CN113633824B - Hydroxyapatite coating based on polyether-ether-ketone and preparation method thereof - Google Patents
Hydroxyapatite coating based on polyether-ether-ketone and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a hydroxyapatite coating based on polyether-ether-ketone and a preparation method thereof, which comprises the steps of adopting polyether-ether-ketone powder and Ca (OH) 2 Mixing the powder, tabletting, forming and carrying out heat treatment to obtain a composite substrate material; pretreating a composite substrate material; placing the substrate material in a hydrothermal solution, and heating to complete hydrothermal deposition; washing, drying and insulating the hydrothermal deposition sample to obtain PEEK and Ca (OH) 2 A hydroxyapatite coating on the surface of the composite material substrate. The coating prepared by the method is of a dense nano columnar structure, is firmly combined with a matrix, can effectively solve the problem of biological inertia of the PEEK surface, realizes better fit with the surface of bone tissues, remarkably promotes the osteogenesis function of cells, and is beneficial to implantation and use of a substrate material; is suitable for industrial large-scale production and has good application prospect.
Description
Technical Field
The invention belongs to the technical field of preparation of biomedical material apatite, relates to a surface coating preparation method, and particularly relates to a preparation method of a hydroxyapatite coating based on polyether-ether-ketone.
Background
Stainless steel, titanium alloy and other materials have high mechanical strength, good biocompatibility, fatigue resistance and other excellent performances, and are widely applied to the field of medical hard tissue repair and replacement, but because the elastic modulus of the traditional metal implant materials is far higher than that of medical bone tissues, the stress stimulation is easily caused to the bone tissues around the implant in practical application, so that the bone tissues around the implant are partially absorbed, the strength is reduced, namely, the so-called stress shielding effect is generated, the implant is loosened, and the use performance is seriously influenced. Meanwhile, the metal implant also has the problems that harmful metal ions are released in the long-term use process, so that osteolysis or allergen generation is caused, the metal implant is incompatible with the common Magnetic Resonance Imaging (MRI) and Computed Tomography (CT) technologies, and the monitoring on bone growth and healing is not facilitated, and the like.
Polyether-ether-ketone (PEEK) is used as a thermoplastic special engineering material, the elastic modulus of the PEEK is similar to that of bones, stress shielding can be weakened or eliminated to a certain extent, so that bone absorption is reduced or avoided, osseointegration between an implant and bone tissues is facilitated, and the PEEK has excellent characteristics of good wear resistance, fatigue resistance, easiness in processing, corrosion resistance and the like. However, PEEK has no bioactivity and cannot form osseointegration with bone tissues, so that further popularization and application of PEEK in the field of hard tissue repair and replacement are limited to a certain extent. Therefore, related researchers put forward the idea of preparing a Hydroxyapatite (HA) coating with good matching property with bone tissues on the surface of PEEK, and partial research is carried out by sequentially utilizing methods such as cold spraying, aerosol deposition, plasma spraying, spin coating and the like, but due to the limitation of a preparation process and various reasons, no remarkable progress is made in the aspect of controlling the appearance and the size of hydroxyapatite crystals so far, and most of obtained coatings have the problems of insufficient bonding with bone tissues, low bonding strength, poor application effect and the like, and cannot be widely applied.
In general, although related researchers and research institutions have conducted partial research on the use of polyetheretherketone as an implant and preparation of a hydroxyapatite coating on the surface of the polyetheretherketone, and have obtained a certain research result, no report has been reported on a preparation method of a hydroxyapatite coating having a nanorod structure and good bonding strength by a hydrothermal method based on PEEK.
Therefore, it is a technical problem to be solved at present to form uniformly covered hydroxyapatite nanorods by using a hydrothermal method to obtain a hydroxyapatite coating with good bonding strength.
Disclosure of Invention
The invention provides a method for preparing a nano rod-shaped hydroxyapatite coating by using a hydrothermal method and the coating based on the PEEK surface inertia, aiming at the problems in the preparation of the existing hydroxyapatite coating, the prepared coating has good bonding with bone tissues and high bonding strength, and the nano rod-shaped hydroxyapatite can be separated out from the composite material substrate coating.
The invention is realized by the following technical scheme.
In one aspect of the invention, a preparation method of a hydroxyapatite coating based on polyether-ether-ketone is provided, which comprises the following steps:
preparing a substrate material: according to the mass ratio (12-10): 1 mixing polyetheretherketone powder with Ca (OH) 2 Mixing the powders, ball milling, tabletting, and heat treating to obtain polyetheretherketone and Ca (OH) 2 A mixed composite substrate material;
pretreatment of the composite substrate material: polishing the composite substrate material, then ultrasonically cleaning, removing dirt on the surface, and naturally drying;
preparing a hydrothermal solution: mixing glycerol sodium phosphate C 3 H 7 Na 2 O 6 P and disodium calcium ethylene tetraacetate C 10 H 12 CaN 2 Na 2 O 8 Dissolving in water in sequence to prepare a hydrothermal solution, and adjusting the pH value to be neutral;
preparing a coating: adding the prepared hydrothermal solution into a reaction kettle, placing the substrate material into the hydrothermal solution, heating to 160-180 ℃, and preserving heat for 5-20 hours to complete hydrothermal deposition;
and (3) post-treatment: washing, drying and insulating the hydrothermal deposition sample to obtain PEEK and Ca (OH) 2 A hydroxyapatite coating on the surface of the composite material substrate.
Preferably, PEEK is blended with Ca (OH) 2 And performing heat treatment after powder ball milling, mixing, tabletting and forming, wherein the temperature is 280-300 ℃, and the heat preservation time is 2 hours.
Preferably, the composite substrate material is pretreated: and (3) sequentially grinding and polishing the composite substrate material by 2500# and 5000# sandpaper, and then sequentially placing the composite substrate material in acetone, deionized water and alcohol solution for ultrasonic cleaning for 10-20min respectively.
Preferably, the sodium dihydrogen glycerophosphate C for preparing the hydrothermal solution 3 H 7 Na 2 O 6 The concentration of P is 0.02mol/L, and the oxalic acid tetraacetic acid disodium calcium disodium salt C 10 H 12 CaN 2 Na 2 O 8 The concentration of (2) was 0.2 mol/L.
Preferably, the pH is adjusted to 6 to 7 with 0.02mol/L NaOH.
Preferably, when the hydroxyapatite coating is prepared, the temperature of the hydrothermal solution is 160-180 ℃, and the heat preservation time is 5-20 h.
Preferably, after the coating is prepared, drying treatment is further carried out at the temperature of 60-80 ℃, and heat preservation is carried out for 20-30 min.
In another aspect of the invention, the method for preparing the hydroxyapatite coating based on the polyether-ether-ketone is provided, and the hydroxyapatite coating is a dense nano columnar structure which can be attached to the surface of bone tissue.
Due to the adoption of the technical scheme, the invention has the following beneficial effects:
1. the preparation of the hydroxyapatite active coating on the surface of the medical implant is carried out based on polyether-ether-ketone, the material has stable physical and chemical properties, the elastic modulus of the material is far lower than that of titanium and titanium alloy materials, the elastic modulus of the material is closer to that of bone tissues, and the implantation stress shielding can be effectively avoided.
2. The invention adds Ca (OH) according to a certain proportion 2 Preparation of PEEK with Ca (OH) 2 The composite substrate material can separate out calcium salt in the hydrothermal reaction process, the hydroxyapatite coating generated in situ is continuous with the interface of the substrate, the bonding strength of the coating can be effectively ensured, and simultaneously, the composite substrate material is prepared by controlling the following main process parameters: the shape and size of the hydroxyapatite crystal can be effectively controlled at the temperature (160-200 ℃) and the time (5-20 hours), the formed nano rod-shaped crystal has no fracture phenomenon, and the bonding strength of the coating and the substrate material is further improved
3. The hydroxyapatite coating prepared by the hydrothermal method effectively solves the problem of surface biological inertia of PEEK, and can promote osseointegration with bone tissues.
4. According to the invention, the hydroxyapatite active coating is prepared by a hydrothermal method, and the dense nano columnar structure coating is separated out on the surface after hydrothermal reaction, so that the surface bonding degree with bone tissues is further improved.
The preparation method adopts a hydrothermal method, has the advantages of simple steps, easy operation, high repeatability, easily obtained raw materials, low price and good application prospect, is expected to replace metal materials as medical implant materials, and is suitable for industrial large-scale production.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this application, illustrate embodiment(s) of the invention and together with the description serve to explain the principles of the invention:
FIG. 1 shows a graph of PEEK/Ca (OH) 2 Preparing a surface topography of a hydroxyapatite coating on the surface of the composite substrate material;
FIG. 2 shows a schematic representation of a process for preparing PEEK/Ca (OH) 2 The sectional shape of the hydroxyapatite coating prepared on the surface of the composite substrate material.
Detailed Description
The present invention will now be described in detail with reference to the drawings and specific embodiments, wherein the exemplary embodiments and descriptions of the present invention are provided to explain the present invention without limiting the invention thereto.
The embodiment of the invention provides a preparation method of a hydroxyapatite coating based on polyether-ether-ketone, which comprises the following steps:
1) preparing a substrate material:
according to the mass ratio (12-10): 1 mixing polyetheretherketone powder with Ca (OH) 2 Mixing the powder, ball milling, tabletting and forming, and then carrying out heat treatment at the temperature of 280-300 ℃ for 2h to obtain polyether-ether-ketone and Ca (OH) 2 A mixed composite substrate material;
2) pretreatment of the composite substrate material:
sequentially grinding and polishing the composite substrate material by 2500# and 5000# abrasive paper, sequentially placing the composite substrate material in acetone, alcohol, deionized water and alcohol solution for ultrasonic cleaning for 10-20min, removing surface dirt, and naturally air-drying to obtain a composite substrate;
3) preparing a hydrothermal solution: at room temperature, 0.02mol/L glycerol sodium dihydrogen phosphate C 3 H 7 Na 2 O 6 P and disodium calcium ethylene glycol tetraacetate C with concentration of 0.2mol/L 10 H 12 CaN 2 Na 2 O 8 Dissolving in water in sequence to prepare a hydrothermal solution, adding 0.02mol/L NaOH to adjust the pH value to 6-7, and stirring until the solution is transparent for later use;
4) preparing a coating: adding the prepared hydrothermal solution into a reaction kettle, placing the base material into the hydrothermal solution, heating to 160-180 ℃, and preserving heat for 5-20 hours;
5) and (3) post-treatment: and after the hydrothermal deposition is finished, taking out the sample, washing the sample with water, and preserving the heat for 20-30 min in a baking oven at the temperature of 60-80 ℃ to obtain the hydroxyapatite coating.
The hydroxyapatite active coating is a dense nano columnar structure coating and can be well attached to the surface of bone tissues.
The invention is further illustrated by the following specific examples.
Example 1
1) Mixing PEEK powder of polyetheretherketone with Ca (OH) 2 The powder is prepared by the following steps: 1, mixing in proportion, ball-milling, tabletting and forming, and carrying out heat treatment at 300 ℃ for 2 hours to obtain a composite substrate;
2) sequentially grinding and polishing the composite substrate with 2500# and 5000# abrasive paper, and then sequentially placing the composite substrate in acetone, alcohol, deionized water and alcohol solution for ultrasonic cleaning for 10min respectively;
3) 0.2mol/L of C 3 H 7 Na 2 O 6 P, 2mol/L of C 10 H 12 CaN 2 Na 2 O 8 Dissolving in deionized water, adding 0.02mol/L NaOH to adjust the pH value to 7, and stirring until the hydrothermal solution is transparent for later use;
4) placing the prepared hydrothermal solution and the composite substrate into a reaction kettle, and preserving heat for 15 hours at 170 ℃ to finish hydrothermal deposition;
5) taking out the sample, washing with water, and maintaining the temperature in an oven at 70 deg.C for 20min to obtain the final product in the form of PEEK and Ca (OH) 2 A hydroxyapatite coating on the surface of the composite material substrate.
The detection of PEEK and Ca (OH) 2 The nano rod-shaped hydroxyapatite is precipitated on the surface of the composite material substrate, and the particle size of the nano rod-shaped hydroxyapatite is 130-150 nm.
Example 2
Mixing PEEK powder and PEEK powderCa(OH) 2 The powder is prepared by the following steps: 1, mixing, ball milling, tabletting and forming, and then carrying out heat treatment at 280 ℃ for 2 hours to obtain a composite substrate;
2) sequentially grinding and polishing the composite substrate with 2500# and 5000# abrasive paper, and then sequentially placing the composite substrate in acetone, alcohol, deionized water and alcohol solution for ultrasonic cleaning for 20min respectively;
3) 0.2mol/L of C 3 H 7 Na 2 O 6 P, 2mol/L of C 10 H 12 CaN 2 Na 2 O 8 Dissolving in deionized water, adding 0.02mol/L NaOH to adjust the pH value to 6, and stirring until the hydrothermal solution is transparent for later use;
4) placing the prepared hydrothermal solution and the composite substrate into a reaction kettle, and preserving heat for 5 hours at 180 ℃ to finish hydrothermal deposition;
5) taking out the sample, washing with water, and maintaining the temperature in an oven at 60 deg.C for 30min to obtain the final product in the form of PEEK and Ca (OH) 2 A hydroxyapatite coating on the surface of the composite material substrate.
Detection of PEEK and Ca (OH) 2 The nano rod-shaped hydroxyapatite is precipitated on the surface of the composite material substrate, and the particle size of the nano rod-shaped hydroxyapatite is 100-130 nm.
Example 3
1) Mixing PEEK powder of polyetheretherketone with Ca (OH) 2 The powder is prepared by the following steps of 12: 1, mixing, ball milling, tabletting and forming, and then carrying out heat treatment at 300 ℃ for 2 hours to obtain a composite substrate;
2) sequentially grinding and polishing the composite substrate with 2500# and 5000# abrasive paper, and then sequentially placing the composite substrate in acetone, alcohol, deionized water and alcohol solution for ultrasonic cleaning for 15min respectively;
3) 0.2mol/L of C 3 H 7 Na 2 O 6 P, 2mol/L of C 10 H 12 CaN 2 Na 2 O 8 Dissolving in deionized water, adding 0.02mol/L NaOH to adjust the pH value to 7, and stirring until the hydrothermal solution is transparent for later use;
4) placing the prepared hydrothermal solution and the composite substrate into a reaction kettle, and preserving heat for 18 hours at 160 ℃ to finish hydrothermal deposition;
5) taking out the sample, washing the sample with water, drying the sample in an oven at the temperature of 80 ℃,maintaining the temperature for 25min to obtain a mixture of PEEK and Ca (OH) 2 A hydroxyapatite coating on the surface of the composite material substrate.
The detection of PEEK and Ca (OH) 2 The nano rod-shaped hydroxyapatite is precipitated on the surface of the composite material substrate, and the particle size of the nano rod-shaped hydroxyapatite is 50-80 nm.
Example 4
1) Mixing PEEK powder of polyetheretherketone with Ca (OH) 2 The powder is prepared by the following steps: 1, mixing, ball milling, tabletting and forming, and then carrying out heat treatment at 300 ℃ for 2 hours to obtain a composite substrate;
2) sequentially grinding and polishing the composite substrate with 2500# and 5000# abrasive paper, and then sequentially placing the composite substrate in acetone, alcohol, deionized water and alcohol solution for ultrasonic cleaning for 16min respectively;
3) 0.2mol/L of C 3 H 7 Na 2 O 6 P, 2mol/L of C 10 H 12 CaN 2 Na 2 O 8 Dissolving in deionized water, adding 0.02mol/L NaOH to adjust the pH value to 6.5, and stirring until the hydrothermal solution is transparent for later use;
4) placing the prepared hydrothermal solution and the composite substrate into a reaction kettle, and preserving heat at 175 ℃ for 10 hours to finish hydrothermal deposition;
5) taking out the sample, washing with water, and maintaining the temperature in a 65 ℃ oven for 30min to obtain the PEEK and Ca (OH) 2 A hydroxyapatite coating on the surface of the composite material substrate.
Detection of PEEK and Ca (OH) 2 The nano rod-shaped hydroxyapatite is precipitated on the surface of the composite material substrate, and the particle size of the nano rod-shaped hydroxyapatite is 110-140 nm.
Example 5
1) Mixing PEEK powder of polyetheretherketone with Ca (OH) 2 The powder is prepared by the following steps of 12: 1, mixing in proportion, ball-milling, tabletting and forming, and then carrying out heat treatment at 285 ℃ for 2 hours to obtain a composite substrate;
2) sequentially polishing the composite substrate with 2500# and 5000# abrasive paper, and then sequentially placing the composite substrate in acetone, alcohol, deionized water and alcohol solution for ultrasonic cleaning for 12min respectively;
3) 0.2mol/L of C 3 H 7 Na 2 O 6 P, 2mol/L of C 10 H 12 CaN 2 Na 2 O 8 Dissolving in deionized water, adding 0.02mol/L NaOH to adjust the pH value to 6, and stirring until the solution is transparent for later use;
4) placing the prepared hydrothermal solution and the composite substrate into a reaction kettle, and preserving heat for 8 hours at 180 ℃ to finish hydrothermal deposition;
5) taking out the sample, washing with water, and maintaining the temperature in an oven at 80 deg.C for 22min to obtain the final product in the form of PEEK and Ca (OH) 2 A hydroxyapatite coating on the surface of the composite material substrate.
Detection of PEEK and Ca (OH) 2 The nano rod-shaped hydroxyapatite is precipitated on the surface of the composite material substrate, and the particle size of the nano rod-shaped hydroxyapatite is 150-200 nm.
FIGS. 1 and 2 show the PEEK/Ca (OH) 2 The surface and cross-sectional topography of the hydroxyapatite coating prepared on the surface of the composite substrate material can be seen, the coating prepared by the method is of a dense nano columnar structure and is firmly combined with a matrix, the problem of biological inertia of the PEEK surface can be effectively solved, the coating can be well attached to the surface of bone tissues, the osteogenesis function of cells is remarkably promoted, and the implantation and use of the substrate material are facilitated.
The present invention is not limited to the above-mentioned embodiments, and based on the technical solutions disclosed in the present invention, those skilled in the art can make some substitutions and modifications to some technical features without creative efforts according to the disclosed technical contents, and these substitutions and modifications are all within the protection scope of the present invention.
Claims (6)
1. A preparation method of a hydroxyapatite coating based on polyether-ether-ketone is characterized by comprising the following steps:
preparing a substrate material: according to the mass ratio (12-10): 1 mixing polyetheretherketone powder with Ca (OH) 2 Mixing the powder, ball milling, tabletting, forming and then carrying out heat treatment at the temperature of 280-300 ℃ for 2h to obtain polyether-ether-ketone and Ca (OH) 2 A mixed composite substrate material;
pretreatment of the composite substrate material: polishing the composite substrate material, then ultrasonically cleaning, removing dirt on the surface, and naturally drying;
preparing a hydrothermal solution: sodium glycerophosphate C 3 H 7 Na 2 O 6 P and disodium calcium ethylene tetraacetate C 10 H 12 CaN 2 Na 2 O 8 Dissolving in water in sequence to prepare a hydrothermal solution, and adjusting the pH value to 6-7;
preparing a hydroxyapatite coating: adding the prepared hydrothermal solution into a reaction kettle, placing the substrate material into the hydrothermal solution, heating to 160-180 ℃, and preserving heat for 5-20 hours to complete hydrothermal deposition;
and (3) post-treatment: washing, drying and insulating the hydrothermal deposition sample to obtain PEEK and Ca (OH) 2 The particle size of the surface of the composite material substrate is 150-200 nm of the nano rod-shaped hydroxyapatite coating.
2. The method for preparing a polyetheretherketone-based hydroxyapatite coating according to claim 1, characterized in that the composite substrate material is pre-treated: and (3) sequentially grinding and polishing the composite substrate material by 2500# and 5000# sandpaper, and then sequentially placing the composite substrate material in acetone, deionized water and alcohol solution for ultrasonic cleaning for 10-20min respectively.
3. The method for preparing a PEEK-based hydroxyapatite coating according to claim 1, wherein the sodium glycerophosphate is prepared as a hydrothermal solution 3 H 7 Na 2 O 6 The concentration of P is 0.02mol/L, and the oxalic acid tetraacetic acid disodium calcium disodium salt C 10 H 12 CaN 2 Na 2 O 8 The concentration of (2) was 0.2 mol/L.
4. The method for preparing a PEEK-based hydroxyapatite coating according to claim 1, wherein the pH is adjusted with 0.02mol/L NaOH.
5. The preparation method of the PEEK-based hydroxyapatite coating according to claim 1, wherein the coating is further subjected to drying treatment at 60-80 ℃ after the preparation, and the temperature is kept for 20-30 min.
6. The PEEK-based hydroxyapatite coating prepared according to any one of claims 1 to 5, wherein the hydroxyapatite coating has a dense nano-columnar structure capable of being attached to a bone tissue surface.
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