CN114712558A - 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

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CN114712558A
CN114712558A CN202210272065.6A CN202210272065A CN114712558A CN 114712558 A CN114712558 A CN 114712558A CN 202210272065 A CN202210272065 A CN 202210272065A CN 114712558 A CN114712558 A CN 114712558A
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powder
laser
polyetheretherketone
codeposition
polyether
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CN114712558B (en
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闫春泽
王浩则
袁熙
陈鹏
苏瑾
伍宏志
张贞
杨操
史玉升
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Huazhong University of Science and Technology
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Abstract

The invention belongs to the technical field related to biological composite materials, and discloses polyether-ether-ketone biological composite powder and a preparation method thereofAnd application, comprising the following steps: (1) carrying out surface modification on the polyether-ether-ketone powder by adopting oxygen plasma; (2) mixing Ca (NO)3)2·4H20 as Ca source, Na3PO4As P source, X (NO)3)yAdding 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 polyether-ether-ketone biological composite powder obtained by the invention 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 matching with human cortical bone, but also has no artifacts in CT or MRI images, does not affect post-operative imaging 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 thought of discrete accumulation forming, and controls a laser 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 and superposed layer by layer. 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 complex structure can be formed, and the method is very suitable for forming and preparing the complex personalized polyether-ether-ketone bone implant.
However, polyetheretherketone is a biologically inert material and has poor osteogenic capacity, which limits its clinical application in orthopedics. 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 in patent CN112276109B, a method and product for forming a peek-based biometal porous bone implant is disclosed, which uses a mechanical mixing method to prepare a peek/mometaphilic composite material for laser selective sintering forming, however, the method is limited to promoting the osteogenic capacity of peek 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 composite material of polyetheretherketone and a method for preparing the same, which increases the bioactivity and abrasion 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. Patent CN105061989A also 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 agglomeration of the nano-material is easily caused by weak binding force of the nano-hydroxyapatite and the polyetheretherketone powder.
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 instantly absorbs overhigh energy to degrade a matrix 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)2·4H20 as Ca source, Na3PO4As P source, X (NO)3)yAdding 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) and 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 12-36 h.
Further, stirring to obtainCo-deposition of Ca (NO) in the reactants3)2·4H20、Na3PO4The concentration of (a) is 20 to 40mol/L and satisfies (n)Ca(NO3)2.4H20+y·nX(NO3)y/2)：nNa3PO4＝10:6，0≤n≤4。
Further, the pH value of the codeposition reactant is 7-10.
Further, (10-n/2) Ca2++(n/y)Xy++6PO4 3-+2H20＝Ca(10-n/2)X(n/y)(PO4)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 firstly scan, and the laser 2 starts scanning when 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/mm3(ii) a Energy density E of laser 2 during machiningvolLower than the laser 1, by a value approximately equal to the energy E required for melting the powder per unit volumem(ii) a Bulk energy density EvolThe formula of (1) is:
Figure BDA0003553899990000041
wherein P is filling power, S is scanning distance, V is filling speed, and h is layer thickness;
Emthe formula of (1) is:
Figure BDA0003553899990000042
wherein E ismIs the energy required for melting the powder per unit volume, CpIs the specific heat capacity of the polyetheretherketone powder,
Figure BDA0003553899990000043
is the equilibrium melting point, T, of the polyetheretherketone powderbIs the powder preheating temperature,. DELTA.HmIs the melting enthalpy, P, of the polyetheretherketone powderdIs the bulk density of the powder.
Generally, compared with the prior art, the polyether-ether-ketone 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, so that the van der Waals force of a polyether-ether-ketone interface and a codeposition layer is improved, 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 codeposition 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 absorbs overhigh energy instantly to degrade a polyetheretherketone matrix is avoided, and the existence of the nano-hydroxyapatite crystal promotes the crystallization of the polyetheretherketone, so that the mechanical property of a printed sample is obviously improved.
5. The pH value of the codeposition reactant is 7-10, when the pH value exceeds 10, the bonding force of the codeposition layer can be rapidly weakened, and when the pH value is lower than 7, the deposition 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 carrier3)2·4H20 and Na3PO4Taking 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 polyether-ether-ketone powder with the particle size of 10-100 mu m, and carrying out surface modification on the medical-grade polyether-ether-ketone powder by using 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: and (3) putting the polyether-ether-ketone powder into a low-temperature plasma treatment instrument, and adjusting the parameters of the instrument to be 50-100W, the vacuum degree to be 25Pa, the oxygen flow to be 10-50 mL/min, and the treatment time to be 5-20 min.
(2) Selecting Ca (NO)3)2·4H20 as Ca source, Na3PO4As P source, X (NO)3)yAdding the functional element source and pH regulator into deionized water, stirring to obtain codeposition reactant, and adding the codeposition reactant into high-pressure reactor with stirring slurryAdding the plasma modified polyether-ether-ketone into the reaction kettle to perform codeposition reaction, and naturally cooling the reaction kettle to room temperature.
Wherein y is the valence of the element X; stirring the resulting co-precipitated Ca (NO) in the reactant3)2·4H20、Na3PO4The concentration of (a) is 20 to 40mol/L and satisfies (n)Ca(NO3)2.4H20+y·nX(NO3)y/2)：nNa3PO410:6, n is more than or equal to 0 and less than or equal to 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 is 0.1-0.4 (kg). In addition, the height of the liquid level cannot 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 12-36 h.
Further, 170-190 ℃ is an optimal reaction temperature range for preparing the co-deposition 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 precipitation reaction cannot occur.
The ion reaction equation for codeposition is:
(10-n/2)Ca2++(n/y)Xy++6PO4 3-+2H20＝Ca(10-n/2)X(n/y)(PO4)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 polyether-ether-ketone biological composite powder which is prepared by the preparation method of the polyether-ether-ketone 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 adopted to form the implant by taking the polyetheretherketone biological composite powder as a raw material, and the method 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, and the filling space is 0.1-03mm, the thickness of the layer 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 energy input by the laser 1 and the laser 2 is 0.314-0.942J/mm3. Energy density E of laser 2 during processingvolLower than the laser 1, by a value approximately equal to the energy E required for melting the powder per unit volumem。
Definition of the volume energy Density EvolThe 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.
EmThe formula of (1) is:
Figure BDA0003553899990000082
wherein E ismIs the energy required for melting the powder per unit volume, CpThe specific heat capacity (2.2J/kg. DEG C) of the polyether-ether-ketone powder,
Figure BDA0003553899990000083
is the equilibrium melting point (380.5 ℃) T of the polyetheretherketone powderbIs the powder preheating temperature (330 ℃), Δ HmIs the melting enthalpy (58.6J/g), P, of the polyetheretherketone powderdIs the bulk density of the powder (0.37 g/cm)3). Calculated to obtain EmIs 0.0628J/mm3。
The invention is described in further 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 10 min.
(2) Co-deposition treatment: selecting Ca (NO)3)2·4H20 solution as Ca source and Na3PO4As P source, Sr (NO)3)2As the required Sr source, Mg (NO)3)2As the desired Mg source, 9mol Ca (NO) was added to 1L of deionized water3)2·4H20、6mol Na3PO4、0.5mol Sr(NO3)2、0.5mol Mg(NO3)2Adding 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. And carrying out codeposition reaction under the conditions that the temperature of the reaction kettle is 150 ℃ and the stirring speed is 50rpm, wherein the reaction time is 12h, and a codeposition layer is formed on the surface of the polyether-ether-ketone powder. And after the reaction is finished, cooling to room temperature, filtering to obtain the polyetheretherketone biological composite powder, putting the polyetheretherketone biological composite powder into an oven, performing 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 laser selective sintering forming.
(3) Selective laser sintering and forming: selecting the prepared polyetheretherketone biological composite powder, placing the powder in selective laser sintering equipment, spreading the powder, heating the powder to a preheating temperature of 330 ℃, 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 15W, the scanning speed is 2000mm/s, the filling space is 0.2mm, and the layer thickness is 0.1 mm; 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 0.1 mm. 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 20 min.
(2) Codeposition treatment: selecting Ca (NO)3)2·4H20 solution as Ca source and Na3PO4As a P source, AgNO3As a desired source of Ag, AuNO3As the required Au source, 4mol Ca (NO) was added to 500ml deionized water3)2·4H20，3mol Na3PO4、1mol AgNO3、1mol AuNO3And 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 36 h. 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, placing the powder in selective laser sintering equipment, spreading the powder, heating the powder to a preheating temperature of 330 ℃, 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 10W, the scanning speed is 1000mm/s, the filling space is 0.2mm, and the layer thickness is 0.1 mm; 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 0.1 mm. 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 15 min.
(2) Codeposition treatment: selecting Ca (NO)3)2·4H20 solution as Ca source and Na3PO4As P source, Zn (NO)3)2AuNO as the required Zn source3As a required Au source, Mg (NO)3)2As a source of Mg, Sr (NO)3)2As the required Sr source, 8mol Ca (NO) is added into 2L deionized water3)2·4H20、6mol Na3PO4、0.5mol Zn(NO3)2、1mol AuNO3、0.5mol Mg(NO3)2、0.5mol Sr(NO3)2After stirring uniformly, adding a pH regulator to make the pH value reach 7.5 so as to obtain a codeposition reaction solution; the codeposition reaction solution was added to a reaction vessel having a volume of 5L, and then the plasma-treated polyetheretherketone powder was added. 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 36 h. 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 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 polyether-ether-ketone biological composite powder, putting the 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 0.15 mm; 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 0.15 mm. 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 15 min.
(2) Codeposition treatment: selecting Ca (NO)3)2·4H20 solution as Ca source and Na3PO4As P source and Zn (NO)3)2As the desired Zn source, 9.5mol Ca (NO) was added to 1.5L of deionized water3)2·4H20、6mol Na3PO4、0.5mol Zn(NO3)2After 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 36 h. 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 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, placing the powder in selective laser sintering equipment, spreading the powder, heating the powder to a preheating temperature of 330 ℃, 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 0.15 mm; 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 0.15 mm. 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 (10)

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)2·4H20 as Ca source, Na3PO4As P source, X (NO)3)yAdding 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.
2. The method of preparing a polyetheretherketone biocomposite powder of claim 1, wherein: 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 1(L) and 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 12-36 h.
3. The method of preparing a polyetheretherketone biocomposite powder of claim 1, wherein: stirring the resulting co-precipitated Ca (NO) in the reactant3)2·4H20、Na3PO4All concentrations of (1) are 20About 40mol/L and satisfies (n)Ca(NO3)2.4H20+y·nX(NO3)y/2)：nNa3PO4＝10:6，0≤n≤4。
4. The method of preparing a polyetheretherketone biocomposite powder of claim 1, wherein: the pH value of the codeposition reactant is 7-10.
5. The method of preparing a polyetheretherketone biocomposite powder of any one of claims 1-4, wherein: (10-n/2) Ca2++(n/y)Xy++6PO4 3-+2H20
＝Ca(10-n/2)X(n/y)(PO4)6(OH)2+2H+；
Wherein n is more than or equal to 0 and less than or equal to 4.
6. The method of preparing a polyetheretherketone biocomposite powder of any one of claims 1-4, wherein: 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.
7. A PEEK biocomposite powder prepared by the method of preparing a PEEK biocomposite powder of any one of claims 1-6.
8. Use of a peek biocomposite powder of claim 7 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 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 firstly scan, and the laser 2 starts scanning when the temperature of a scanning area is reduced to 350 ℃ under the monitoring of a thermal infrared imager.
9. Use of a peek biocomposite powder according to claim 8 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.
10. Use of a peek biocomposite powder according to claim 8 in selective laser sintering of implants, wherein: the energy density input by the laser 1 and the laser 2 is 0.314-0.942J/mm3(ii) a Energy density E of laser 2 during machiningvolLower than the laser 1, by a value approximately equal to the energy E required for melting the powder per unit volumem(ii) a Bulk energy density EvolThe formula of (1) is:
Figure FDA0003553899980000021
wherein P is filling power, S is scanning distance, V is filling speed, and h is layer thickness;
Emthe formula of (1) is:
Figure FDA0003553899980000031
wherein E ismIs the energy required for melting the powder per unit volume, CpIs the specific heat capacity of the polyetheretherketone powder,
Figure FDA0003553899980000032
is the equilibrium melting point, T, of the polyetheretherketone powderbIs the powder preheating temperature,. DELTA.HmIs the melting enthalpy, P, of the polyetheretherketone powderdIs the bulk density of the powder.
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011125531A (en) * 2009-12-18 2011-06-30 Ngk Spark Plug Co Ltd Bioimplant
CN105061989A (en) * 2015-09-02 2015-11-18 广东银禧科技股份有限公司 Polyetheretherketone/nano-hydroxyapatite composite for SLS technology and preparation method of polyetheretherketone/nano-hydroxyapatite composite
CN112705707A (en) * 2019-10-25 2021-04-27 灿美工程股份有限公司 Dual scanner three-dimensional printer using selective laser sintering
US20210237158A1 (en) * 2018-04-23 2021-08-05 Materialise N.V. Thermal control in laser sintering
WO2021243979A1 (en) * 2020-06-03 2021-12-09 深圳先进技术研究院 Polyether-ether-ketone composite implant, preparation method therefor and application thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011125531A (en) * 2009-12-18 2011-06-30 Ngk Spark Plug Co Ltd Bioimplant
CN105061989A (en) * 2015-09-02 2015-11-18 广东银禧科技股份有限公司 Polyetheretherketone/nano-hydroxyapatite composite for SLS technology and preparation method of polyetheretherketone/nano-hydroxyapatite composite
US20210237158A1 (en) * 2018-04-23 2021-08-05 Materialise N.V. Thermal control in laser sintering
CN112705707A (en) * 2019-10-25 2021-04-27 灿美工程股份有限公司 Dual scanner three-dimensional printer using selective laser sintering
WO2021243979A1 (en) * 2020-06-03 2021-12-09 深圳先进技术研究院 Polyether-ether-ketone composite implant, preparation method therefor and application thereof

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