CN113633824A - A kind of hydroxyapatite coating based on polyetheretherketone and preparation method thereof - Google Patents
A kind of hydroxyapatite coating based on polyetheretherketone and preparation method thereof Download PDFInfo
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- CN113633824A CN113633824A CN202110984579.XA CN202110984579A CN113633824A CN 113633824 A CN113633824 A CN 113633824A CN 202110984579 A CN202110984579 A CN 202110984579A CN 113633824 A CN113633824 A CN 113633824A
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- 239000004696 Poly ether ether ketone Substances 0.000 title claims abstract description 66
- 229920002530 polyetherether ketone Polymers 0.000 title claims abstract description 66
- 238000000576 coating method Methods 0.000 title claims abstract description 59
- 239000011248 coating agent Substances 0.000 title claims abstract description 58
- 229910052588 hydroxylapatite Inorganic materials 0.000 title claims abstract description 56
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000000758 substrate Substances 0.000 claims abstract description 64
- 239000002131 composite material Substances 0.000 claims abstract description 56
- 239000000463 material Substances 0.000 claims abstract description 39
- 238000002156 mixing Methods 0.000 claims abstract description 21
- 239000000843 powder Substances 0.000 claims abstract description 20
- 210000000988 bone and bone Anatomy 0.000 claims abstract description 18
- 238000000151 deposition Methods 0.000 claims abstract description 13
- 230000008021 deposition Effects 0.000 claims abstract description 13
- 238000010438 heat treatment Methods 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 7
- JUPQTSLXMOCDHR-UHFFFAOYSA-N benzene-1,4-diol;bis(4-fluorophenyl)methanone Chemical compound OC1=CC=C(O)C=C1.C1=CC(F)=CC=C1C(=O)C1=CC=C(F)C=C1 JUPQTSLXMOCDHR-UHFFFAOYSA-N 0.000 claims abstract 10
- 239000011575 calcium Substances 0.000 claims description 30
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 239000011734 sodium Substances 0.000 claims description 20
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 239000008367 deionised water Substances 0.000 claims description 13
- 229910021641 deionized water Inorganic materials 0.000 claims description 13
- 238000000498 ball milling Methods 0.000 claims description 10
- 238000005498 polishing Methods 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 8
- 238000000227 grinding Methods 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 238000004321 preservation Methods 0.000 claims description 4
- -1 oxalic acid tetraacetic acid disodium calcium disodium salt Chemical compound 0.000 claims description 3
- SOEPCIGHLITESD-UHFFFAOYSA-J C(C)(=O)[O-].C(C)(=O)[O-].C(C)(=O)[O-].C(C)(=O)[O-].C=C.[Na+].[Na+].[Ca+2] Chemical compound C(C)(=O)[O-].C(C)(=O)[O-].C(C)(=O)[O-].C(C)(=O)[O-].C=C.[Na+].[Na+].[Ca+2] SOEPCIGHLITESD-UHFFFAOYSA-J 0.000 claims description 2
- QMIDDQFZXOSYIL-UHFFFAOYSA-K [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O.OCC(O)CO Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O.OCC(O)CO QMIDDQFZXOSYIL-UHFFFAOYSA-K 0.000 claims description 2
- 238000004140 cleaning Methods 0.000 claims description 2
- 230000007935 neutral effect Effects 0.000 claims description 2
- XJOHAKBCTNXARA-UHFFFAOYSA-M sodium;dihydrogen phosphate;propane-1,2,3-triol Chemical compound [Na+].OP(O)([O-])=O.OCC(O)CO XJOHAKBCTNXARA-UHFFFAOYSA-M 0.000 claims description 2
- 238000002203 pretreatment Methods 0.000 claims 1
- 238000002513 implantation Methods 0.000 abstract description 4
- DMGNFLJBACZMRM-UHFFFAOYSA-N O[P] Chemical compound O[P] DMGNFLJBACZMRM-UHFFFAOYSA-N 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 238000000465 moulding Methods 0.000 abstract 1
- 230000002188 osteogenic effect Effects 0.000 abstract 1
- 239000007943 implant Substances 0.000 description 10
- 238000001027 hydrothermal synthesis Methods 0.000 description 8
- 238000003756 stirring Methods 0.000 description 6
- 238000001514 detection method Methods 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 239000012467 final product Substances 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 239000013078 crystal Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000010883 osseointegration Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 229910001069 Ti alloy Inorganic materials 0.000 description 2
- 238000002591 computed tomography Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002073 nanorod Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 230000017423 tissue regeneration Effects 0.000 description 2
- 238000012876 topography Methods 0.000 description 2
- 208000003076 Osteolysis Diseases 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000443 aerosol Substances 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 239000013566 allergen Substances 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- AWUCVROLDVIAJX-UHFFFAOYSA-N alpha-glycerophosphate Natural products OCC(O)COP(O)(O)=O AWUCVROLDVIAJX-UHFFFAOYSA-N 0.000 description 1
- 229910052586 apatite Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003519 biomedical and dental material Substances 0.000 description 1
- 230000008468 bone growth Effects 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 238000010288 cold spraying Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000035876 healing Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 208000029791 lytic metastatic bone lesion Diseases 0.000 description 1
- 238000002595 magnetic resonance imaging Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- XONPDZSGENTBNJ-UHFFFAOYSA-N molecular hydrogen;sodium Chemical compound [Na].[H][H] XONPDZSGENTBNJ-UHFFFAOYSA-N 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 230000011164 ossification Effects 0.000 description 1
- VSIIXMUUUJUKCM-UHFFFAOYSA-D pentacalcium;fluoride;triphosphate Chemical compound [F-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O VSIIXMUUUJUKCM-UHFFFAOYSA-D 0.000 description 1
- 238000007750 plasma spraying Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- AWUCVROLDVIAJX-GSVOUGTGSA-N sn-glycerol 3-phosphate Chemical compound OC[C@@H](O)COP(O)(O)=O AWUCVROLDVIAJX-GSVOUGTGSA-N 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 230000004938 stress stimulation Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/28—Materials for coating prostheses
- A61L27/30—Inorganic materials
- A61L27/32—Phosphorus-containing materials, e.g. apatite
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/02—Inorganic materials
- A61L27/025—Other specific inorganic materials not covered by A61L27/04 - A61L27/12
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/14—Macromolecular materials
- A61L27/18—Macromolecular materials obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L2400/00—Materials characterised by their function or physical properties
- A61L2400/12—Nanosized materials, e.g. nanofibres, nanoparticles, nanowires, nanotubes; Nanostructured surfaces
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L2400/00—Materials characterised by their function or physical properties
- A61L2400/18—Modification of implant surfaces in order to improve biocompatibility, cell growth, fixation of biomolecules, e.g. plasma treatment
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L2420/00—Materials or methods for coatings medical devices
- A61L2420/02—Methods for coating medical devices
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L2430/00—Materials or treatment for tissue regeneration
- A61L2430/02—Materials or treatment for tissue regeneration for reconstruction of bones; weight-bearing implants
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Abstract
本发明公开了一种基于聚醚醚酮的羟基磷灰石涂层及制备方法，包括采用聚醚醚酮粉末与Ca(OH)2粉末混合，压片成型、热处理，得到复合基底材料；复合基底材料预处理；将基底材料置于水热溶液，加热，完成水热沉积；水热沉积试样冲洗、烘干、保温，即得在PEEK与Ca(OH)2复合材料基底表面的羟基磷灰石涂层。该方法制备的涂层为密集纳米柱状结构，与基体结合牢固，可有效解决PEEK表面生物惰性问题，实现与骨组织表面较好贴合，显著促进细胞的成骨功能，有助于基底材料的植入使用；适用于工业化大规模生产，具有良好的应用前景。
The invention discloses a polyether ether ketone-based hydroxyapatite coating and a preparation method, which include mixing polyether ether ketone powder and Ca(OH) 2 powder, tablet molding and heat treatment to obtain a composite base material; Pretreatment of the base material; placing the base material in a hydrothermal solution and heating to complete the hydrothermal deposition; rinsing, drying, and keeping warm of the hydrothermal deposition sample, that is, to obtain the hydroxyphosphorus on the surface of the PEEK and Ca(OH) 2 composite substrate Greystone coating. The coating prepared by this method has a dense nano-column structure, which is firmly combined with the substrate, which can effectively solve the problem of biological inertness on the surface of PEEK, achieve better adhesion with the surface of bone tissue, significantly promote the osteogenic function of cells, and help the substrate material. Implantation use; suitable for industrial mass production, with good application prospects.
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)2Mixing the powders, ball milling, tabletting, and heat treating to obtain polyetheretherketone and Ca (OH)2A 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 C3H7Na2O6P and disodium calcium ethylene tetraacetate C10H12CaN2Na2O8Dissolving 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)2A hydroxyapatite coating on the surface of the composite material substrate.
Preferably, PEEK is reacted with Ca (OH)2And 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 solution3H7Na2O6The concentration of P is 0.02mol/L, and the oxalic acid tetraacetic acid disodium calcium disodium salt C10H12CaN2Na2O8The 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 proportion2Preparation of PEEK with Ca (OH)2Composite substrateThe 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 main process parameters are controlled: 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)2Preparing a surface topography of a hydroxyapatite coating on the surface of the composite substrate material;
FIG. 2 shows a graph of PEEK/Ca (OH)2The 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)2Mixing 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)2A 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 C3H7Na2O6P and disodium calcium ethylene glycol tetraacetate C with concentration of 0.2mol/L10H12CaN2Na2O8Dissolving 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 tissue.
The invention is further illustrated by the following specific examples.
Example 1
1) Mixing PEEK powder of polyetheretherketone with Ca (OH)2The 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 C3H7Na2O6P, 2mol/L of C10H12CaN2Na2O8Dissolving 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)2A hydroxyapatite coating on the surface of the composite material substrate.
Detection of PEEK and Ca (OH)2The 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 of polyetheretherketone with Ca (OH)2The 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 C3H7Na2O6P, 2mol/L of C10H12CaN2Na2O8Dissolving 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)2A hydroxyapatite coating on the surface of the composite material substrate.
Detection of PEEK and Ca (OH)2The 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)2The 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 C3H7Na2O6P, 2mol/L of C10H12CaN2Na2O8Dissolving 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 with water, and maintaining the temperature in an oven at 80 deg.C for 25min to obtain the final product in the form of PEEK and Ca (OH)2A hydroxyapatite coating on the surface of the composite material substrate.
Detection of PEEK and Ca (OH)2The 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)2The powder is prepared by the following steps of 11: 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 C3H7Na2O6P, 2mol/L of C10H12CaN2Na2O8Dissolving 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 testWashing with water, and maintaining in 65 deg.C oven for 30min to obtain a mixture of PEEK and Ca (OH)2A hydroxyapatite coating on the surface of the composite material substrate.
Detection of PEEK and Ca (OH)2The 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)2The 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) polishing the composite substrate by using 2500# and 5000# abrasive paper in sequence, 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 C3H7Na2O6P, 2mol/L of C10H12CaN2Na2O8Dissolving 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)2A hydroxyapatite coating on the surface of the composite material substrate.
Detection of PEEK and Ca (OH)2The 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 results in PEEK/Ca (OH)2The surface and cross-sectional topography of the hydroxyapatite coating prepared on the surface of the composite substrate material can be seen from the figure, 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 tissue, the osteogenesis function of cells is remarkably promoted, and the implantation use of the substrate material is 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 (8)
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)2Mixing the powders, ball milling, tabletting, and heat treating to obtain polyetheretherketone and Ca (OH)2A 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 C3H7Na2O6P and disodium calcium ethylene tetraacetate C10H12CaN2Na2O8Dissolving 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)2A hydroxyapatite coating on the surface of the composite material substrate.
2. The method for preparing a PEEK-based hydroxyapatite coating according to claim 1, wherein PEEK is mixed with Ca (OH)2And 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.
3. The method for preparing a polyetheretherketone-based hydroxyapatite coating according to claim 1, characterized in that the composite substrate material pre-treatment: 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.
4. The method for preparing a PEEK-based hydroxyapatite coating according to claim 1, wherein the glycerol sodium dihydrogen phosphate (HCP) is used as a hydrothermal solution3H7Na2O6The concentration of P is 0.02mol/L, and the oxalic acid tetraacetic acid disodium calcium disodium salt C10H12CaN2Na2O8The concentration of (2) was 0.2 mol/L.
5. The method for preparing a PEEK-based hydroxyapatite coating according to claim 1, wherein the pH value is adjusted to 6-7 with 0.02mol/L NaOH.
6. The method for preparing a PEEK-based hydroxyapatite coating according to claim 1, wherein the temperature of the hydrothermal solution is 160-180 ℃ and the holding time is 5-20 hours when the hydroxyapatite coating is prepared.
7. 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.
8. The PEEK-based hydroxyapatite coating prepared according to any one of claims 1 to 7, wherein the hydroxyapatite coating has a dense nano-columnar structure capable of conforming to a bone tissue surface.
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