of 60nm were weighed. And (3) respectively putting the weighed raw materials into a vacuum drying oven, and drying for 12 hours at 120 ℃ until the moisture is completely removed for later use.
Adding 100mL of absolute ethyl alcohol into a beaker at room temperature, adding dried alpha nano-alumina powder, and magnetically stirring at the rotating speed of 500r/min for 1h to obtain a suspension. Then, the dried other raw materials (comprising polyether ether ketone powder, polytetrafluoroethylene powder and hydroxyapatite, the same below) and 2g of silane coupling agent KH560 are slowly added into the suspension, and the mixture is continuously stirred at the same rotating speed for 1 hour at room temperature to obtain polyether ether ketone/alumina suspension. The suspension is placed in an ultrasonic water bath device and is subjected to ultrasonic treatment for 2h at room temperature at the frequency of 50-60 KHz. And then transferring the mixture into an oven, and drying for 12h at 80 ℃ to obtain the composite powder.
Adding 100g of 3 zirconium oxide grinding balls with different sizes and quantities (the diameter is 3mm, the diameter is 8mm, the diameter is 15mm, and the quantity ratio is 1:3:6) in a ball mill in advance, transferring the dried composite powder into the ball mill, and carrying out ball milling for 2 hours at the rotating speed of 400 r/min. And conveying the mixed powder subjected to ball milling to a double-screw melt extruder and injection molding machine combined device, and performing injection molding to obtain the composite material. The temperature of each section in the double-screw melt extruder is respectively as follows: the first zone is 300-320 ℃, the second zone is 310-330 ℃, the third zone is 320-340 ℃, the fourth zone is 330-350 ℃, the fifth zone is 350-355 ℃, the sixth zone is 355-365 ℃, the length-diameter ratio of the screw is 30-50, and the rotation speed of the screw is 80-100 rpm. The injection molding machine has the following setting parameters: the total pressure is 0.9-1Mpa, the injection pressure is 1.9-1 Mpa, the injection pressure is 2.4-0.5 Mpa, the mold closing time is 2-3s, the injection time is 1-5 s, the injection time is 2-12 s, the temperature of the template area is 220-.
Example 2
95g of polyetheretherketone powder having a particle size of 50 μm, 5g of alpha-nano-alumina powder having a particle size of 30nm, 1g of polytetrafluoroethylene powder having a particle size of 15 μm, and 5g of hydroxyapatite having a particle size of 60nm were weighed. And (3) respectively putting the weighed raw materials into a vacuum drying oven, and drying for 3 hours at 150 ℃ until the moisture is completely removed for later use.
Adding 100mL of absolute ethyl alcohol into a beaker at room temperature, adding dried alpha nano-alumina powder, and magnetically stirring at the rotating speed of 500r/min for 1h to obtain a suspension. Then, the dried other raw materials and 2g of silane coupling agent KH560 are slowly added into the suspension, and the stirring is continued for 1h at the same rotating speed at room temperature, so as to obtain the polyetheretherketone/alumina suspension. The suspension is placed in an ultrasonic water bath device and is subjected to ultrasonic treatment for 2h at room temperature at the frequency of 50-60 KHz. And then transferring the mixture into an oven, and drying for 12h at 80 ℃ to obtain the composite powder.
The dried composite powder was ball milled for 2 hours at a rotation speed of 400r/min using the same method as in example 1. The mixed powder after ball milling was transferred to a twin-screw melt extruder and injection molding machine combined apparatus, and injection molding was performed under the conditions in example 1 to obtain a composite material.
Example 3
85g of polyetheretherketone powder having a particle size of 50 μm, 15g of alpha nano-alumina powder having a particle size of 200nm, 1g of polytetrafluoroethylene powder having a particle size of 15 μm, and 5g of hydroxyapatite having a particle size of 60nm were weighed. And (3) respectively putting the weighed raw materials into a vacuum drying oven, and drying for 12 hours at 120 ℃ until the moisture is completely removed for later use.
Adding 100mL of absolute ethyl alcohol into a beaker at room temperature, adding dried alpha nano-alumina powder, and magnetically stirring at the rotating speed of 800r/min for 0.5h to obtain a suspension. Then, the dried other raw materials and 2g of silane coupling agent KH560 are slowly added into the suspension, and the stirring is continued for 0.5h at the same rotating speed at room temperature, so as to obtain the polyetheretherketone/alumina suspension. The suspension is placed in an ultrasonic water bath device and is subjected to ultrasonic treatment for 2h at room temperature at the frequency of 50-60 KHz. And then transferring the mixture into an oven, and drying for 12h at 80 ℃ to obtain the composite powder.
The dried composite powder was ball milled for 2 hours at a rotation speed of 400r/min using the same method as in example 1. The mixed powder after ball milling was transferred to a twin-screw melt extruder and injection molding machine combined apparatus, and injection molding was performed under the conditions in example 1 to obtain a composite material.
Example 4
95g of polyetheretherketone powder having a particle size of 50 μm, 5g of alpha nano-alumina powder having a particle size of 200nm, 1g of polytetrafluoroethylene powder having a particle size of 15 μm, and 5g of hydroxyapatite having a particle size of 60nm were weighed. And (3) respectively putting the weighed raw materials into a vacuum drying oven, and drying for 3 hours at 150 ℃ until the moisture is completely removed for later use.
Adding 100mL of absolute ethyl alcohol into a beaker at room temperature, adding dried alpha nano-alumina powder, and magnetically stirring at the rotating speed of 500r/min for 1h to obtain a suspension. Then, the dried other raw materials and 2g of silane coupling agent KH560 are slowly added into the suspension, and the stirring is continued for 1h at the same rotating speed at room temperature, so as to obtain the polyetheretherketone/alumina suspension. The suspension is placed in an ultrasonic water bath device and is subjected to ultrasonic treatment for 2h at room temperature at the frequency of 50-60 KHz. And then transferring the mixture into an oven, and drying for 12h at 80 ℃ to obtain the composite powder.
The dried composite powder was ball milled for 3 hours at a rotation speed of 300r/min in the same manner as in example 1. The mixed powder after ball milling was transferred to a twin-screw melt extruder and injection molding machine combined apparatus, and injection molding was performed under the conditions in example 1 to obtain a composite material.
Comparative example 1
85g of polyetheretherketone powder having a particle size of 50 μm, 15g of alpha nano-alumina powder having a particle size of 30nm, 1g of polytetrafluoroethylene powder having a particle size of 15 μm, and 5g of hydroxyapatite having a particle size of 60nm were weighed. And (3) respectively putting the weighed raw materials into a vacuum drying oven, and drying for 12 hours at 120 ℃ until the moisture is completely removed for later use.
Adding 100mL of absolute ethyl alcohol into a beaker at room temperature, adding dried alpha nano-alumina powder, and magnetically stirring at the rotating speed of 500r/min for 1h to obtain a suspension. Then, the dried other raw materials and 2g of silane coupling agent KH560 are slowly added into the suspension, and the stirring is continued for 1h at the same rotating speed at room temperature, so as to obtain the polyetheretherketone/alumina suspension. The suspension is placed in an ultrasonic water bath device and is subjected to ultrasonic treatment for 2h at room temperature at the frequency of 50-60 KHz. And then transferring the mixture into an oven, and drying for 12h at 80 ℃ to obtain the composite powder.
Adding 100g of zirconia grinding balls with single diameter (3mm) into the ball mill in advance, transferring the dried composite powder into the ball mill, and carrying out ball milling for 2h at the rotating speed of 400 r/min. The mixed powder after ball milling was transferred to a twin-screw melt extruder and injection molding machine combined apparatus, and injection molding was performed under the conditions in example 1 to obtain a composite material.
Comparative example 2
Pure polyetheretherketone was used as a raw material (dried in advance), and the mixture was fed to a twin-screw melt extruder and injection molding machine combination, and injection-molded under the conditions described in example 1 to obtain a composite material.
Firstly, testing mechanical properties
Mechanical property tests were performed on the composite materials prepared in examples 1 to 4 and comparative examples 1 to 2 according to the standards of international ISO 527:2012, ISO 178:2010, ISO 179-1:2000, ISO 6507-1:2018, etc., and the results are shown in Table 1.
Table 1 table of mechanical property test results of different samples
Note: the more "+" indicates the better biocompatibility of the composite.
Comparing various parameters of examples 1-2 and 3-4 in table 1, it can be found that the composite material with more excellent thermal property and biocompatibility can be prepared by adopting the alpha-phase nano alumina with smaller particle size as the mechanical property enhancing phase; comparing example 1 with comparative example 1, it can be found that grinding balls with different particle sizes are graded for use, so that the grinding effect is better, and the performance of the composite material is more favorably improved; the composite material prepared in example 1 has the highest tensile strength, impact strength and elastic modulus, but relatively low bending strength; the composite materials prepared in examples 1-4 all have better properties than pure polyetheretherketone materials.
The fracture cross-sections of the composite materials prepared in examples 1 to 4 after the mechanical strength test (ISO 527:2012) were observed by a scanning electron microscope (JSM-IT200 type, Japan Electron Co., Ltd.), and the results are shown in FIGS. 1 to 4, respectively. The SEM images show that the alpha nano alumina is dispersed in the polyetheretherketone matrix very uniformly and has almost no agglomeration phenomenon, the multi-layer structure of the samples of examples 1-2 is obvious, and the multi-layer structure of the samples of examples 3-4 is not obvious.
Second, cell activity test
Preparing a leaching solution of a cell experiment sample: the leaching ratio was 0.2g/mL and the leaching medium was the minimum essential cell culture medium (MEM). 4g of each sample material was added to 20mL of leaching medium and leached at 37 ℃ for 24 h. The negative control group was made of High Density Polyethylene (HDPE) at 6cm2The positive control group was 10% dimethyl sulfoxide (DMSO) and the blank control group was MEM.
The cell experiment method comprises the following steps: l929 cells in logarithmic growth phase were trypsinized to produce 1X 104The cell suspension was seeded in 96-well plates. Blank control, negative control, positive control and test sample groups were set, each group was 6 wells, and 100 μ L of cell suspension was inoculated per well. Placing 96-well plate in CO with the volume fraction of 5% at 37 DEG C2Culturing in an incubator for 24h, removing the original culture solution, adding 100 μ L blank, negative, positive and sample leaching solutions into each hole, and continuously culturing for 72 h; and then adding 20 mu L of CCK-8 solution with the mass concentration of 5g/L into each hole, culturing for 4h again, removing liquid in the hole, adding 150 mu L of DMSO, oscillating for 10min, measuring optical density in a microplate reader at the wavelength of 570nm and 630nm, and comparing to obtain the cell activity.
The morphology of the cells after culturing the L929 cells with the extract of the material leaching solution for 3 days was observed by an inverted fluorescence microscope (model IX71, Olympus, Japan), and the results are shown in FIG. 5. The figure shows that the cells of each sample are well-formed and have no atrophic cells.
Claims (7)
1. The preparation method of the alpha-phase nano alumina reinforced polyetheretherketone biological composite material is characterized by comprising the following steps:
(a) adding alpha-phase nano alumina into ethanol, stirring uniformly, adding polyether-ether-ketone, polytetrafluoroethylene, a silane coupling agent and hydroxyapatite, and continuously stirring to obtain a suspension;
(b) carrying out ultrasonic water bath treatment on the suspension, and then removing the solvent to obtain composite powder;
(c) performing injection molding after ball milling of the composite powder;
according to the weight parts, the mass ratio of the polyether-ether-ketone to the alpha-phase nano-alumina to the silane coupling agent KH560 to the polytetrafluoroethylene to the hydroxyapatite is 80-100:5-15:1-5:1-5:1-5, and the addition amount of the ethanol is equal to the sum of the mass of the raw materials; the particle size of the polyetheretherketone in the raw materials is 45-55 μm, the particle size of the alpha-phase nano-alumina is 30-200 nm, the particle size of the polytetrafluoroethylene is 15-20 μm, and the particle size of the hydroxyapatite is 55-65 nm;
in the step (c), 3 zirconia grinding balls with different particle sizes are adopted to ball-mill the composite powder, the rotating speed of the ball mill is 350-450r/min, and the ball-milling time is 1-2 h; the diameters of the grinding balls are respectively 3mm, 8mm and 15mm from small to large, the corresponding quantity ratio of the grinding balls is 1:3:6, and the total weight of the grinding balls is equivalent to the weight of the input composite powder.
2. The method of claim 1, wherein: in the step (a), the polyether-ether-ketone, the alpha-phase nano-alumina, the polytetrafluoroethylene and the hydroxyapatite need to be dewatered before being used, and the water content of the raw materials is ensured to be below 20 ppm; the water removal mode is vacuum drying, the drying temperature is 120 ℃ and 150 ℃, and the drying time is 3-12 h.
3. The method of claim 1, wherein: in the step (a), the two times of stirring are both 0.5-1.0h, the rotating speed of the stirrer is 500-.
4. The method of claim 1, wherein: in the step (b), the temperature of the ultrasonic water bath is 20-60 ℃, the ultrasonic treatment time is 1-2h, and the ultrasonic frequency is 50-60 kHz.
5. The method of claim 1, wherein: and (b) drying to remove the solvent in the suspension, wherein the drying temperature is 70-90 ℃, and the drying time is 10-14 h.
6. The method of claim 1, wherein: the temperature of each section of the double-screw extruder used for injection molding in the step (c) is respectively as follows: the first zone is 300-320 ℃, the second zone is 310-330 ℃, the third zone is 320-340 ℃, the fourth zone is 330-350 ℃, the fifth zone is 350-355 ℃, the sixth zone is 355-365 ℃, the length-diameter ratio of the screw is 30-50, and the rotation speed of the screw is 80-100 rpm; the corresponding injection molding conditions are as follows: the total pressure is 0.9-1MPa, the injection pressure 1 is 0.9-1MPa, the injection pressure 2 is 0.4-0.5MPa, the mold closing time is 2-3s, the injection time 1 is 4-5s, the injection time 2 is 10-12s, the temperature of the template zone is 220-.
7. An alpha-phase nano alumina reinforced polyetheretherketone biocomposite, characterized in that the biocomposite is prepared according to any one of claims 1 to 6.
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