CN110172199B - Preparation method of hydroxyapatite/ultra-high molecular weight polyethylene nano composite - Google Patents

Preparation method of hydroxyapatite/ultra-high molecular weight polyethylene nano composite Download PDF

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CN110172199B
CN110172199B CN201910553376.8A CN201910553376A CN110172199B CN 110172199 B CN110172199 B CN 110172199B CN 201910553376 A CN201910553376 A CN 201910553376A CN 110172199 B CN110172199 B CN 110172199B
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石国军
曹臻
颜笑天
王秋义
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Abstract

The invention relates to a preparation method of a hydroxyapatite/ultra-high molecular weight polyethylene nano composite in the field of high polymer materials. The invention utilizes the surfactant to uniformly disperse UHMWPE powder with higher hydrophobicity in water, and then adds Ca into the system2+And HPO4 2‑Under the catalysis of alkaline environment, two ions react on the surface of the substrate to synthesize nano HAP, and after hydrothermal treatment, the prepared suspension is filtered, dried and subjected to hot press molding, so that the in-situ filling of nano HAP in UHMWPE is realized through the processes. The method of the invention realizes high dispersion of nano HAP in UHMWPE matrix, and improves the rigidity, strength, toughness, glass transition temperature, hydrophilicity and tribology performance of the matrix material.

Description

Preparation method of hydroxyapatite/ultra-high molecular weight polyethylene nano composite
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a preparation method of a hydroxyapatite/ultrahigh molecular weight polyethylene nano composite for improving the tribological performance of a high polymer material.
Background
The ultra-high molecular weight polyethylene (UHMWPE) has the advantages of good self-lubricating capability, small friction coefficient, high impact strength, low creep deformation, high fatigue resistance, good biological inertia and the like, and can be widely applied to the fields of industrial bearings, mechanical parts, artificial joints and the like as a wear-resistant material.
Although UHMWPE has extremely excellent comprehensive performance, the defects of small surface hardness, lower elastic modulus and bending strength, poor abrasive particle wear resistance and the like exist. Therefore, in order to meet the use requirements of UHMWPE under industrial friction conditions, it is necessary to modify it in order to further improve the mechanical and tribological properties of UHMWPE. The excellent physical and chemical properties of the nano filler can be fully exerted by filling the nano particles into the high molecular resin, and the nano filler can generate stronger interaction and better interface combination with the matrix material. The nano particles are filled into UHMWPE by using an in-situ filling method, so that the particle size advantage of the nano filler can be effectively exerted, and the defect that the nano filler is not easy to disperse caused by a conventional mechanical mixing mode can be overcome.
The most common application of UHMWPE in clinical orthopaedics is the acetabulum of a hip joint prosthesis. Matthew et al (surf. topogr. in metals. prop., in 2018, 11 months) implanted UHMWPE into humans as a lining of the acetabulum, and then recovered UHMWPE joints after frictional use and subjected their surfaces to tribological analysis. It was found that the UHMWPE joint surface texture after rubbing was more smooth, the density of protrusions on the surface of the wear area was lower and the difference between the highest and lowest points was reduced. Shahemi et al (J. biomed. Mater. Res. A, 2018, 11 months) recovered and studied UHMWPE artificial hip prostheses that eventually failed after years of use in humans, and analyzed the failure mechanism of UHMWPE acetabular cups in long-term use after total hip replacement. The results show that the UHMWPE joint mortar is oxidized in the use for years, so that the mechanical property is degraded, and the abrasive dust generates corrugated valleys on the surface of the material. In practice, it has been found that UHMWPE artificial joints are susceptible to failure due to aging and wear caused by long-term heavy loads and reciprocating motion with hard materials such as stainless steel, titanium alloy, and ceramics (mater. sci. technol., 2018). On the one hand, the wear-induced abrasive dust accumulates and stimulates the immune system to cause a series of adverse biological reactions in soft tissues, which leads to osteolysis around the prosthesis and loosening of the prosthesis which is originally well fixed (Acta biomater, 2019, month 1). On the other hand, the requirements of the artificial joint on the hardness and the wear resistance of materials are relatively high, and the UHMWPE can creep in the long-term use process to cause the replacement joint to generate large wear, thereby influencing the stability of the replacement joint.
The biological tribology and the surface engineering are still in the beginning stage at home and abroad as a new cross subject, and from the current situation of Wear characteristics and modification research of UHMWPE, systematic research is carried out on the Wear of modified materials by combining with the actual replacement environment, so that the biocompatibility is improved, the Wear resistance is enhanced, the service life is prolonged, and the like (Wear, 10 months in 2001) are the key points of future research of experts of the home and abroad.
Researchers in the field of biomedicine have tried a wide variety of materials to increase the bioactivity of UHMWPE. Researches show that various natural or artificial materials such as coral powder, ceramics, carbon materials, silicate, Hydroxyapatite (HAP) and the like can be used for improving the biocompatibility of UHMWPE. Among them, the major inorganic component of bones and teeth of vertebrates is Hydroxyapatite (HAP), which is a relatively common phosphate that can be implanted into human bodies. HAP accounts for about 60% in bone, and more than 90% in enamel, and is a needle-like crystal 20-40 nm in length and 15-30 nm in diameter. It has biocompatibility, chemical stability at neutral pH value, strong ability of combining with bone, and can raise the bone conduction ability of metal implant, so that it is a widely used bone grafting substitute. Studies have shown that the smaller the size of the HAP grains, the higher the bioactivity. Thus, the nano-sized HAP particles have higher biological activity than ordinary HAP particles.
The HAP nano particles are dispersed in the UHMWPE matrix by using an in-situ filling mode, so that the influence of the nano particles which are possibly peeled off from the surface in the abrasion process on human tissues can be reduced. However, the use of nano-grade fillers in the blending process of composite materials can cause the problem of uneven mixing, compared with fillers with particle sizes above micron, the surface energy of nano-particles is higher, and HAP is not easy to disperse uniformly by a mechanical mixing method, and the HAP is agglomerated with each other in the mixing process, so that the mixing effect is affected.
Disclosure of Invention
The invention provides a preparation method of a hydroxyapatite/ultrahigh molecular weight polyethylene nano composite based on in-situ filling, which enables nano fillers to be uniformly dispersed and has good comprehensive performance, aiming at the problem of uneven mixing caused by the fact that nano fillers are not easily and uniformly dispersed in the blending processing process of composite materials in the prior art.
The invention aims to realize the purpose, and the preparation method of the hydroxyapatite/ultra-high molecular weight polyethylene nano composite comprises the following steps:
1) ca (NO) with a molar ratio of 10-20:1 under the condition of a room-temperature water bath3)2·4H2Dissolving O and Cetyl Trimethyl Ammonium Bromide (CTAB) in deionized water, stirring, adjusting pH to 10-12 with ammonia water to obtain Ca (NO) with concentration of 0.02-0.16 mol/L3)2·4H2O solution;
2) ca (NO) to step 1) under stirring3)2·4H2Adding ultrahigh molecular weight polyethylene powder into the O solution, transferring into an ultrasonic water bath, and continuously stirring for 30 min to obtain an ultrahigh molecular weight polyethylene suspension;
3) will be (NH)4)2HPO4Dissolving in deionized water to prepare (NH) with the concentration of 0.035-0.3 mol/L4)2HPO4Adjusting the pH value of the aqueous solution to 10-12 by using ammonia water;
4) preparing (NH) from step 3)4)2HPO4Mixing the solution with the ultra-high molecular weight polyethylene suspension prepared in the step 2) according to the volume ratio of (NH) to (NH 3)4)2HPO4Slowly adding the solution into the ultra-high molecular weight polyethylene suspension, heating the system to 40-80 ℃, continuously stirring for 3 hours, and then standing and aging at 25 ℃;
5) filtering the liquid aged in the step 4) to obtain a filter cake, washing the filter cake with ethanol, and drying at 120 ℃ for 12-36 h to obtain hydroxyapatite/ultrahigh molecular weight polyethylene nano composite powder and HAP/UHMWPE nano composite powder;
6) and hot-pressing and then cold-pressing the hydroxyapatite/ultrahigh molecular weight polyethylene nano composite powder to obtain a hydroxyapatite/ultrahigh molecular weight polyethylene nano composite blank.
In the process of the invention, surfactants are usedCTAB uniformly disperses UHMWPE matrix in Ca (NO)3)2·4H2O in aqueous solution by slow addition of (NH)4)2HPO4Making Ca in solution of (2)2+And HPO4 2-Nucleating and growing on the surface of UHMWPE in an alkaline environment, and then carrying out hydrothermal treatment, filtering, drying and hot-press molding to realize in-situ filling of nano hydroxyapatite on the surface of UHMWPE. In the preparation process, the nano HAP is synthesized in situ in the liquid phase and is attached to the surface of the UHMWPE, so that the interface combination of the nano HAP and the UHMWPE and the dispersion degree of the nano filler in a matrix can be improved, better wear resistance and biocompatibility are obtained, and the service life of a material part is prolonged.
Further, in the step 6), the mass content of the hydroxyapatite in the hydroxyapatite/ultrahigh molecular weight polyethylene nano composite material blank is 0.5-5%.
Further, the concentration of the hexadecyl trimethyl ammonium bromide is 0.001-0.008 mol/L. In the invention, Cetyl Trimethyl Ammonium Bromide (CTAB) is used as a cationic surfactant, lipophilic groups of the cationic surfactant are easier to contact with UHMWPE, and hydrophilic groups of the cationic surfactant are contacted with water, and the surfactant enhances the dispersion effect of UHMWPE in an aqueous solution by the mechanism. In the in-situ filling process of the HAP, the hydrophilic group of CTAB is attached to the surface of the HAP, so that the particle size of the HAP can be controlled, the agglomeration of nano HAP particles is inhibited, and the dispersion degree of the HAP particles in the UHMWPE matrix is improved.
Further, in the step 2), the particle size of the ultra-high molecular weight polyethylene powder is 100-200 μm, and the viscosity average molecular weight is 200-400 ten thousand.
Further, in the step 2), the mass percentage of the ultra-high molecular weight polyethylene in the suspension of the ultra-high molecular weight polyethylene is 20-40%. The polyethylene powder with high molecular weight and poor hydrophilicity can be uniformly dispersed in the solution by ultrasonic stirring, and the solvent can be promoted to fully enter microscopic pores of the polyethylene powder with high molecular weight, so that the dispersion degree of HAP on the surface of UHMWPE can be improved.
Further, the aging time in the step 4) is 12-36 h。Ca2+And HPO4 2-The process of generating HAP by mutual reaction requires a certain aging time, but the aging time is too long, and CO in the air2Dissolving in solution to form CO3 2-Substituted PO4 3-The HAP solubility is increased by entering crystal lattices, so that the aging reaction time needs to be reasonably controlled.
Further, in the step 6), the temperature of hot pressing the composite powder is 190-210 ℃, the pressure is 10-15 MPa, and the action time is 5-15 min. During hot pressing, the UHMWPE can be softened by the action of temperature rise, and then certain pressure is applied and the pressure is maintained for a certain time to remove air in the powder to the maximum extent. With the increase of pressure, the defects of the composite material are reduced, the shrinkage rate is reduced, and the density is increased; and the hot-pressing pressure is too high, the shrinkage rate of the composite material has no larger difference any more, the density is not obviously increased, and the product is warped, deformed and even cracked due to the too high pressure.
Further, in the step 6), the cold pressing is carried out at room temperature, the pressure is 10-20 MPa, and the action time is 3-10 min. The sample is cooled to room temperature under certain pressure conditions through a cold pressing process, so that the material has proper crystallinity, and good toughness while hardness is maintained.
Drawings
Fig. 1 is a flow chart of the preparation method of the hydroxyapatite/ultra-high molecular weight polyethylene nanocomposite of the present invention.
Fig. 2 is an SEM image of a hydroxyapatite/ultra high molecular weight polyethylene nanocomposite prepared by the method of the present invention and prepared by a mechanical mixing method, respectively.
Detailed Description
Example 1
According to the process shown in fig. 1, the method specifically comprises the following steps: 1.4188 g Ca (NO) was added under 25 ℃ water bath condition3)2·4H2O is added into a three-necked flask containing 150 ml of deionized water, stirred until dissolved, then 0.1415 g of CTAB is added and stirred until dissolved, then the pH value of the solution is adjusted to 11 by using ammonia water, finally 65 g of UHMWPE powder is added,and transferring the mixture into an ultrasonic water bath at 25 ℃ to continue stirring at 200 r/min for 30 min to obtain UHMWPE suspension.
Weighing 0.4741 g (NH)4)2HPO4Adding 50 ml deionized water to prepare (NH)4)2HPO4Aqueous solution, and the pH of the solution was adjusted to 11 using ammonia. Will be (NH)4)2HPO4Slowly dripping the solution into UHMWPE suspension, controlling the dripping time to be about 1 h, heating the system to 60 ℃ after finishing dripping, continuing stirring for 3 h, standing and aging for 24 h at 25 ℃, finally filtering redundant liquid through a Buchner funnel, washing a filter cake for 3 times by using ethanol, drying for 36h at 120 ℃, and finally obtaining the hydroxyapatite/ultrahigh molecular weight polyethylene nano composite powder with the HAP mass fraction of 1%. Placing the composite powder in a mould pressing die, preheating for 15 min at 190 ℃ in a hydraulic forming machine, then hot-pressing for 10 min under the pressure of 15 MPa, and cold-pressing for 3 min by a flat vulcanizing machine to obtain the nano HAP/UHMWPE composite material block, wherein the properties of the nano HAP/UHMWPE composite material block are summarized in Table 1 after testing.
Comparative example 1:
placing pure UHMWPE powder in a mould, preheating for 15 min at 190 ℃ in a hydraulic forming machine, then hot-pressing for 10 min under the pressure of 15 MPa, and obtaining a pure UHMWPE material sample wafer by cold pressing for 3 min through a flat vulcanizing machine, and the performance of the pure UHMWPE material sample wafer is summarized in table 1 after testing.
Comparative example 2:
HAP nanoparticles with a particle size of about 20 nm prepared in a laboratory are mixed with UHMWPE powder according to a mass ratio of 1:100, and are mixed for three times for 10 s each time by using a high-speed stirrer with a rotating speed of 29000 r/min. The nano-scale HAP/UHMWPE composite powder with the mass fraction of 1.0 percent, which is obtained by the mechanical mixing method, is placed in a mould, preheated for 15 min at 190 ℃ in a hydraulic forming machine, then hot-pressed for 10 min under the pressure of 15 MPa, and cold-pressed for 3 min by a flat vulcanizing machine to obtain a nano-HAP/UHMWPE composite material sample wafer prepared by dry mixing, and the performance of the sample wafer is summarized in Table 1 after testing.
Comparative example 3:
commercially available micron-sized HAP powder was mixed with UHMWPE powder in a mass ratio of 1:100 and mixed three times for 10 s each using a high speed stirrer rotating at 29000 r/min. The micron-scale HAP/UHMWPE composite powder material with the HAP powder mass fraction of 1.0 percent obtained by the mechanical mixing method is placed in a mould, preheated for 15 min at 190 ℃ in a hydraulic forming machine, then hot-pressed for 10 min under the pressure of 15 MPa, and cold-pressed for 3 min by a flat vulcanizing machine to obtain a micron HAP/UHMWPE composite material sample wafer prepared by dry mixing, and the performances of the sample wafer are summarized in Table 1 after testing.
Table 1 is a comparison of the basic performance parameters of the composites obtained in example 1 and comparative examples 1 to 3
Figure 119915DEST_PATH_IMAGE002
As shown in fig. 2A, which is an SEM image of the hydroxyapatite/ultra-high molecular weight polyethylene nanocomposite prepared in example 1, HAP nanoparticles filled in situ are uniformly dispersed and sized in the prepared composite material, are uniformly distributed in the pore structure of UHMWPE crystals, and can be well interface-bonded with a matrix; and fig. 2B is an SEM image of the HAP/UHMWPE nanocomposite prepared by the mechanical mixing method in comparative example 2, showing that HAP nanoparticles are agglomerated and have a non-uniform particle size distribution, which is difficult to uniformly disperse on the inner and outer surfaces of UHMWPE.
In the invention, HAP nano particles are synthesized on the surface of UHMWPE by a hydrothermal synthesis method, and the in-situ filling of nano HAP in UHMWPE can be realized. As can be seen from table 1, the HAP/UHMWPE nanocomposite prepared by in situ filling has significant improvements in stiffness, strength, toughness, glass transition temperature, and hydrophilicity over the UHMWPE matrix and the HAP/UHMWPE composite prepared by mechanical mixing. More importantly, the in-situ filled HAP/UHMWPE nanocomposites of the present invention exhibit significantly reduced coefficient of friction and volumetric wear rates.
In conclusion, the HAP nano particles in the HAP/UHMWPE nano composite prepared by the method are uniform in size and highly dispersed, and the interface combination of the HAP nano particles and the UHMWPE is good, so that the tribological performance of the UHMWPE can be obviously improved, and the HAP nano particles are superior to a sample prepared by a conventional mechanical mixing method.

Claims (7)

1. A preparation method of a hydroxyapatite/ultra-high molecular weight polyethylene nano composite comprises the following steps:
step 1, Ca (NO) with a molar ratio of 10-20:1 is added under the condition of room temperature water bath3)2·4H2Dissolving O and hexadecyl trimethyl ammonium bromide in deionized water, stirring, adjusting pH to 10-12 with ammonia water to obtain Ca (NO) with concentration of 0.02-0.16 mol/L3)2·4H2O solution;
step 2, adding Ca (NO) to the step 1) under stirring3)2·4H2Adding ultrahigh molecular weight polyethylene powder into the O solution, transferring into an ultrasonic water bath, and continuously stirring for 30 min to obtain an ultrahigh molecular weight polyethylene suspension;
step 3, mixing (NH)4)2HPO4Dissolving in deionized water to prepare (NH) with the concentration of 0.035-0.30 mol/L4)2HPO4Adjusting the pH value of the aqueous solution to 10-12 by using ammonia water;
step 4, preparing (NH) from the step 3)4)2HPO4Mixing the solution with the ultra-high molecular weight polyethylene suspension prepared in the step 2) according to the volume ratio of (NH) to (NH 3)4)2HPO4Slowly adding the solution into the ultra-high molecular weight polyethylene suspension, heating the system to 40-80 ℃, continuously stirring for 3 hours, and then standing and aging at 25 ℃;
step 5, filtering the liquid aged in the step 4) to obtain a filter cake, washing the filter cake with ethanol, and drying at 120 ℃ for 12-36 h to obtain hydroxyapatite/ultrahigh molecular weight polyethylene nano composite powder;
step 6, hot-pressing and then cold-pressing the hydroxyapatite/ultrahigh molecular weight polyethylene nano composite powder to form a hydroxyapatite/ultrahigh molecular weight polyethylene nano composite material blank; the mass content of the hydroxyapatite in the hydroxyapatite/ultrahigh molecular weight polyethylene nano composite material blank is 0.5-5%.
2. The method according to claim 1, wherein the concentration of cetyltrimethylammonium bromide in step 1) is 0.001-0.008 mol/L.
3. The method as claimed in claim 1, wherein the particle size of the ultra-high molecular weight polyethylene powder in step 2) is 100-200 μm, and the viscosity average molecular weight is 200-400 ten thousand.
4. The method according to claim 1, wherein in step 2), the suspension of the ultra-high molecular weight polyethylene has a mass percentage of the ultra-high molecular weight polyethylene of 20% to 40%.
5. The process according to claim 1, wherein the aging time in step 4) is 12 to 36 hours.
6. The preparation method according to claim 1, wherein in the step 6), the composite powder is hot pressed at a temperature of 190 ℃ to 210 ℃, under a pressure of 10 MPa to 15 MPa, and for an action time of 5 min to 15 min.
7. The method for preparing the nano-particles according to claim 1, wherein the pressure of 10-20 MPa is applied for 3-10 min at room temperature in the cold pressing in the step 6).
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