CN112076345B - CoFe 2 O 4 PVDF (polyvinylidene fluoride) composite bone scaffold and preparation method thereof - Google Patents

CoFe 2 O 4 PVDF (polyvinylidene fluoride) composite bone scaffold and preparation method thereof Download PDF

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CN112076345B
CN112076345B CN202010925914.4A CN202010925914A CN112076345B CN 112076345 B CN112076345 B CN 112076345B CN 202010925914 A CN202010925914 A CN 202010925914A CN 112076345 B CN112076345 B CN 112076345B
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pvdf
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CN112076345A (en
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戚方伟
帅词俊
杨友文
刘国峰
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Jiangxi University of Science and Technology
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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/14—Macromolecular materials
    • A61L27/16—Macromolecular materials obtained 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
    • A61L27/02—Inorganic materials
    • A61L27/025—Other specific inorganic materials not covered by A61L27/04 - A61L27/12
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/50—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
    • A61L2430/00—Materials or treatment for tissue regeneration
    • A61L2430/02—Materials or treatment for tissue regeneration for reconstruction of bones; weight-bearing implants

Abstract

The invention relates to a CoFe 2 O 4 PVDF composite bone scaffold and preparation method thereof, wherein the CoFe 2 O 4 The PVDF composite bone scaffold is made of CoFe 2 O 4 The ethanol suspension and the ethanol suspension of PVDF are mixed and stirred, and the CoFe obtained is 2 O 4 Filtering solid-liquid phase separation of PVDF mixed suspension, drying and ball milling the obtained solid phase to obtain composite powder, and selectively laser sintering the composite powder to obtain the CoFe 2 O 4 PVDF composite bone scaffold. CoFe provided by the invention 2 O 4 The PVDF composite bone scaffold can realize remote non-contact electrical stimulation on bone cells by externally applying an alternating magnetic field, thereby promoting the growth of osteoblasts and the regeneration and reconstruction of defective tissues.

Description

CoFe 2 O 4 PVDF (polyvinylidene fluoride) composite bone scaffold and preparation method thereof
Technical Field
The invention relates to the technical field of artificial bone scaffolds, in particular to CoFe 2 O 4 PVDF composite bone scaffold and preparation method thereof.
Background
At present, the problems of low biological activity, low bone regeneration and low bone integration speed of the artificial bone scaffold exist. The research proves that: the bone has piezoelectricity, and a proper amount of electric stimulation can regulate the functions of cell membranes in the bone repair process, activate cell channels and regulate the expression of genes related to the bone so as to promote the adhesion, proliferation and differentiation of bone cells on a bone scaffold and further accelerate the regeneration and reconstruction of the bone. In addition, the biological piezoelectric material can generate electric charge under the action of external mechanical stress to form an endogenous electric microenvironment required for promoting the growth of human bones, and is a hot spot and a key point of research in the field of bone transplantation at present.
Polyvinylidene fluoride (PVDF) is used as a high-molecular piezoelectric material, has the advantages of high piezoelectric coefficient, good biocompatibility, strong mechanical property, easiness in processing and the like, and shows great potential in the field of bone repair. However, the bone injury patients are often in poor health and are not suitable for exercise, so that it is difficult to provide the stress required for exciting the piezoelectric effect, the piezoelectric effect of the stent is difficult to exert, and the electrical stimulation effect of the stent on the cells around the injured part cannot be realized. Ferromagnetic materials, on the other handAnd the ferrimagnetic material can generate size and volume change under the action of an external alternating magnetic field, and shows a magnetostrictive phenomenon. Among them, spinel type cobalt ferrite (CoFe) 2 O 4 ) Has high saturation magnetization and coercive force, large magnetocrystalline anisotropy and magnetostriction, good chemical stability and biocompatibility without rare earth elements, and draws wide attention in the field of biological medicine. In view of CoFe 2 O 4 Considering the advantages of excellent magnetostriction and stability of magnetic field in human body, CoFe 2 O 4 Compounding with PVDF, and inducing CoFe by external alternating magnetic field 2 O 4 Deformation is generated to make the PVDF matrix in CoFe 2 O 4 Generates electric charge under the deformation action of the magnetic field.
However, in the prior art, CoFe has not yet been prepared 2 O 4 The bone scaffold compounded with PVDF cannot completely overcome the problem that the piezoelectric effect of the scaffold is difficult to exert due to poor health and inappropriate movement of patients with bone defects.
Disclosure of Invention
Based on this, the purpose of the invention is to solve the problem that CoFe is not prepared in the prior art 2 O 4 The bone scaffold compounded with PVDF cannot completely overcome the problem that the piezoelectric effect of the scaffold is difficult to exert due to poor health and inappropriate movement of patients with bone defects.
The invention provides a CoFe 2 O 4 PVDF composite bone scaffold, wherein the CoFe 2 O 4 The PVDF composite bone scaffold is made of CoFe 2 O 4 The obtained ethanol suspension and PVDF ethanol suspension are mixed and stirred, and the obtained CoFe 2 O 4 Filtering solid-liquid phase separation of PVDF mixed suspension, drying and ball milling the obtained solid phase to obtain composite powder, and selectively laser sintering the composite powder to obtain the CoFe 2 O 4 PVDF composite bone scaffold, wherein said CoFe 2 O 4 The composite material is spinel type cobalt ferrite, and the PVDF is polyvinylidene fluoride.
The CoFe 2 O 4 PVDF composite bone branchA shelf wherein said CoFe 2 O 4 In PVDF composite bone scaffolds, CoFe 2 O 4 The weight percentage of (A) is 5-25 wt%, the weight percentage of PVDF is 75-95 wt%, the particle diameter of PVDF is 40-100 μm, and CoFe 2 O 4 Has a particle diameter of 30 to 200nm, and the PVDF and the CoFe 2 O 4 The purity of (A) was 99%.
The CoFe 2 O 4 The PVDF composite bone scaffold is characterized in that when sintering is carried out in the selective laser sintering system, the laser power is 6-16W, the scanning speed is 100-200 mm/s, the scanning interval is 0.1-0.2 mm, the corresponding light spot diameter is 0.3-0.6 mm, and the CoFe is 2 O 4 The thickness of the powder layer of PVDF powder is 0.1-0.2 mm, and the corresponding preset temperature of the powder bed is 140-160 ℃.
The CoFe 2 O 4 PVDF composite bone scaffold, wherein the CoFe 2 O 4 The residual polarization intensity of the PVDF composite bone scaffold is 4.1-18.1 mu C/cm 2 The piezoelectric constant is 14.8-29.2 Pc/N, the saturation intensity is 2.4-38.1 emu/g, and the magnetoelectric coefficient is 0.6-15.3 mV/cmOe.
The invention also provides CoFe 2 O 4 The preparation method of the PVDF composite bone scaffold comprises the following steps:
the method comprises the following steps: weighing CoFe 2 O 4 Adding the powder into a three-neck flask containing absolute ethyl alcohol solution, and pre-dispersing the powder through mechanical stirring and ultrasonic dispersion to obtain CoFe 2 O 4 Wherein the CoFe 2 O 4 Is spinel type cobalt ferrite;
step two: weighing PVDF powder, adding the PVDF powder into a three-neck flask containing absolute ethyl alcohol solution, performing mechanical stirring and ultrasonic dispersion to realize pre-dispersion, further obtaining an ethyl alcohol suspension of PVDF, and dropwise adding the ethyl alcohol suspension of PVDF to CoFe 2 O 4 To obtain a mixed solution, and controlling CoFe in the mixed solution 2 O 4 The mass ratio of the powder to the PVDF powder is a first mass ratio, and the obtained mixed solution is added into a first solutionCarrying out ultrasonic stirring for a first preset time at a rotating speed of a first stirring speed in a preset temperature environment, then filtering the mixed solution, carrying out vacuum drying for a second preset time at a second preset temperature, and carrying out ball milling to obtain CoFe 2 O 4 PVDF powder;
step three: subjecting the CoFe 2 O 4 Placing PVDF powder in a selective laser sintering system, sintering layer by layer according to a three-dimensional model, and removing unsintered powder after sintering to obtain CoFe 2 O 4 PVDF composite bone scaffold.
The CoFe 2 O 4 The preparation method of the PVDF composite bone scaffold comprises the step two, wherein the first mass ratio is 5-25: 75-95, the first preset temperature is 30-60 ℃, the first stirring speed is 700-1000 r/min, the first preset time is 60-120 min, the second preset temperature is 50-70 ℃, and the second preset time is 10-12 h.
The CoFe 2 O 4 The preparation method of the PVDF composite bone scaffold comprises the third step, wherein when sintering is carried out in the selective laser sintering system, the laser power is 6-16W, the scanning speed is 100-200 mm/s, the scanning interval is 0.1-0.2 mm, the diameter of a corresponding light spot is 0.3-0.6 mm, and the CoFe 2 O 4 The thickness of the powder layer of PVDF powder is 0.1-0.2 mm, and the corresponding preset temperature of the powder bed is 140-160 ℃.
The CoFe 2 O 4 The preparation method of the PVDF composite bone scaffold is that the CoFe 2 O 4 In the PVDF composite bone scaffold, the particle size of PVDF is 40-100 mu m, and CoFe 2 O 4 Has a particle diameter of 30 to 200nm, and the PVDF and the CoFe 2 O 4 The purity of (A) was 99%.
The CoFe 2 O 4 Preparation method of PVDF composite bone scaffold, wherein the CoFe 2 O 4 The residual polarization intensity of the PVDF composite bone scaffold is 4.1-18.1 mu C/cm 2 The piezoelectric constant is 14.8-29.2 Pc/N, the saturation intensity is 2.4-38.1 emu/g, and the magnetoelectric coefficient is 0.6-15.3 mVcmOe。
The CoFe 2 O 4 A method for preparing a PVDF composite bone scaffold, wherein after step three, the method further comprises:
subjecting the CoFe 2 O 4 The PVDF composite bone support is placed in a closed container, stands for 0.5h and is taken out, wherein the closed container is positioned in an electric field with the preset electric field intensity of 2-4 KV/mm.
Additional features and advantages of the disclosure will be set forth in the description which follows, or in part may be learned by the practice of the above-described techniques of the disclosure, or may be learned by practice of the disclosure.
In order to make the aforementioned and other objects, features and advantages of the present invention comprehensible, preferred embodiments accompanied with figures are described in detail below.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the embodiments or the prior art descriptions will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 shows CoFe according to the present invention 2 O 4 Schematic diagram of preparation and test method of PVDF compound bone support;
FIG. 2 is a scanning electron micrograph of PVDF powder according to a first embodiment of the present invention;
FIG. 3 is a first embodiment of the present invention of CoFe 2 O 4 Scanning electron microscope images of the powder;
FIG. 4 is a first embodiment of the present invention of CoFe 2 O 4 A scanning electron microscope image of the PVDF composite bone scaffold;
FIG. 5 is a fluorescent image of cells on a PVDF scaffold according to the first embodiment of the present invention;
FIG. 6 shows CoFe in cells of the first embodiment of the present invention 2 O 4 PVDF composite bone branchFluorescence images on the shelf.
Detailed Description
To facilitate an understanding of the invention, the invention will now be described more fully with reference to the accompanying drawings. Preferred embodiments of the present invention are shown in the drawings. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
In the prior art, CoFe is not prepared yet 2 O 4 The bone scaffold compounded with PVDF cannot completely overcome the problem that the piezoelectric effect of the scaffold is difficult to exert for patients with bone defects due to poor health and difficult movement.
In order to solve the technical problem, the invention provides CoFe 2 O 4 A preparation method of a PVDF composite bone scaffold. CoFe proposed by the present invention is illustrated in the following examples 2 O 4 The preparation method of the PVDF composite bone scaffold is explained in more detail.
Example 1
CoFe according to the first embodiment of the present invention 2 O 4 The preparation method of the PVDF composite bone scaffold specifically comprises the following steps:
(1) 0.5g of CoFe was weighed using an electronic balance 2 O 4 Powder, CoFe 2 O 4 The particle size of the powder is 40nm, the powder is added into a three-mouth beaker filled with 75mL of absolute ethyl alcohol solution, pre-dispersion is realized through mechanical stirring and ultrasonic dispersion, and then uniform and stable CoFe is obtained 2 O 4 In which CoFe 2 O 4 Is spinel type cobalt ferrite;
(2) weighing 9.5g of PVDF powder by using an electronic balance, wherein the particle size of the PVDF powder is 80 mu m, adding the PVDF powder into a three-opening beaker filled with 100mL of absolute ethanol solution, and pre-dispersing the PVDF powder by mechanical stirring and ultrasonic dispersion to obtain uniform and stable PVDF ethanol suspension;
(3) the ethanol suspension of PVDF was added dropwise to CoFe 2 O 4 Then the mixed solution is stirred by magnetic force and dispersed and mixed evenly by ultrasonic. Wherein, the corresponding mechanical stirring time is 70min, the rotating speed is 800r/min, the temperature is 50 ℃, then the evenly mixed suspension is filtered and dried in vacuum for 12h at the temperature of 60 ℃, and finally the uniform CoFe is obtained by grinding 2 O 4 PVDF composite powder;
(4) the CoFe obtained above is added 2 O 4 The PVDF composite powder is paved in a selective laser sintering system, laser is utilized to melt the composite material powder according to a set track, and the composite material powder is superposed layer by layer and formed in a three-dimensional mode. And after sintering is finished, removing unsintered powder by adopting compressed air, and finally constructing the bio-piezoelectric bone scaffold consistent with the three-dimensional model. Wherein, the main sintering technological parameters are as follows: laser power of 8W, scanning speed of 150mm/s, scanning interval of 0.15mm, spot diameter of 0.4mm, and CoFe 2 O 4 The thickness of the powder layer of the PVDF composite powder is 0.15mm, and the preheating temperature of the corresponding powder bed is 155 ℃.
In example one, the CoFe obtained by the preparation method 2 O 4 The PVDF composite bone scaffold is used for performance characterization. The specific performance test results are as follows:
(a) the test of a ferroelectric analyzer shows that CoFe is added under the experimental conditions of the example 1 2 O 4 The remanent polarization Pr of the prepared composite scaffold is 9.1 mu C/cm 2 Piezoelectric constant d 33 20.3Pc/N, 10.2emu/g of magnetic saturation intensity Ms and magneto-electric coefficient alpha 33 ＝2.3mV/cmOe。
(b) The CoFe in the first example is found by cell activity test 2 O 4 PVDF composite bone scaffoldAfter the cells are cultured for 7 days, the cell adhesion, proliferation and differentiation capacities are obviously better than those of a pure PVDF scaffold.
Specifically, the fluorescence staining of bone cells after 7 days of culture on magnetoelectric scaffolds is shown in fig. 5 and 6. As can be seen from the figure, CoFe 2 O 4 The number of cells on the PVDF scaffold was significantly greater than that on the pure PVDF scaffold. Under the action of external magnetic field, the magnetic-electric coupling effect is generated in CoFe 2 O 4 The PVDF scaffold surface generates a charge. The charges further affect calcium ion signal channels on cell membranes, thereby promoting calcium ions to flow into cells and finally promoting the proliferation and differentiation of bone cells. However, pure PVDF does not respond to magnetic fields and its surface does not generate charges. The cells are thus in CoFe 2 O 4 The adhesion, proliferation and differentiation capacity on the PVDF scaffold is obviously superior to that of the pure PVDF scaffold.
Example 2
CoFe as set forth in the second embodiment of the present invention 2 O 4 The preparation method of the PVDF composite bone scaffold comprises the following steps:
(1) 1.5g of CoFe was weighed using an electronic balance 2 O 4 Powder, CoFe 2 O 4 The particle size of the powder is 40nm, the powder is added into a three-mouth beaker filled with 75mL of absolute ethyl alcohol solution, pre-dispersion is realized through mechanical stirring and ultrasonic dispersion, and then uniform and stable CoFe is obtained 2 O 4 The ethanol suspension of (a);
(2) weighing 8.5g of PVDF powder by using an electronic balance, wherein the particle size of the PVDF powder is 80 microns, adding the PVDF powder into a three-opening beaker filled with 100mL of absolute ethanol solution, and pre-dispersing the PVDF powder by mechanical stirring and ultrasonic dispersion to obtain uniform and stable PVDF ethanol suspension;
(3) the PVDF ethanol suspension was added dropwise to CoFe 2 O 4 Then the mixed solution is stirred by magnetic force and dispersed and mixed evenly by ultrasonic. Wherein, the corresponding mechanical stirring time is 70min, the rotating speed is 800r/min, the temperature is 50 ℃, then the evenly mixed suspension is filtered and dried in vacuum for 12h at the temperature of 60 ℃, and finally the uniform CoFe is obtained by grinding 2 O 4 PVDF composite powder;
(4) the CoFe obtained above is added 2 O 4 And the PVDF composite powder is paved in a selective laser sintering system, the composite powder is melted by laser according to a set track, and the composite powder is superposed layer by layer and formed in a three-dimensional mode. And after sintering is finished, removing unsintered powder by adopting compressed air, and finally constructing the bio-piezoelectric bone scaffold consistent with the three-dimensional model. Wherein, the main sintering technological parameters are as follows: laser power of 8W, scanning speed of 150mm/s, scanning interval of 0.15mm, spot diameter of 0.4mm, and CoFe 2 O 4 The thickness of a powder layer of the PVDF composite powder is 0.15mm, and the preheating temperature of a powder bed is 155 ℃.
In example two, the CoFe obtained by the preparation 2 O 4 The PVDF composite bone scaffold is used for performance characterization. The specific performance test results are as follows:
(a) the test of a ferroelectric analyzer shows that CoFe is added under the experimental conditions of the example 2 2 O 4 The residual polarization intensity Pr of the prepared composite scaffold is 16.3 mu C/cm 2 Piezoelectric constant d 33 25.4Pc/N, 18.5emu/g magnetic saturation intensity Ms and magneto-electric coefficient alpha 33 ＝7.3mV/cmOe。
(b) The CoFe in the second example was found to be present in cell viability assays 2 O 4 After the cells on the PVDF composite material are cultured for 7 days, the cell adhesion, proliferation and differentiation capacities are obviously better than those of a pure PVDF scaffold.
Example 3
CoFe according to the third embodiment of the present invention 2 O 4 The preparation method of the PVDF composite bone scaffold specifically comprises the following steps:
(1) 2.5g of CoFe was weighed using an electronic balance 2 O 4 Powder of CoFe 2 O 4 The particle size of the powder is 40nm, the powder is added into a three-mouth beaker filled with 75mL of absolute ethyl alcohol solution, pre-dispersion is realized through mechanical stirring and ultrasonic dispersion, and then uniform and stable CoFe is obtained 2 O 4 The ethanol suspension of (a);
(2) weighing 7.5g of PVDF powder by using an electronic balance, wherein the particle size of the PVDF powder is 80 microns, adding the PVDF powder into a three-opening beaker filled with 100mL of absolute ethanol solution, and pre-dispersing the PVDF powder by mechanical stirring and ultrasonic dispersion to obtain uniform and stable PVDF ethanol suspension;
(3) the PVDF ethanol suspension was added dropwise to CoFe 2 O 4 Then the mixed solution is stirred by magnetic force and dispersed and mixed evenly by ultrasonic. Wherein, the corresponding mechanical stirring time is 70min, the rotating speed is 800r/min, the temperature is 50 ℃, then the evenly mixed suspension is filtered and dried in vacuum for 12h at the temperature of 60 ℃, and finally the uniform CoFe is obtained by grinding 2 O 4 PVDF composite powder;
(4) the CoFe obtained above is added 2 O 4 The PVDF composite powder is paved in a selective laser sintering system, laser is utilized to melt the composite material powder according to a set track, and the composite material powder is superposed layer by layer and formed in a three-dimensional mode. And after sintering is finished, removing unsintered powder by adopting compressed air, and finally constructing the bio-piezoelectric bone scaffold consistent with the three-dimensional model. Wherein, the main sintering technological parameters are as follows: laser power of 8W, scanning speed of 150mm/s, scanning interval of 0.15mm, spot diameter of 0.4mm, and CoFe 2 O 4 The thickness of a powder layer of the PVDF composite powder is 0.15mm, and the preheating temperature of a powder bed is 155 ℃.
In example three, the CoFe obtained by preparation 2 O 4 The PVDF composite bone scaffold is used for performance characterization. The specific performance test results are as follows:
(a) the test of a ferroelectric analyzer shows that CoFe is added under the experimental conditions of the example 3 2 O 4 The remanent polarization Pr of the prepared composite scaffold is 18.1 mu C/cm 2 Piezoelectric constant d 33 29.2Pc/N, 26.1emu/g magnetic saturation intensity Ms and magneto-electric coefficient alpha 33 ＝15.3mV/cmOe。
(b) The cell activity test shows that the CoFe in the third embodiment 2 O 4 After the cells on the PVDF composite bone scaffold are cultured for 7 days, the cell adhesion, proliferation and differentiation capacities are obviously superior to those of a pure PVDF scaffold.
Example 4
CoFe according to the fourth embodiment of the present invention 2 O 4 The preparation method of the PVDF composite bone scaffold specifically comprises the following steps:
(1) 2.5g of CoFe were weighed using an electronic balance 2 O 4 Powder, CoFe 2 O 4 The particle size of the powder is 40nm, the powder is added into a three-mouth beaker filled with 75mL of absolute ethyl alcohol solution, pre-dispersion is realized through mechanical stirring and ultrasonic dispersion, and then uniform and stable CoFe is obtained 2 O 4 The ethanol suspension of (a);
(2) weighing 7.5g of PVDF powder by using an electronic balance, wherein the particle size of the PVDF powder is 80 microns, adding the PVDF powder into a three-opening beaker filled with 100mL of absolute ethanol solution, and pre-dispersing the PVDF powder by mechanical stirring and ultrasonic dispersion to obtain uniform and stable PVDF ethanol suspension;
(3) the PVDF ethanol suspension was added dropwise to CoFe 2 O 4 Then the mixed solution is stirred by magnetic force and dispersed and mixed evenly by ultrasonic. Wherein, the corresponding mechanical stirring time is 70min, the rotating speed is 800r/min, the temperature is 50 ℃, then the evenly mixed suspension is filtered and dried in vacuum for 12h at the temperature of 60 ℃, and finally the uniform CoFe is obtained by grinding 2 O 4 PVDF composite powder;
(4) treating the CoFe subjected to magnetic field and electric field treatment 2 O 4 And putting the PVDF powder into a selective laser sintering system, melting the composite material powder by using laser according to a set track, superposing layer by layer, and forming in a three-dimensional way. And after sintering is finished, removing unsintered powder by adopting compressed air, and finally constructing the bio-piezoelectric bone scaffold consistent with the three-dimensional model. Wherein, the main sintering technological parameters are as follows: laser power of 8W, scanning speed of 150mm/s, scanning interval of 0.15mm, spot diameter of 0.4mm, and CoFe 2 O 4 The thickness of a powder layer of the PVDF composite powder is 0.15mm, and the preheating temperature of a powder bed is 155 ℃.
(5) Subjecting the CoFe 2 O 4 Placing the PVDF composite bone scaffold in a closed container, standing for 0.5h, and taking out, wherein the closed container is positioned at a preset positionThe electric field intensity is 2-4 KV/mm. It should be noted that, under the action of the external polarizing electric field, the electric domains originally randomly arranged in the PVDF can be unidirectionally arranged along the external electric field, and after the external electric field is removed, most of the electric domains in the PVDF still maintain unidirectional arrangement. Poled CoFe 2 O 4 The piezoelectric performance of the PVDF composite bone scaffold can be further greatly improved.
In example four, the CoFe obtained by the preparation 2 O 4 The PVDF composite bone scaffold is used for performance characterization. The specific performance test results are as follows:
(a) the test of the ferroelectric analyzer shows that under the experimental conditions of the example 4, CoFe is added 2 O 4 The remanent polarization Pr of the prepared composite scaffold is 17.1 mu C/cm 2 Piezoelectric constant d3 3 28.2Pc/N, 25.8emu/g of magnetic saturation intensity Ms and magneto-electric coefficient alpha 33 ＝16.3mV/cmOe。
(b) The cell activity test shows that the CoFe in the third embodiment 2 O 4 After the cells on the PVDF composite bone scaffold are cultured for 7 days, the cell adhesion, proliferation and differentiation capacities are obviously superior to those of a pure PVDF scaffold.
The following conclusions can be drawn by combining the performance characterization results of the above examples 1 to 4:
(1)CoFe 2 O 4 the particle size of (a) has a certain influence on the properties of the composite. Specifically, if the particle size is too small, the nanoparticles are easily agglomerated and are not uniformly dispersed. The particle size is too small, the specific surface area is rapidly increased, but CoFe on the surface of the particle 2 O 4 Does not contribute to the magnetization, but only contributes to the magnetization inside the crystal grains. Therefore, an excessively small particle size results in low magnetization and thus a decrease in the magnetic-electric coefficient. In addition, if the particle size is too large, the effect of reinforcing the nanoparticles is not obtained, resulting in a decrease in the mechanical properties of the bone scaffold.
(2) The particle size of the PVDF has some effect on the performance of the composite. In particular, the invention relates to the preparation of CoFe by a selective laser sintering technology 2 O 4 PVDF composite scaffolds, if the particle size of PVDF is too small, although the powder may be during sinteringThe powder is melted rapidly, but the particle size is too small, the powder is stuck on a powder spreading roller shaft due to electrostatic force generated by large specific surface area of the powder, and the powder is agglomerated into small blocks, so that the powder spreading and forming are difficult. If the particle size is too large, the compactness of the powder bed after powder laying is reduced, and the porosity is increased. Meanwhile, the excessive particle size will cause partial melting of the polymer particles, and under the condition of a certain viscosity, the filling of the gaps between the powders is difficult, and finally the density of the sample will be reduced.
(3) In the present invention, the composition of the composite bone scaffold needs to be effectively controlled. In particular, if CoFe 2 O 4 If the content of (b) is too small, the stress generated for exciting the piezoelectric effect is limited, which may result in too low electromagnetic coupling coefficient and difficulty in satisfying the requirement of electrical stimulation. If CoFe 2 O 4 The content of (a) is too much, the nanoparticles are unevenly distributed, so that the interface bonding between two phases is poor, and the stress transfer efficiency is too low. Excessive CoFe during sample polarization 2 O 4 The nano particles can prevent electric domains in the PVDF from being orderly arranged in a single direction, so that the overall piezoelectric coefficient of the composite is reduced. Further CoFe 2 O 4 Too much (c) content (c) results in a reduced PVDF content and a reduced overall dipole for charge generation, which in combination result in a too low electromagnetic coupling coefficient.
(4) In the invention, the process parameters of selective laser sintering have certain influence on the performance of the composite material, so that the laser power, the scanning speed, the scanning interval, the powder laying thickness and the preheating temperature need to be adjusted within a reasonable range. In the sintering process, the laser power, the scanning speed, the scanning interval and the powder laying thickness jointly determine the laser energy density. If the laser energy density is too low, the powder is not completely melted, the porosity is high, and the mechanical properties are insufficient. If the laser energy density is too high, the powder is burnt and gasified, the molecular structure is damaged, so that air holes are formed in the sample, and the compactness and the mechanical property of the composite support are seriously reduced.
The invention has the advantages and positive effects that:
(1) using CoFe 2 O 4 The magnetostriction effect of the PVDF stimulates the piezoelectric effect of the PVDF, so that an endogenous electrical microenvironment for osteoblast growth is constructed in a bionic manner, uniform and stable electrical stimulation can regulate the functions of cell membranes in the bone repair process, activate cell signal pathways, and regulate gene expression related to bones, so that the adhesion, proliferation and differentiation of osteoblasts on a bone scaffold are promoted, and the regeneration and reconstruction of the bones are accelerated.
(2)CoFe 2 O 4 The abundant charges on the surface can act with PVDF, on one hand, the formation of beta crystals in the PVDF is promoted, on the other hand, the effective transmission of stress at an interface is enhanced, the electromechanical coupling efficiency is improved, and the magnetoelectric property, the mechanical property and the biological property of the composite material support are improved.
(3) The preparation method is simple and controllable, and the obtained CoFe 2 O 4 The PVDF magnetoelectric composite scaffold has good magnetoelectric property, mechanical property and biological property.
Comparative example 1
CoFe proposed in comparative example 1 of the invention 2 O 4 The preparation method of the PVDF composite bone scaffold comprises the following steps:
(1) 0.1g of CoFe was weighed using an electronic balance 2 O 4 Powder, CoFe 2 O 4 The particle size of the powder is 40nm, the powder is added into a three-mouth beaker filled with 75mL of absolute ethyl alcohol solution, pre-dispersion is realized through mechanical stirring and ultrasonic dispersion, and then uniform and stable CoFe is obtained 2 O 4 The ethanol suspension of (a);
(2) weighing 9.9g of PVDF powder by using an electronic balance, wherein the particle size of the PVDF powder is 80 microns, adding the PVDF powder into a three-opening beaker filled with 100mL of absolute ethyl alcohol solution, and pre-dispersing the PVDF powder by mechanical stirring and ultrasonic dispersion to obtain uniform and stable PVDF suspension;
(3) the ethanol suspension of PVDF was added dropwise to CoFe 2 O 4 Then the mixed solution is stirred by magnetic force and dispersed and mixed evenly by ultrasonic. Wherein the corresponding mechanical stirring time is 70min, the rotating speed is 800r/min, and the temperature is 50 DEG CThen filtering the uniformly mixed suspension, drying the suspension in vacuum at 60 ℃ for 12h, and finally grinding the suspension to obtain uniform CoFe 2 O 4 A PVDF composite powder.
(4) The CoFe obtained in the above step 2 O 4 And the PVDF composite powder is paved in a selective laser sintering system, the composite powder is melted by laser according to a set track, and the composite powder is superposed layer by layer and formed in a three-dimensional mode. And after sintering is finished, removing unsintered powder by adopting compressed air, and finally constructing the bio-piezoelectric bone scaffold consistent with the three-dimensional model. Wherein, the main sintering technological parameters are as follows: laser power of 8W, scanning speed of 150mm/s, scanning interval of 0.15mm, spot diameter of 0.4mm, and CoFe 2 O 4 The thickness of a powder layer of the PVDF composite powder is 0.15mm, and the preheating temperature of a powder bed is 155 ℃.
In comparative example one, the CoFe prepared 2 O 4 The PVDF composite bone scaffold is used for performance characterization. The specific performance test results are as follows:
(a) the test of the ferroelectric analyzer shows that CoFe is added under the experimental conditions of the comparative example 1 2 O 4 The remanent polarization Pr of the prepared composite scaffold is 5.1 mu C/cm 2 Piezoelectric constant d 33 14.8Pc/N, 2.4emu/g magnetic saturation intensity Ms and magneto-electric coefficient alpha 33 0.6 mV/cmOe. Magnetic saturation intensity proportional to CoFe 2 O 4 Content of CoFe in this case 2 O 4 Too low a content results in too low a magnetic saturation intensity and finally a relatively low magneto-electric coupling coefficient.
(b) The cell activity test shows that CoFe 2 O 4 After the cells on the PVDF composite material are cultured for 7 days, the adhesion, proliferation and differentiation capacities of the cells displayed by the scaffold are not obviously different from those of a pure PVDF scaffold.
Comparative example 2
CoFe proposed in comparative example 2 of the invention 2 O 4 The preparation method of the PVDF composite bone scaffold specifically comprises the following steps:
(1) 3.5g of CoFe was weighed using an electronic balance 2 O 4 Powder of CoFe 2 O 4 The particle size of the powder is 40nm, the powder is added into a three-mouth beaker filled with 75mL of absolute ethyl alcohol solution, pre-dispersion is realized through mechanical stirring and ultrasonic dispersion, and then uniform and stable CoFe is obtained 2 O 4 The ethanol suspension of (a);
(2) weighing 6.5g of PVDF powder by using an electronic balance, wherein the particle size of the PVDF powder is 80 mu m, adding the PVDF powder into a three-opening beaker filled with 100mL of absolute ethyl alcohol solution, and pre-dispersing the PVDF powder by mechanical stirring and ultrasonic dispersion to obtain uniform and stable PVDF suspension;
(3) the PVDF ethanol suspension was added dropwise to CoFe 2 O 4 Then the mixed solution is stirred by magnetic force and dispersed and mixed evenly by ultrasonic. Wherein, the corresponding mechanical stirring time is 70min, the rotating speed is 800r/min, the temperature is 50 ℃, then the evenly mixed suspension is filtered and dried in vacuum for 12h at the temperature of 60 ℃, and finally the uniform CoFe is obtained by grinding 2 O 4 A PVDF composite powder.
(4) And flatly paving the obtained composite material powder in a selective laser sintering system, melting the composite material powder according to a set track by using laser, and carrying out layer-by-layer superposition and three-dimensional forming. And after sintering is finished, removing unsintered powder by adopting compressed air, and finally constructing the bio-piezoelectric bone scaffold consistent with the three-dimensional model. Wherein, the main sintering technological parameters are as follows: the laser power is 8W, the scanning speed is 150mm/s, the scanning interval is 0.15mm, the spot diameter is 0.4mm, the thickness of the powder layer is 0.15mm, and the preheating temperature of the powder bed is 155 ℃.
In comparative example two, the CoFe obtained by the preparation method 2 O 4 The PVDF composite bone scaffold is used for performance characterization. The specific performance test results are as follows:
(a) the test of the ferroelectric analyzer shows that CoFe is added under the experimental conditions of the comparative example 2 2 O 4 The remanent polarization Pr of the prepared composite scaffold is 4.1 mu C/cm 2 Piezoelectric constant d 33 10.3Pc/N, 38.1emu/g magnetic saturation intensity Ms and magneto-electric coefficient alpha 33 ＝1.3mV/cmOe。
Furthermore, it should be noted that: CoFe 2 O 4 The content of (a) is too much, the nanoparticles are unevenly distributed, so that the interface bonding between two phases is poor, and the stress transfer efficiency is too low. Excessive CoFe during sample polarization 2 O 4 The nano particles can prevent electric domains in the PVDF from being orderly arranged in a single direction, so that the overall piezoelectric coefficient of the composite is reduced. Further CoFe 2 O 4 Too much (c) content (c) results in a reduced PVDF content and a reduced overall dipole for charge generation, which in combination result in a too low electromagnetic coupling coefficient.
(b) The cell activity test shows that CoFe 2 O 4 After the cells on the PVDF composite material are cultured for 7 days, the adhesion, proliferation and differentiation capacities of the cells displayed by the scaffold are not obviously different from those of a pure PVDF scaffold.
Comparative example 3
In comparative example three, the CoFe obtained by the preparation method 2 O 4 The PVDF composite bone scaffold is used for performance characterization. The specific performance test results are as follows:
(1) 1.5g of CoFe was weighed by an electronic balance, respectively 2 O 4 Powder of CoFe 2 O 4 The particle size of the powder is 40nm, the powder is added into a three-mouth beaker filled with 75mL of absolute ethyl alcohol solution, pre-dispersion is realized through mechanical stirring and ultrasonic dispersion, and then uniform and stable CoFe is obtained 2 O 4 The ethanol suspension of (a);
(2) weighing 8.5g of PVDF powder by using an electronic balance, wherein the particle size of the PVDF powder is 80 microns, adding the PVDF powder into a three-opening beaker filled with 100mL of absolute ethyl alcohol solution, and pre-dispersing the PVDF powder by mechanical stirring and ultrasonic dispersion to obtain uniform and stable PVDF suspension;
(3) the ethanol suspension of PVDF was added dropwise to CoFe 2 O 4 Then the mixed solution is stirred by magnetic force and dispersed and mixed evenly by ultrasonic. And (3) uniformly mixing the mixed solution by magnetic stirring and ultrasonic dispersion. Wherein the mechanical stirring time is 70min, the rotation speed is 800r/min, the temperature is 50 ℃, and then the mixture is uniformly mixedThe homogeneous suspension was filtered and dried under vacuum at 60 ℃ for 12h, and finally ground to give homogeneous CoFe 2 O 4 PVDF composite powder;
(4) and flatly paving the obtained composite material powder in a selective laser sintering system, melting the composite material powder by using laser according to a set track, superposing layer by layer, and forming in a three-dimensional mode. And after sintering is finished, removing unsintered powder by adopting compressed air, and finally constructing the bio-piezoelectric bone scaffold consistent with the three-dimensional model. Wherein, the main sintering technological parameters are as follows: the laser power is 8W, the scanning speed is 150mm/s, the scanning interval is 0.15mm, the spot diameter is 0.4mm, the thickness of the powder layer is 0.15mm, and the preheating temperature of the powder bed is 155 ℃.
In comparative example III, the CoFe obtained by the preparation method is used 2 O 4 The PVDF composite bone scaffold is used for performance characterization. The specific performance test results are as follows:
(a) it was found by the test of the ferroelectric analyzer that CoFe was added under the experimental conditions of this comparative example 3 2 O 4 The remanent polarization Pr of the prepared composite scaffold is 9.1 mu C/cm 2 Piezoelectric constant d 33 19.4Pc/N magnetic saturation Ms-12.1 emu/g and magneto-electric coefficient alpha 33 4.3 mV/cmOe. Each test index decreased compared to example 2. Is prepared from CoFe in the process of preparing powder 2 O 4 And PVDF powder was not separately dispersed in the ethanol solution but directly mixed, resulting in uneven mixing of the initial powders. So that CoFe 2 O 4 The distribution in the rack is not uniform. CoFe 2 O 4 Due to the agglomeration of the nano particles, the interface bonding between two phases is poor, the stress transfer efficiency is too low, and the magnetoelectric coefficient is reduced.
(b) The CoFe in this comparative example was found to be present in the cell viability assay 2 O 4 After 7 days of culture of the cells on the/PVDF composite, the scaffolds in this comparative example exhibited poorer cell adhesion, proliferation and differentiation abilities, compared to example 2.
Finally, it should be noted that: the above-mentioned embodiments are only specific embodiments of the present invention, which are used for illustrating the technical solutions of the present invention and not for limiting the same, and the protection scope of the present invention is not limited thereto, although the present invention is described in detail with reference to the foregoing embodiments, those skilled in the art should understand that: any person skilled in the art can modify or easily conceive the technical solutions described in the foregoing embodiments or equivalent substitutes for some technical features within the technical scope of the present disclosure; such modifications, changes or substitutions do not depart from the spirit and scope of the embodiments of the present invention, and they should be construed as being included therein. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.

Claims (7)

1. CoFe 2 O 4 PVDF composite bone scaffold, characterized in that said CoFe 2 O 4 The PVDF composite bone scaffold is made of CoFe 2 O 4 The ethanol suspension and the ethanol suspension of PVDF are mixed and stirred, and the CoFe obtained is 2 O 4 Filtering solid-liquid phase separation of PVDF mixed suspension, drying and ball milling the obtained solid phase to obtain composite powder, and selectively laser sintering the composite powder to obtain the CoFe 2 O 4 PVDF composite bone scaffold, wherein said CoFe 2 O 4 The composite material is spinel type cobalt ferrite, and the PVDF is polyvinylidene fluoride;
the CoFe 2 O 4 The residual polarization intensity of the PVDF composite bone scaffold is 4.1-18.1 mu C/cm 2 The piezoelectric constant is 14.8-29.2 Pc/N, the magnetic saturation intensity is 2.4-38.1 emu/g, and the magnetoelectric coefficient is 0.6-15.3 mV/cmOe;
wherein, CoFe 2 O 4 The cell adhesion, proliferation and differentiation capacities of the PVDF composite bone scaffold are superior to those of a pure PVDF scaffold;
CoFe 2 O 4 the number of cells on the PVDF composite bone scaffold is larger than that on the pure PVDF scaffold, and CoFe is generated by magnetoelectric coupling effect under the action of external magnetic field 2 O 4 The PVDF compound bone scaffold generates electric charge on the surface, and the electric charge affects the cell membraneCalcium ion signal channels, which further promote the calcium ions to flow into the cells so as to promote the proliferation and differentiation of bone cells;
in the CoFe 2 O 4 In PVDF composite bone scaffolds, CoFe 2 O 4 The mass fraction of the composite is 5-25 wt%, the mass fraction of PVDF is 75-95 wt%, the particle size of PVDF is 40-100 mu m, and CoFe 2 O 4 The particle size of (A) is 30-200 nm;
when sintering is carried out in the selective laser sintering system, the laser power is 6-16W, the scanning speed is 100-200 mm/s, the scanning interval is 0.1-0.2 mm, the corresponding light spot diameter is 0.3-0.6 mm, the powder spreading thickness is 0.1-0.2 mm, and the corresponding powder bed preset temperature is 140-160 ℃.
2. CoFe according to claim 1 2 O 4 PVDF composite bone scaffold, characterized in that said PVDF and said CoFe 2 O 4 The purity of (A) was 99%.
3. CoFe according to any one of claims 1 to 2 2 O 4 The preparation method of the PVDF composite bone scaffold is characterized by comprising the following steps:
the method comprises the following steps: weighing CoFe 2 O 4 Adding the powder into a three-neck flask containing absolute ethyl alcohol solution, and pre-dispersing the powder through mechanical stirring and ultrasonic dispersion to obtain CoFe 2 O 4 Wherein the CoFe 2 O 4 Is spinel type cobalt ferrite;
step two: weighing PVDF powder, adding the PVDF powder into a three-neck flask containing absolute ethyl alcohol solution, pre-dispersing the PVDF powder through mechanical stirring and ultrasonic dispersion to obtain an ethyl alcohol suspension of the PVDF, and dropwise adding the ethyl alcohol suspension of the PVDF to the CoFe 2 O 4 To obtain a mixed solution, and controlling CoFe in the mixed solution 2 O 4 The mass ratio of the powder to the PVDF powder is a first mass ratio, and the obtained mixed solution is stirred at a first stirring speed in a first preset temperature environmentUltrasonically stirring at a rotating speed for a first preset time, filtering the mixed solution, drying in vacuum at a second preset temperature for a second preset time, and ball-milling to obtain CoFe 2 O 4 PVDF powder;
step three: subjecting the CoFe 2 O 4 Placing PVDF powder in a selective laser sintering system, sintering layer by layer according to a three-dimensional model, and removing unsintered powder after sintering to obtain CoFe 2 O 4 PVDF composite bone scaffold;
the CoFe 2 O 4 The residual polarization intensity of the PVDF composite bone scaffold is 4.1-18.1 mu C/cm 2 The piezoelectric constant is 14.8-29.2 Pc/N, the magnetic saturation intensity is 2.4-38.1 emu/g, and the magnetoelectric coefficient is 0.6-15.3 mV/cmOe;
wherein, CoFe 2 O 4 The cell adhesion, proliferation and differentiation capacities of the PVDF composite bone scaffold are superior to those of a pure PVDF scaffold;
CoFe 2 O 4 the number of cells on the PVDF composite bone scaffold is larger than that on the pure PVDF scaffold, and CoFe is generated by magnetoelectric coupling effect under the action of external magnetic field 2 O 4 The surface of the PVDF composite bone scaffold generates charges which affect calcium ion signal channels on cell membranes, thereby promoting the flow of calcium ions into cells and promoting the proliferation and differentiation of bone cells.
4. CoFe according to claim 3 2 O 4 The preparation method of the PVDF composite bone scaffold is characterized in that in the second step, the first mass ratio is 5-25: 75-95, the first preset temperature is 30-60 ℃, the first stirring speed is 700-1000 r/min, the first preset time is 60-120 min, the second preset temperature is 50-70 ℃, and the second preset time is 10-12 h.
5. CoFe according to claim 3 2 O 4 The preparation method of the PVDF composite bone scaffold is characterized in that in the third step, when sintering is carried out in the selective laser sintering system, the sintering is carried outThe optical power is 6-16W, the scanning speed is 100-200 mm/s, the scanning interval is 0.1-0.2 mm, the corresponding spot diameter is 0.3-0.6 mm, and the CoFe 2 O 4 The thickness of a powder layer of PVDF powder is 0.1-0.2 mm, and the corresponding preset temperature of a powder bed is 140-160 ℃.
6. CoFe according to claim 3 2 O 4 The preparation method of the PVDF composite bone scaffold is characterized in that the CoFe 2 O 4 In the PVDF composite bone scaffold, the particle size of PVDF is 40-100 mu m, and CoFe 2 O 4 Has a particle diameter of 30 to 200nm, and the PVDF and the CoFe 2 O 4 The purity of (A) was 99%.
7. CoFe according to claim 3 2 O 4 The preparation method of the PVDF composite bone scaffold is characterized in that after the third step, the method further comprises the following steps:
subjecting the CoFe 2 O 4 The PVDF composite bone support is placed in a closed container, stands for 0.5h and is taken out, wherein the closed container is positioned in an electric field with the preset electric field intensity of 2-4 KV/mm.
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