CN114712558B - Polyether-ether-ketone biological composite powder and preparation method and application thereof - Google Patents

Polyether-ether-ketone biological composite powder and preparation method and application thereof Download PDF

Info

Publication number
CN114712558B
CN114712558B CN202210272065.6A CN202210272065A CN114712558B CN 114712558 B CN114712558 B CN 114712558B CN 202210272065 A CN202210272065 A CN 202210272065A CN 114712558 B CN114712558 B CN 114712558B
Authority
CN
China
Prior art keywords
powder
laser
polyetheretherketone
codeposition
ether
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202210272065.6A
Other languages
Chinese (zh)
Other versions
CN114712558A (en
Inventor
闫春泽
王浩则
袁熙
陈鹏
苏瑾
伍宏志
张贞
杨操
史玉升
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Huazhong University of Science and Technology
Original Assignee
Huazhong University of Science and Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Huazhong University of Science and Technology filed Critical Huazhong University of Science and Technology
Priority to CN202210272065.6A priority Critical patent/CN114712558B/en
Publication of CN114712558A publication Critical patent/CN114712558A/en
Application granted granted Critical
Publication of CN114712558B publication Critical patent/CN114712558B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • 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
    • A61L27/28—Materials for coating prostheses
    • A61L27/30—Inorganic materials
    • A61L27/306—Other specific inorganic materials not covered by A61L27/303 - A61L27/32
    • 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
    • A61L27/50—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
    • 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
    • A61L27/54—Biologically active materials, e.g. therapeutic substances
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
    • B29C64/10—Processes of additive manufacturing
    • B29C64/141—Processes of additive manufacturing using only solid materials
    • B29C64/153—Processes of additive manufacturing using only solid materials using layers of powder being selectively joined, e.g. by selective laser sintering or melting
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y10/00—Processes of additive manufacturing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y70/00—Materials specially adapted for additive manufacturing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y80/00—Products made by additive manufacturing
    • 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
    • A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
    • A61L2300/10—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices containing or releasing inorganic materials
    • A61L2300/102—Metals or metal compounds, e.g. salts such as bicarbonates, carbonates, oxides, zeolites, silicates
    • 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
    • A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
    • A61L2300/10—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices containing or releasing inorganic materials
    • A61L2300/102—Metals or metal compounds, e.g. salts such as bicarbonates, carbonates, oxides, zeolites, silicates
    • A61L2300/104—Silver, e.g. silver sulfadiazine
    • 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
    • A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
    • A61L2300/40—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices characterised by a specific therapeutic activity or mode of action
    • A61L2300/404—Biocides, antimicrobial agents, antiseptic agents
    • 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
    • A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
    • A61L2300/40—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices characterised by a specific therapeutic activity or mode of action
    • A61L2300/416—Anti-neoplastic or anti-proliferative or anti-restenosis or anti-angiogenic agents, e.g. paclitaxel, sirolimus
    • 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
    • A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
    • A61L2300/40—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices characterised by a specific therapeutic activity or mode of action
    • A61L2300/426—Immunomodulating agents, i.e. cytokines, interleukins, interferons
    • 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
    • A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
    • A61L2300/60—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices characterised by a special physical form
    • A61L2300/606—Coatings
    • 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
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/25—Process efficiency

Landscapes

  • Health & Medical Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Medicinal Chemistry (AREA)
  • Public Health (AREA)
  • Transplantation (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Oral & Maxillofacial Surgery (AREA)
  • Veterinary Medicine (AREA)
  • Dermatology (AREA)
  • Epidemiology (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Physics & Mathematics (AREA)
  • Inorganic Chemistry (AREA)
  • Optics & Photonics (AREA)
  • Biomedical Technology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Molecular Biology (AREA)
  • Mechanical Engineering (AREA)
  • Materials For Medical Uses (AREA)

Abstract

The invention belongs to the technical field related to biological composite materials, and discloses polyether-ether-ketone biological composite powder as well as a preparation method and application thereof, wherein the preparation method comprises the following steps: (1) Carrying out surface modification on the polyether-ether-ketone powder by adopting oxygen plasma; (2) Mixing Ca (NO) 3 ) 2 ·4H 2 0 as Ca source, na 3 PO 4 As P source, X (NO) 3 ) y Adding the polyether-ether-ketone powder serving as a required functional element source and a pH regulator into deionized water to obtain a codeposition reactant, and then adding the polyether-ether-ketone powder into the codeposition reactant to perform codeposition reaction so as to obtain polyether-ether-ketone biological composite powder; x includes any one or more of an antibacterial element, an element having an immunoregulatory and anticancer function, an element having a photothermal anticancer property, and an element promoting an angiogenic property. The polyetheretherketone biological composite powder obtained by the method can simultaneously have the characteristics of osteogenesis, antibiosis, immunoregulation, cancer resistance and the like.

Description

Polyether-ether-ketone biological composite powder and preparation method and application thereof
Technical Field
The invention belongs to the technical field related to biological composite materials, and particularly relates to polyether-ether-ketone biological composite powder and a preparation method and application thereof.
Background
Polyetheretherketone is a semi-crystalline polymer, which not only has excellent biocompatibility, chemical stability, wear resistance and elastic modulus matched with human cortical bone, but also has no artifacts in CT or MRI images, does not affect postoperative image analysis, and thus has wide clinical applications. On the other hand, due to the clinical need of individuation and complicated porous lattice implants in orthopedics, the 3D printing technology becomes an effective way to prepare the polyetheretherketone bone implant. The selective laser sintering is a mainstream 3D printing technology, and is based on the thinking of discrete accumulation forming, a laser is controlled to selectively sinter powder layers according to interface information of each layer of a CAD model, and the designed three-dimensional solid parts are manufactured layer by layer and superposed. In the printing process, the unsintered powder can support the cavity and the cantilever part of the workpiece without additional design support, so that a more complicated structure can be formed, and the method is very suitable for forming and preparing a complicated and personalized polyether-ether-ketone bone implant.
However, polyetheretherketone is a biologically inert material and has a weak osteogenic capacity, which limits its clinical application in orthopaedics. In addition, there are many problems other than osteogenesis in orthopedics clinic, such as inflammation, bacterial infection, and incomplete removal of tumor cells involved in osteosarcoma surgery, which may be caused after implantation.
In order to solve the problems, the method adopted at present is to carry out biological blending modification on the polyetheretherketone powder to realize osteogenesis and other biological functions. Some solutions have been proposed in the prior art, for example, patent CN112276109B discloses a forming method and product of a porous bone implant of polyetheretherketone parent metal, which uses a mechanical mixing method to prepare a polyetheretherketone/parent metal composite material for laser selective sintering forming, however, the method is limited to promoting the bone forming ability of polyetheretherketone powder. In addition, because of the large difference in density between metal and polyetheretherketone, it is difficult to prepare a uniformly mixed composite powder material; for another example, patent CN108517104B discloses a polyetheretherketone composite material and a preparation method thereof, which increases the bioactivity and wear resistance of polyetheretherketone by mechanically mixing nano-diamond alkene and nano-titanium dioxide. However, in the composite material prepared by the method, the nano particles are easy to agglomerate, so that the biological performance and the mechanical performance of the composite material are reduced, and even the sintering forming in the laser selection area fails. And patent CN105061989A discloses a polyetheretherketone/nano-hydroxyapatite composite material for SLS technology and a preparation method thereof, wherein the composite material prepared by the method has single function, and the nano-hydroxyapatite and polyetheretherketone powder are easy to agglomerate due to weak binding force.
Disclosure of Invention
Aiming at the defects or improvement requirements of the prior art, the invention provides the polyetheretherketone biological composite powder, and the preparation method and the application thereof, the polyetheretherketone biological composite powder is prepared by depositing a layer of nano multi-element hydroxyapatite coating on the surface of matrix powder in a multi-element codeposition mode, so that the polyetheretherketone biological composite powder not only has osteogenesis performance, but also selectively has antibacterial, immune and anticancer functions, and the problems of single function and uneven dispersion of the traditional polyetheretherketone biological activity composite powder are solved. In addition, the problem that the surface of the polyether-ether-ketone composite material instantaneously absorbs overhigh energy to degrade a base material when the polyether-ether-ketone composite material is irradiated by laser due to the change of the surface thermal property and the laser absorption property in the forming process is solved.
In order to achieve the above object, according to one aspect of the present invention, there is provided a method for preparing a peek bio-composite powder, comprising the steps of:
(1) Oxygen plasma is adopted to carry out surface modification on the polyether-ether-ketone powder so as to introduce polar groups;
(2) Mixing Ca (NO) 3 ) 2 ·4H 2 0 as Ca source, na 3 PO 4 As P source, X (NO) 3 ) y Adding the PEEK powder modified by oxygen plasma into the codeposition reactant to carry out codeposition reaction, and forming a codeposition layer on the surface of the PEEK powder so as to obtain PEEK biological composite powder;
wherein X is a functional element, and comprises one or more of antibacterial element, element with immunoregulation and anticancer functions, element with photothermal anticancer property, and element with angiogenesis promoting property.
Further, the ratio of the volume of the codeposition reactant to the mass of the polyetheretherketone powder is 1 (L) to 0.1-0.4 (kg); the temperature of the codeposition reaction is 150-200 ℃, the stirring speed is 50-100 rpm, and the reaction time is 12-36h.
Further, ca (NO) in the co-deposition reactant obtained by stirring 3 ) 2 ·4H 2 0、Na 3 PO 4 All the concentrations of (a) and (b) are 20 to 40mol/L and satisfy (n) Ca(NO3)2.4H20 +y·n X(NO3)y /2)：n Na3PO4 ＝10:6，0≤n≤4。
Further, the pH value of the codeposition reactant is 7-10.
Further, (10-n/2) Ca 2+ +(n/y)X y+ +6PO 4 3- +2H 2 0＝Ca (10-n/2) X (n/y) (PO 4 ) 6 (OH) 2 +2H + ；
Wherein n is more than or equal to 0 and less than or equal to 4.
Further, the step (2) is followed by a step of heat treatment of the polyetheretherketone biological composite material; wherein the heat treatment temperature is 270-310 ℃, and the heat treatment time is 4-12 h.
According to another aspect of the present invention, the present invention provides a polyetheretherketone biocomposite powder prepared by the method for preparing a polyetheretherketone biocomposite powder as described above.
The invention also provides application of the polyetheretherketone biological composite powder in selective laser sintering and forming of an implant, which comprises the following steps:
(1) Putting the polyether-ether-ketone biological composite powder into selective laser sintering equipment for powder paving;
(2) Adopting a laser 1 and a laser 2 to perform interval printing to obtain a sample, and performing sand blasting treatment on the sample to obtain an implant; wherein, each layer of scanning paths of the laser 1 and the laser 2 are set to be the same, the laser 1 is set to scan firstly, and the laser 2 starts scanning after the temperature of a scanning area is reduced to 350 ℃ under the monitoring of a thermal infrared imager.
Further, the preheating temperature during processing is set to 330 ℃, and the process parameters of the laser 1 are as follows: the laser power is 5-45W, the scanning speed is 1000-4000 mm/s, the filling space is 0.1-0.3 mm, and the layer thickness is 0.05-0.25 mm; the process parameters of the laser 2 are as follows: the laser power is 5-45W, the scanning speed is 1000-4000 mm/s, the filling space is 0.1-0.3 mm, and the layer thickness is 0.05-0.25 mm.
Furthermore, the energy density of the energy input by the laser 1 and the laser 2 is 0.314-0.942J/mm 3 (ii) a Energy density E of laser 2 during machining vol Lower than the laser 1, by a value approximately equal to the energy E required for melting the powder per unit volume m (ii) a Bulk energy density E vol The formula of (1) is:
Figure BDA0003553899990000041
wherein P is the filling power, S is the scanning distance, V is the filling speed, and h is the layer thickness;
E m the formula of (1) is:
Figure BDA0003553899990000042
wherein E is m Is the energy required for melting the powder per unit volume, C p Is the specific heat capacity of the polyetheretherketone powder,
Figure BDA0003553899990000043
is the equilibrium melting point, T, of the polyetheretherketone powder b Is the powder preheating temperature,. DELTA.H m Is the melting enthalpy, P, of the polyetheretherketone powder d Is the bulk density of the powder.
Generally, compared with the prior art, the polyetheretherketone biological composite powder and the preparation method and application thereof provided by the invention have the following beneficial effects:
1. the invention can simultaneously introduce nano hydroxyapatite and a plurality of functional elements by a multi-element codeposition mode, and the obtained polyetheretherketone biological composite powder can simultaneously have the characteristics of osteogenesis, antibiosis, immunoregulation, cancer resistance and the like.
2. The polar group is introduced to the surface of the polyether-ether-ketone powder in an oxygen plasma modification mode, the van der Waals force of a polyether-ether-ketone interface and a co-deposition layer is improved, so that the binding force is improved, the composite powder is subjected to heat treatment to eliminate internal stress, the polyether-ether-ketone is subjected to fine viscous deformation to be bonded with the nano co-deposition layer, and the binding force is further improved.
3. The co-deposition is adopted to ensure that the bioactive material is attached to the polyetheretherketone powder in a coating mode, so that the distribution of nano-hydroxyapatite and functional elements of a printed sample is more uniform, agglomeration cannot be caused, the sphericity of the powder can be increased, and the printability of the powder is improved.
4. By adopting a forming mode of double-laser interval printing, the situation that the surface of the polyetheretherketone composite powder instantly absorbs too high energy to degrade a polyetheretherketone matrix is avoided, and the crystallization of polyetheretherketone is promoted due to the existence of the nano-hydroxyapatite crystals, so that the mechanical property of a printed sample is remarkably improved.
5. The pH value of the codeposition reactant is 7-10, when the pH value exceeds 10, the binding force of the codeposition layer can be rapidly weakened, and when the pH value is lower than 7, the codeposition reaction can not occur.
Drawings
FIG. 1 is a schematic diagram of the preparation method and application process of the polyetheretherketone biological composite powder provided by the invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
In the prior art, the common blending biological modification has the problems of difficult uniform dispersion and easy agglomeration, so that the polyether-ether-ketone composite powder is difficult to be used for selective laser sintering and forming. Aiming at the technical defect, the invention provides a novel method for preparing polyetheretherketone biological composite powder, which utilizes multi-element codeposition reaction to codeposit a layer of nano-hydroxyapatite coating containing specific functional elements on the surface of the polyetheretherketone powder, so that the polyetheretherketone biological composite powder not only has biological activity and specific functional characteristics, but also is suitable for laser selective sintering forming, but the realization of the purpose in experiments is found to face the following technical difficulties: (1) The weak bonding force of the codeposition layer and the powder can cause the part of the codeposition layer to fall off in the printing process; (2) The prepared polyetheretherketone biological composite material has the advantages that the surface of the prepared polyetheretherketone biological composite material is wrapped by a multi-element codeposition layer, so that the thermal property and the laser absorption property of the prepared polyetheretherketone biological composite material are greatly changed, if a printing method of pure polyetheretherketone is adopted, the material is severely degraded, and if the process parameters are changed to reduce the energy density, the mechanical property of a printed sample is poor.
Referring to fig. 1, the present invention provides a method for preparing polyetheretherketone bio-composite powder, wherein the method comprises using polyetheretherketone powder as a matrix and Ca (NO) as a carrier 3 ) 2 ·4H 2 0 and Na 3 PO 4 Taking specific salt as an element source of a required element as a precursor, and codepositing a layer of nano hydroxyapatite coating containing the specific element on the surface of the polyetheretherketone powder by utilizing a hydrothermal codeposition reaction, and the method comprises the following specific steps:
(1) Screening medical grade polyetheretherketone powder with the grain diameter of 10-100 mu m, and carrying out surface modification on the medical grade polyetheretherketone powder by an oxygen plasma method so as to introduce polar groups.
The oxygen plasma treatment is carried out on the polyether-ether-ketone powder so as to introduce polar groups, and then the van der Waals force is improved so as to greatly improve the bonding force between the codeposition layer and the polyether-ether-ketone matrix. The oxygen plasma treatment comprises the following specific steps: the polyether-ether-ketone powder is put into a low-temperature plasma processing instrument, the parameters of the instrument are adjusted to be 50-100W, the vacuum degree is 25Pa, the oxygen flow is 10-50 mL/min, and the processing time is 5-20 min.
(2) Selecting Ca (NO) 3 ) 2 ·4H 2 0 as Ca source, na 3 PO 4 As P source, X (NO) 3 ) y Adding the co-deposition reactant serving as a required functional element source and a pH regulator into deionized water, uniformly stirring to obtain a co-deposition reactant, adding the co-deposition reactant into a high-pressure reaction kettle with a stirring paddle inside, adding the plasma-modified polyether-ether-ketone to perform a co-deposition reaction, and naturally cooling to room temperature along with the reaction kettle.
Wherein y is the valence of the element X; stirring the resulting co-precipitated Ca (NO) in the reactant 3 ) 2 ·4H 2 0、Na 3 PO 4 All the concentrations of (a) and (b) are 20 to 40mol/L and satisfy (n) Ca(NO3)2.4H20 +y·n X(NO3)y /2)：n Na3PO4 6,0. Ltoreq. N.ltoreq.4. When the concentration of the reactant is too high, the deposited layer may be too thick to be peeled off. X can be Ag, cu, zn and other antibacterial elements, sr and other elements with immunoregulation and anticancer functions, au and other elements with photothermal anticancer properties, mg and other elements with angiogenesis promoting properties, and X can be one or more of the above elements. The ratio of the volume of the codeposition reactant to the mass of the polyetheretherketone is 1 (L) and 0.1-0.4 (kg). In addition, the height of the liquid level can not exceed 2/3 of the height of the reaction kettle, the temperature of the reaction kettle is 150-200 ℃, the stirring speed is 50-100 rpm, and the reaction time is 12-36h.
Further, 170-190 ℃ is the optimal reaction temperature interval for preparing the codeposition coating; the pH value of the reaction is 7-10, when the pH value exceeds 10, the binding force of the codeposition layer can be rapidly weakened, and when the pH value is lower than 7, the sedimentation reaction can not occur.
The ion reaction equation for codeposition is:
(10-n/2)Ca 2+ +(n/y)X y+ +6PO 4 3- +2H 2 0＝Ca (10-n/2) X (n/y) (PO 4 ) 6 (OH) 2 +2H +
wherein n is more than or equal to 0 and less than or equal to 4.
(3) And filtering and taking out the reacted polyether-ether-ketone biological composite material, putting the material into an oven for heat treatment to reduce the internal stress of the co-deposition layer on the powder, enabling the polyether-ether-ketone to generate fine viscous deformation to adhere to the nano co-deposition layer, further increasing the contact area between the co-deposition layer and the matrix so as to improve the bonding force, and finally naturally cooling the material to room temperature to obtain the required polyether-ether-ketone biological composite powder.
Wherein the heat treatment temperature of the obtained polyetheretherketone biological composite powder is 270-310 ℃, and the heat treatment time is 4-12 h.
The invention also provides the polyetheretherketone biological composite powder which is prepared by the preparation method of the polyetheretherketone biological composite powder.
The invention also provides application of the polyetheretherketone biological composite powder in selective laser sintering and forming of an implant, wherein the selective laser sintering and forming method is used for forming the implant by taking the polyetheretherketone biological composite powder as a raw material, and specifically comprises the following steps:
(a) And (3) placing the prepared polyether-ether-ketone biological composite powder into selective laser sintering equipment for powder paving.
(b) After the temperature rises to the preheating temperature, a double-laser interval printing mode is adopted, namely the scanning paths of each layer of the laser 1 and the laser 2 are set to be the same, the laser 1 is set to scan firstly, and under the monitoring of a thermal infrared imager, when the temperature of a scanning area is reduced to 350 ℃, the laser 2 starts scanning. And after printing is finished, naturally cooling, taking out the sample, and carrying out sand blasting treatment on the sample to obtain the implant.
Wherein, the time required for the material to absorb the laser energy is far less than the time required for heat transfer in the selective laser sintering forming process. The surface of the material absorbs all laser energy in a very short time, so that the temperature rises to a very high value, and then the heat is transferred to other areas to be cooled. The surface of the polyether-ether-ketone biological composite material prepared by the embodiment has a multi-element codeposition layer with high thermal conductivity and low specific heat capacity, and the main body of the material is nano-hydroxyapatite, so that the material has high laser absorption rate and the temperature is obviously improved compared with a pure polyether-ether-ketone material. Therefore, the polyether-ether-ketone composite material is printed at intervals by adopting double lasers, heat transfer is buffered, and the surface is prevented from being degraded due to instantaneous absorption of overhigh energy.
In some embodiments, the preheating temperature during processing is set to 330 ℃, and the process parameters of the laser 1 are as follows: the laser power is 5-45W, the scanning speed is 1000-4000 mm/s, the filling space is 0.1-0.3 mm, and the layer thickness is 0.05-0.25 mm. The process parameters of the laser 2 are as follows: the laser power is 5-45W, the scanning speed is 1000-4000 mm/s, the filling space is 0.1-0.3 mm, and the layer thickness is 0.05-0.25 mm. The energy density of the input energy of the laser 1 and the laser 2 is 0.314-0.942J/mm 3 . Energy density E of laser 2 during machining vol Lower than the laser 1, by a value approximately equal to the energy E required for melting the powder per unit volume m 。
Definition of the volume energy Density E vol The formula of (1) is:
Figure BDA0003553899990000081
where P is the fill power, S is the scan pitch, V is the fill velocity, and h is the layer thickness.
E m The formula of (1) is:
Figure BDA0003553899990000082
wherein, E m Is the energy required for melting the powder per unit volume, C p The specific heat capacity (2.2J/kg. DEG C) of the polyether-ether-ketone powder,
Figure BDA0003553899990000083
is the equilibrium melting point (380.5 ℃) of the polyetheretherketone powder b Is the powder preheating temperature (330 ℃), Δ H m Is the melting enthalpy (58.6J/g), P, of the polyetheretherketone powder d Is the bulk density of the powder (0.37 g/cm) 3 ). Calculated to obtain E m Is 0.0628J/mm 3 。
The present invention is further described in detail below with reference to several specific examples.
Example 1
(1) Powder plasma treatment: screening 400g of medical grade polyetheretherketone powder with the particle size of 10-100 mu m, putting the polyetheretherketone powder into a low-temperature plasma treatment instrument, adjusting the parameters of the instrument to be 50W, the vacuum degree to be 25Pa, the oxygen flow to be 50mL/min, and carrying out plasma treatment for 10min.
(2) Co-deposition treatment: selecting Ca (NO) 3 ) 2 ·4H 2 0 solution as Ca source and Na 3 PO 4 As P source, sr (NO) 3 ) 2 As a desired Sr source, mg (NO) 3 ) 2 As the desired Mg source, 9mol Ca (NO) was added to 1L of deionized water 3 ) 2 ·4H 2 0、6mol Na 3 PO 4 、0.5mol Sr(NO 3 ) 2 、0.5mol Mg(NO 3 ) 2 Adding a pH regulator to enable the pH value to reach 8 after uniform stirring to obtain a codeposition reaction solution, adding the codeposition reaction solution into a reaction kettle with the volume of 2L, and then adding the polyether-ether-ketone powder subjected to plasma treatment. The codeposition reaction is carried out under the conditions that the temperature of the reaction kettle is 150 ℃ and the stirring speed is 50rpm, the reaction time is 12h, and a codeposition layer is formed on the surface of the polyetheretherketone powder. And after the reaction is finished, cooling to room temperature, filtering to take out the polyetheretherketone biological composite powder, putting the polyetheretherketone biological composite powder into an oven to perform heat treatment for 4 hours at 270 ℃ to reduce the internal stress of the codeposition layer, and then cooling to obtain the polyetheretherketone biological composite powder suitable for selective laser sintering forming.
(3) Selective laser sintering and forming: selecting the prepared polyetheretherketone biological composite powder, putting the polyetheretherketone biological composite powder into selective laser sintering equipment for powder paving, heating the powder to a preheating temperature of 330 ℃, and printing the powder by adopting a double-laser interval printing mode, namely setting the scanning paths of each layer of the laser 1 and the laser 2 to be the same, setting the laser 1 to firstly scan, and starting scanning by the laser 2 when the temperature of a scanning area is reduced to 350 ℃ under the monitoring of a thermal infrared imager. The parameters of the laser 1 are set as follows: the laser power is 15W, the scanning speed is 2000mm/s, the filling space is 0.2mm, and the layer thickness is 0.1mm; the process parameters of the laser 2 are as follows: the laser power was 12.5W, the scanning rate was 2000mm/s, the filling pitch was 0.2mm and the layer thickness was 0.1mm. And after the scanning is finished, naturally cooling, taking out the sample, and performing sand blasting treatment on the sample.
Example 2
(1) Powder plasma treatment: screening 200g of medical grade polyetheretherketone powder with the particle size of 10-100 mu m, putting the polyetheretherketone powder into a low-temperature plasma treatment instrument, adjusting the parameters of the instrument to be 100W, the vacuum degree to be 25Pa, the oxygen flow to be 20mL/min, and carrying out plasma treatment for 20min.
(2) Co-deposition treatment: selecting Ca (NO) 3 ) 2 ·4H 2 0 solution as Ca source and Na 3 PO 4 As a P source, agNO 3 As a desired source of Ag, auNO 3 As the required Au source, 4mol Ca (NO) was added to 500ml deionized water 3 ) 2 ·4H 2 0，3mol Na 3 PO 4 、1mol AgNO 3 、1mol AuNO 3 And after stirring uniformly, adding a pH regulator to make the pH value reach 8.5 to obtain a codeposition reaction solution. Adding the codeposition reaction solution into a reaction kettle with the volume of 1L, and then adding the polyether-ether-ketone powder subjected to plasma treatment. The codeposition reaction is carried out under the conditions that the temperature of the reaction kettle is 200 ℃ and the stirring speed is 100rpm, and the reaction time is 36h. And after the reaction is finished, cooling to room temperature, filtering to take out the polyetheretherketone biological composite powder, putting the polyetheretherketone biological composite powder into an oven to perform heat treatment for 12 hours at the temperature of 310 ℃ to reduce the internal stress of the codeposition layer, and then cooling to obtain the polyetheretherketone biological composite powder for selective laser sintering forming.
(3) Selective laser sintering and forming: selecting the prepared polyetheretherketone biological composite powder, putting the polyetheretherketone biological composite powder into selective laser sintering equipment for powder paving, heating the powder to a preheating temperature of 330 ℃, and printing the powder by adopting a double-laser interval printing mode, namely setting the scanning paths of each layer of the laser 1 and the laser 2 to be the same, setting the laser 1 to firstly scan, and starting scanning by the laser 2 when the temperature of a scanning area is reduced to 350 ℃ under the monitoring of a thermal infrared imager. The parameters of the laser 1 are set as follows: the laser power is 10W, the scanning speed is 1000mm/s, the filling space is 0.2mm, and the layer thickness is 0.1mm; the process parameters of the laser 2 are as follows: the laser power was 8.75W, the scanning rate was 1000mm/s, the filling pitch was 0.2mm, and the layer thickness was 0.1mm. And after the scanning is finished, naturally cooling, then taking out the sample, and carrying out sand blasting treatment on the sample.
Example 3
(1) Powder plasma treatment: screening 800g of medical grade polyetheretherketone powder with the particle size of 10-100 mu m, putting the polyetheretherketone powder into a low-temperature plasma treatment instrument, adjusting the parameters of the instrument to be 100W, the vacuum degree to be 25Pa, the oxygen flow to be 50mL/min, and carrying out plasma treatment for 15min.
(2) Co-deposition treatment: selecting Ca (NO) 3 ) 2 ·4H 2 0 solution as Ca source and Na 3 PO 4 As P source, zn (NO) 3 ) 2 AuNO as the required Zn source 3 As a required Au source, mg (NO) 3 ) 2 As a source of Mg, sr (NO) 3 ) 2 As the required Sr source, 8mol Ca (NO) is added into 2L deionized water 3 ) 2 ·4H 2 0、6mol Na 3 PO 4 、0.5mol Zn(NO 3 ) 2 、1mol AuNO 3 、0.5mol Mg(NO 3 ) 2 、0.5mol Sr(NO 3 ) 2 Stirring uniformly, and adding a pH regulator to enable the pH value to reach 7.5 so as to obtain a codeposition reaction solution; adding the codeposition reaction liquid into a reaction kettle with the volume of 5L, and then adding the polyether-ether-ketone powder subjected to plasma treatment. The codeposition reaction is carried out under the conditions that the temperature of the reaction kettle is 180 ℃ and the stirring speed is 100rpm, and the reaction time is 36h. After the reaction is finished, cooling to room temperature, filtering and taking out the polyetheretherketone biological compositeAnd (3) putting the powder into an oven, performing heat treatment for 8 hours at the temperature of 300 ℃ to reduce the internal stress of a codeposition layer on the polyetheretherketone biological composite powder, and then cooling to obtain the polyetheretherketone biological composite powder for selective laser sintering forming.
(3) Selective laser sintering and forming: selecting the prepared polyetheretherketone biological composite powder, putting the polyetheretherketone biological composite powder into selective laser sintering equipment for powder paving, heating the powder to a preheating temperature of 330 ℃, and printing the powder by adopting a double-laser interval printing mode, namely setting the scanning paths of each layer of the laser 1 and the laser 2 to be the same, setting the laser 1 to scan firstly, and setting the laser 2 to scan when the temperature of a scanning area is reduced to 350 ℃ under the monitoring of a thermal infrared imager; the parameters of the laser 1 are set as follows: the laser power is 20W, the scanning speed is 4000mm/s, the filling space is 0.2mm, and the layer thickness is 0.15mm; the process parameters of the laser 2 are as follows: the laser power was 12.5W, the scanning rate was 4000mm/s, the filling pitch was 0.2mm, and the layer thickness was 0.15mm. And after the scanning is finished, naturally cooling, then taking out the sample, and carrying out sand blasting treatment on the sample.
Example 4
(1) Powder plasma treatment: screening 400g of medical grade polyetheretherketone powder with the particle size of 10-100 mu m, putting the polyetheretherketone powder into a low-temperature plasma treatment instrument, adjusting the parameters of the instrument to be 100W, the vacuum degree to be 25Pa, the oxygen flow to be 25mL/min, and carrying out plasma treatment for 15min.
(2) Co-deposition treatment: selecting Ca (NO) 3 ) 2 ·4H 2 0 solution as Ca source and Na 3 PO 4 As P source, zn (NO) 3 ) 2 As the desired Zn source, 9.5mol Ca (NO) was added to 1.5L of deionized water 3 ) 2 ·4H 2 0、6mol Na 3 PO 4 、0.5mol Zn(NO 3 ) 2 After stirring uniformly, adding a pH regulator to make the pH value reach 8 so as to obtain a deposition reaction solution; adding the codeposition reaction liquid into a reaction kettle with the volume of 3L, and then adding the polyether-ether-ketone powder subjected to plasma treatment. The codeposition reaction is carried out under the conditions that the temperature of the reaction kettle is 180 ℃ and the stirring speed is 100rpm, and the reaction time is 36h. After the reaction is finished, cooling to room temperature, filtering and taking out the polyetheretherketone biological compositeAnd (3) putting the powder into an oven, performing heat treatment for 8 hours at the temperature of 300 ℃ to reduce the internal stress of a codeposition layer on the polyetheretherketone biological composite powder, and then cooling to obtain the polyetheretherketone biological composite powder for laser selective sintering forming.
(3) Selective laser sintering and forming: selecting the prepared polyetheretherketone biological composite powder, putting the polyetheretherketone biological composite powder into selective laser sintering equipment for powder paving, heating the powder to a preheating temperature of 330 ℃, and printing the powder by adopting a double-laser interval printing mode, namely setting the scanning paths of each layer of the laser 1 and the laser 2 to be the same, setting the laser 1 to firstly scan, and starting scanning by the laser 2 when the temperature of a scanning area is reduced to 350 ℃ under the monitoring of a thermal infrared imager. The parameters of the laser 1 are set as follows: the laser power is 20W, the scanning speed is 4000mm/s, the filling space is 0.2mm, and the layer thickness is 0.15mm; the process parameters of the laser 2 are as follows: the laser power was 6.25W, the scanning rate was 2000mm/s, the filling pitch was 0.2mm, and the layer thickness was 0.15mm. And after the scanning is finished, naturally cooling, then taking out the sample, and carrying out sand blasting treatment on the sample.
It will be understood by those skilled in the art that the foregoing is only a preferred embodiment of the present invention, and is not intended to limit the invention, and that any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the scope of the present invention.

Claims (6)

1. A preparation method of polyetheretherketone biological composite powder is characterized by comprising the following steps:
(1) Oxygen plasma is adopted to carry out surface modification on the polyether-ether-ketone powder so as to introduce polar groups;
(2) Mixing Ca (NO) 3 ) 2 ·4H 2 O as Ca source, na 3 PO 4 As P source, X (NO) 3 ) y Adding the PEEK powder modified by oxygen plasma into the codeposition reactant to carry out codeposition reaction, and forming codeposition on the surface of the PEEK powderLayering to obtain polyether-ether-ketone biological composite powder;
wherein X is a functional element; the step (2) is followed by a step of heat treatment of the polyetheretherketone biological composite material; x comprises any one or more of antibacterial elements, elements with immunoregulation and anticancer functions, elements with photo-thermal anticancer properties and elements with angiogenesis promoting properties; the ratio of the volume of the codeposition reactant to the mass of the polyetheretherketone powder is 1L; the temperature of the codeposition reaction is 150-200 ℃, the stirring speed is 50-100 rpm, and the reaction time is 12-36h; the pH value of the codeposition reactant is 7-10; the heat treatment temperature is 270-310 ℃, and the heat treatment time is 4-12 h.
2. The method of preparing a polyetheretherketone biocomposite powder of claim 1, wherein: stirring the resulting co-precipitated Ca (NO) in the reactant 3 ) 2 ·4H 2 O、Na 3 PO 4 All the concentrations of (a) and (b) are 20 to 40mol/L and satisfy (n) Ca(NO3)2·4H2O +y·n X(NO3)y /2)：n Na3PO4 ＝10:6。
3. The method of preparing a polyetheretherketone biocomposite powder of any of claims 1-2, wherein: the equation for the codeposition reaction is: (10-n/2) Ca 2+ +(n/y)
X y+ +6PO 4 3- +2H 2 O＝Ca (10-n/2) X (n/y) (PO 4 ) 6 (OH) 2 +2H + ；
Wherein n is more than or equal to 0 and less than or equal to 4.
4. A peek biocomposite powder prepared using the method of preparing a peek biocomposite powder of any one of claims 1-3.
5. Use of a peek biocomposite powder of claim 4 in selective laser sintering of implants, wherein: the application comprises the following steps:
(1) Putting the polyether-ether-ketone biological composite powder into selective laser sintering equipment for powder paving;
(2) Adopting a laser 1 and a laser 2 to carry out interval printing to obtain a sample, and carrying out sand blasting treatment on the sample to obtain an implant; wherein, each layer of scanning paths of the laser 1 and the laser 2 are set to be the same, the laser 1 is set to scan firstly, and the laser 2 starts scanning after the temperature of a scanning area is reduced to 350 ℃ under the monitoring of a thermal infrared imager.
6. Use of a peek biocomposite powder according to claim 5 in selective laser sintering of implants, wherein: the preheating temperature during processing is set to 330 ℃, and the process parameters of the laser 1 are as follows: the laser power is 5-45W, the scanning speed is 1000-4000 mm/s, the filling space is 0.1-0.3 mm, and the layer thickness is 0.05-0.25 mm; the process parameters of the laser 2 are as follows: the laser power is 5-45W, the scanning speed is 1000-4000 mm/s, the filling space is 0.1-0.3 mm, and the layer thickness is 0.05-0.25 mm.
CN202210272065.6A 2022-03-18 2022-03-18 Polyether-ether-ketone biological composite powder and preparation method and application thereof Active CN114712558B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202210272065.6A CN114712558B (en) 2022-03-18 2022-03-18 Polyether-ether-ketone biological composite powder and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202210272065.6A CN114712558B (en) 2022-03-18 2022-03-18 Polyether-ether-ketone biological composite powder and preparation method and application thereof

Publications (2)

Publication Number Publication Date
CN114712558A CN114712558A (en) 2022-07-08
CN114712558B true CN114712558B (en) 2023-03-28

Family

ID=82236749

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202210272065.6A Active CN114712558B (en) 2022-03-18 2022-03-18 Polyether-ether-ketone biological composite powder and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN114712558B (en)

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5484030B2 (en) * 2009-12-18 2014-05-07 日本特殊陶業株式会社 Biological implant
CN105061989B (en) * 2015-09-02 2017-12-15 广东银禧科技股份有限公司 A kind of polyether-ether-ketone/nano hydroxyapatite composite material for SLS technologies and preparation method thereof
EP3784477A1 (en) * 2018-04-23 2021-03-03 Materialise N.V. Thermal control in laser sintering
KR102300828B1 (en) * 2019-10-25 2021-09-09 참엔지니어링(주) Dual scanner 3D printer using selective laser sintering
CN113750290A (en) * 2020-06-03 2021-12-07 深圳先进技术研究院 Polyether-ether-ketone composite implant and preparation method and application thereof

Also Published As

Publication number Publication date
CN114712558A (en) 2022-07-08

Similar Documents

Publication Publication Date Title
CN107598166B (en) Method for preparing porous tantalum medical implant material based on electron beam selective melting technology
Attarilar et al. 3D printing technologies in metallic implants: a thematic review on the techniques and procedures
EP3159141A1 (en) Powder material to be used in powder lamination shaping and powder lamination shaping method using same
Moeini et al. In-situ solvothermal processing of polycaprolactone/hydroxyapatite nanocomposites with enhanced mechanical and biological performance for bone tissue engineering
Vaezi et al. A novel bioactive PEEK/HA composite with controlled 3D interconnected HA network
EP2039668B1 (en) Method of producing a porous ceramic material
EP2147906B1 (en) Method for production of porous ceramic material
Zhang et al. Spark plasma sintering, microstructures, and mechanical properties of macroporous titanium foams
CN113304323B (en) Porous polyether-ether-ketone-hydroxyapatite composite material and preparation method and application thereof
Francis et al. Additive manufacturing of polyetheretherketone and its composites: A review
Wang et al. Applications of calcium phosphate nanoparticles in porous hard tissue engineering scaffolds
US20120107612A1 (en) Hydroxyapatite poly(etheretherketone) nanocomposites and method of manufacturing same
Sudan et al. Processing of hydroxyapatite and its composites using ceramic fused filament fabrication (CF3)
CN114191617A (en) Polyether-ether-ketone implant with controllable drug slow release and preparation method thereof
CN114712558B (en) Polyether-ether-ketone biological composite powder and preparation method and application thereof
CN116438054B (en) Methods for forming implantable medical devices having varying compositions and porous structures
Diao et al. The applications and latest progress of ceramic 3D printing
KR20070084436A (en) Silicon structure
CN112458514A (en) Method for generating nanotube array oxide film on surface of medical porous titanium or titanium alloy
CN114850469B (en) Metal bone cement, porous metal microspheres and preparation method thereof
CN112276109B (en) Forming method and product of polyether-ether-ketone bio-philic metal porous bone implant
Qin et al. Preparation and characterization of different micro/nano structures on the surface of bredigite scaffolds
CN111299585B (en) Preparation method of artificial bone
CN115433932B (en) Pure titanium surface gradient micro-nano TiZn 3 -TiZn X Composite coating and preparation method thereof
CN110420358A (en) It can promote bone growth and can be completely by bone nail of bone absorption and preparation method thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant