CN108943700B - Preparation method of poly-L-lactic acid/ferroferric oxide composite bone scaffold - Google Patents

Preparation method of poly-L-lactic acid/ferroferric oxide composite bone scaffold Download PDF

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CN108943700B
CN108943700B CN201810788518.4A CN201810788518A CN108943700B CN 108943700 B CN108943700 B CN 108943700B CN 201810788518 A CN201810788518 A CN 201810788518A CN 108943700 B CN108943700 B CN 108943700B
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plla
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bone scaffold
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CN108943700A (en
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冯佩
帅词俊
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Central South University
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
    • B29C64/10—Processes of additive manufacturing
    • B29C64/141—Processes of additive manufacturing using only solid materials
    • B29C64/153—Processes of additive manufacturing using only solid materials using layers of powder being selectively joined, e.g. by selective laser sintering or melting
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y10/00—Processes of additive manufacturing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y70/00—Materials specially adapted for additive manufacturing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2067/00—Use of polyesters or derivatives thereof, as moulding material
    • B29K2067/04—Polyesters derived from hydroxycarboxylic acids
    • B29K2067/046—PLA, i.e. polylactic acid or polylactide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2505/00—Use of metals, their alloys or their compounds, as filler
    • B29K2505/08—Transition metals
    • B29K2505/12—Iron

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Mechanical Engineering (AREA)
  • Materials For Medical Uses (AREA)

Abstract

The invention relates to a preparation method of a poly-L-lactic acid/ferroferric oxide composite bone scaffold, which is prepared by dispersing Fe3O4Dropwise adding the ethanol solution of the powder into the ethanol solution dispersed with PLLA powder, performing ultrasonic dispersion and ball milling to obtain a mixed solution, performing solid-liquid separation to obtain a solid phase, drying and grinding to obtain composite powder, and performing selective laser sintering on the composite powder to obtain PLLA/Fe3O4A composite bone scaffold. Fe is dispersed and ball-milled by ultrasound under a liquid phase system3O4Uniformly dispersing the particles and PLLA particles in a mixed solution, and preparing the magnetic PLLA/Fe by a selective laser sintering technology3O4Composite bone scaffolds, uniformly dispersed Fe3O4The particles and PLLA have good interface binding performance, and the mechanical property of the bone scaffold can be effectively improved. The obtained magnetic PLLA/Fe3O4Composite bone scaffold, nano-Fe3O4The magnetic property of the magnetic material can generate magnetic stimulation on osteoblasts, thereby promoting the adhesion, proliferation and differentiation of osteoblasts on the bone scaffold.

Description

Preparation method of poly-L-lactic acid/ferroferric oxide composite bone scaffold
Technical Field
The invention relates to a preparation method of a poly-L-lactic acid/ferroferric oxide composite bone scaffold, belonging to the technical field of bone scaffold preparation.
Background
At present, artificial bone transplantation can be customized and designed according to needs to get wide attention of researchers at home and abroad due to unlimited sources. The polymer material has good biological properties and is widely used as an artificial bone graft material, wherein poly-L-lactic acid (PLLA) is a biodegradable polymer material with good biocompatibility and no toxicity, and is considered as a promising bone scaffold material. However, PLLA bone scaffolds have delayed healing or no healing due to loss of cellular activity or death during bone repair after implantation into a bone defect site, and PLLA is brittle and hydrophobic, which is not conducive to adhesion and proliferation of cells on the scaffold, thus limiting its application to some extent.
Nano ferroferric oxide (Fe)3O4) Is a magnetic nanoparticle with superparamagnetism and each Fe particle3O4The particles can generate a magnetic field in a nanometer scale, so that Fe is absorbed3O4The nanoparticles are incorporated into the PLLA scaffold and may beEndowing the bone scaffold with magnetism, so that the scaffold continuously generates magnetic stimulation to cells in the bone repair process, regulates the functions of cell membranes, activates cell signal channels, regulates gene expression related to bones, thereby enhancing cell activity and promoting bone regeneration. In addition Fe3O4The good hydrophilicity of the nano particles can effectively improve the hydrophilic capability of the bone scaffold, and Fe is utilized3O4The strong chemical interaction between the particles and the PLLA molecular chains can improve the mechanical properties of the bone scaffold.
However Fe3O4The nanoparticles have the problem of easy agglomeration in the polymer matrix, because PLLA/Fe prepared by the current existing technology3O4Composite material Fe3O4Surface modification such as polyethylene glycol, silica, etc., and then dispersion in an organic solvent such as chloroform, which lowers Fe3O4The magnetic saturation strength of nanoparticles or the residual toxic agents limit their application in biomedicine.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide poly-L-lactic acid/ferroferric oxide (PLLA/Fe) with good mechanical property and biological property3O4) A preparation method of a composite bone scaffold.
In order to achieve the above purpose, the invention provides the following technical scheme:
a preparation method of poly-L-lactic acid/ferroferric oxide composite bone scaffold comprises dispersing Fe3O4Dropwise adding the ethanol solution of the powder into the ethanol solution dispersed with PLLA powder, performing ultrasonic dispersion and ball milling to obtain a mixed solution, performing solid-liquid separation to obtain a solid phase, drying and grinding to obtain composite powder, and performing selective laser sintering on the composite powder to obtain PLLA/Fe3O4A composite bone scaffold.
The technical scheme of the invention is to mix Fe3O4The powder is dispersed in advance and added dropwise to the ethanol solution containing PLLA powder, which is beneficial to Fe3O4Uniformly dispersing in PLLA solution, and mixing the solutionFurther performing ultrasonic treatment and ball milling to obtain uniformly dispersed mixed solution, and performing solid-liquid separation to obtain Fe in solid phase3O4The particles are uniformly dispersed in a polymer PLLA matrix, and then magnetic PLLA/Fe is prepared by a selective laser sintering technology3O4Composite bone scaffolds, uniformly dispersed Fe3O4The particles and PLLA have good interface binding performance, and the mechanical property of the bone scaffold can be effectively improved. The obtained magnetic PLLA/Fe3O4Composite bone scaffold, nano-Fe3O4The magnetic property of the magnetic material can generate magnetic stimulation on osteoblasts, thereby promoting the adhesion, proliferation and differentiation of osteoblasts on the bone scaffold.
Preferably, in the composite powder, the mass fraction of the PLLA powder is 90-97.5 wt%, and the weight fraction of the PLLA powder is Fe3O4The mass fraction of the powder is 2.5-10 wt%.
The inventors found that Fe3O4The addition of the powder has certain influence on the performance of the composite scaffold, and Fe in a PLLA matrix3O4Too low a content has a limited stimulatory effect on cell activity, while Fe3O4The excessive content of the Fe-B-Fe alloy can still cause agglomeration and influence Fe3O4And the PLLA molecular chain, thereby influencing the mechanical property of the composite scaffold.
More preferably, in the composite powder, the mass fraction of the PLLA powder is 92.5-95 wt%, and the weight fraction of the PLLA powder is Fe3O4The mass fraction of the powder is 5-7.5 wt%.
In a preferred scheme, the particle size of the PLLA powder is 40-100 mu m, the viscosity is 0.3-5dl/g, the purity is more than or equal to 99%, and the melting point is 150-190 ℃.
In a preferred embodiment, said Fe3O4The particle size of the powder is 5-30 nm, and the purity is more than or equal to 99%.
Fe used in the present invention3O4The powder had a molecular weight of 231.54 and a density of 5.18g/cm3。
Preferably, Fe will be dispersed3O4Dropping the alcoholic solution of the powder into the alcoholic solution of the PLLA dispersed powder, the dropThe acceleration is 1-1.5 ml/s.
More preferably, Fe will be dispersed3O4And dropwise adding the ethanol solution of the powder into the ethanol solution dispersed with the PLLA powder, wherein the dropwise adding speed is 1.2-1.5 ml/s.
In the preferable scheme, the ultrasonic dispersion time is 20-40 min, and the ultrasonic dispersion temperature is 50-60 ℃.
In a preferable scheme, the ball milling time is 1-4 h, and the ball milling speed is 100-300 r/min.
More preferably, the ball milling time is 3-4 h, and the ball milling speed is 200-300 r/min.
The inventor finds that the ball milling time is too short to play a role in uniform dispersion, and the ball milling time is too long to influence the structure of the material.
In the preferable scheme, the temperature of the solid phase drying is 50-60 ℃, and the time is 10-24 h. In the invention, the ethanol solution is used as a dispersion solution, and the ethanol can be quickly volatilized by drying a solid phase in the preparation process of the composite powder, so that no organic solvent residue exists.
In the preferred scheme, the selective laser sintering process parameters are as follows: the laser power is 2-5W, the scanning speed is 60-120 mm/min, the scanning interval is 0.8-1.5 mm, the spot diameter is 0.3-0.5 mm, and the preheating temperature of the powder bed is 200-220 ℃.
The inventor finds that the technological parameters of laser sintering have certain influence on the performance of the composite material, and the optimal magnetic PLLA/Fe with excellent performance can be finally obtained through the synergistic effect of the laser power, the scanning speed and the spot diameter within a reasonable range3O4The composite bone scaffold is characterized in that the laser power, the scanning speed and the spot diameter in the laser sintering process jointly determine the energy density of laser sintering, if the energy density is too low, the sintering is not compact, the mechanical property is not enough, if the energy density is too high, the overburning phenomenon including carbonization and burning loss, blistering, cracking and the like can occur, and the mechanical property of the bone scaffold is seriously reduced.
As a further preferred, the selective laser sintering process parameters are: the laser power is 2-4W, the scanning speed is 100-120 mm/min, the scanning interval is 0.9-1.2 mm, the diameter of a light spot is 0.3-0.4 mm, and the preheating temperature of a powder bed is 200-210 ℃;
preferably, Fe is dispersed3O4The preparation method of the ethanol solution of the powder comprises the following steps: mixing Fe3O4Adding the powder into ethanol, and performing ultrasonic dispersion to obtain Fe-dispersed powder3O4And (3) an ethanol solution of the powder, wherein the ultrasonic dispersion time is 20-40 min, and the ultrasonic dispersion temperature is 50-60 ℃. Fe3O4The powder is firstly dispersed in ethanol solution by ultrasonic, and then is added into ethanol solution containing PLLA powder in a dropwise adding mode, and the method is beneficial to Fe3O4Homogeneous dispersion in PLLA solution.
Preferably, said Fe is dispersed3O4In ethanolic solution of the powder, Fe3O4The solid-liquid mass-volume ratio of the powder to the ethanol is 0.01-0.04 (g/ml).
Preferably, the preparation method of the ethanol solution dispersed with the PLLA powder is as follows: adding PLLA powder into ethanol, and performing ultrasonic dispersion for 20-40 min at 50-60 ℃ to obtain an ethanol solution in which the PLLA powder is dispersed.
In a preferable scheme, in the ethanol solution dispersed with the PLLA powder, the solid-liquid mass-volume ratio of the PLLA powder to ethanol is 0.072-0.078 (g/ml).
PLLA/Fe of the invention3O4The preparation method of the composite bone scaffold mainly comprises the following steps:
(1) and designing a three-dimensional model according to the bone tissue structure of the bone defect part.
(2) According to the solid-liquid mass-volume ratio of the PLLA powder to the ethanol of 0.072-0.078 g/ml, adding the PLLA powder into an ethanol cup, and performing ultrasonic dispersion to obtain an ethanol solution with the PLLA powder uniformly dispersed, wherein the ultrasonic dispersion time is 20-40 min; according to Fe3O4The solid-liquid mass-volume ratio of the powder to the ethanol is 0.01-0.04 g/ml, and Fe is taken3O4The powder is added into an ethanol cup,the evenly dispersed Fe is obtained by ultrasonic dispersion3O4The ultrasonic dispersion time is 20-40 min, and the ultrasonic dispersion temperature is 50-60 ℃;
(3) will be dispersed with Fe3O4Dropwise adding the ethanol solution of the powder into the ethanol solution dispersed with the PLLA powder at the speed of 1-1.5 ml/s, and uniformly mixing by ultrasonic dispersion and ball milling to obtain a mixed solution, wherein the ultrasonic dispersion time is 20-40 min, the ultrasonic dispersion temperature is 50-60 ℃, the ball milling time is 1-4 h, and the ball milling speed is 100-300 r/min;
(4) after the mixed solution is subjected to liquid-solid separation, drying the solid phase to obtain mixed powder, wherein the drying temperature is 50-60 ℃, and the drying time is 10-24 hours;
(5) putting the dried mixed powder into a mortar for grinding for 20-30 min to obtain PLLA/Fe3O4Compounding powder;
(6) placing the composite powder in a selective laser sintering system, sintering layer by layer according to a three-dimensional model, and removing the unsintered powder after sintering to obtain PLLA/Fe3O4The selective laser sintering process parameters of the composite bone scaffold are as follows: the laser power is 2-5W, the scanning speed is 60-120 mm/min, the scanning interval is 0.8-1.5 mm, the spot diameter is 0.3-0.5 mm, and the preheating temperature of the powder bed is 200-220 ℃.
The invention has the advantages and positive effects that:
nano ferroferric oxide (Fe)3O4) Is a magnetic nanoparticle with superparamagnetism and each Fe particle3O4The particles can generate a magnetic field in a nanometer scale, so that Fe is absorbed3O4The nano particles are incorporated into the PLLA scaffold, so that the magnetic property can be endowed to the bone scaffold, the scaffold can continuously generate magnetic stimulation to cells in the bone repair process, the functions of cell membranes are regulated, cell signal channels are activated, and the gene expression related to bones is regulated, thereby enhancing the cell activity and promoting the bone regeneration. However, the nano ferroferric oxide has the characteristic of easy agglomeration, so that PLLA/Fe prepared by the prior art3O4The composite material must be firstly mixed with Fe3O4The surface is modified, howeverSample will reduce Fe3O4The magnetic saturation strength of nanoparticles or the residual toxic agents limit their application in biomedicine.
The technical scheme of the invention is to mix Fe3O4The powder is ultrasonically dispersed in advance and added into the ethanol solution containing the PLLA powder in a dropwise manner, which is beneficial to Fe3O4Uniformly dispersing in PLLA solution, further performing ultrasonic treatment and ball milling on the mixed solution to obtain uniformly dispersed mixed solution, and performing solid-liquid separation to obtain Fe in solid phase3O4The particles are uniformly dispersed in a polymer PLLA matrix, and the designed bone scaffold model is sintered layer by using a selective laser sintering technology to obtain the magnetic PLLA/Fe with an internal interconnected porous structure and an individualized appearance3O4Composite bone scaffolds, uniformly dispersed Fe3O4The particles and PLLA have good interface binding performance, and the mechanical property of the bone scaffold can be effectively improved. The obtained magnetic PLLA/Fe3O4Composite bone scaffold, nano-Fe3O4The magnetic property of the magnetic material can generate magnetic stimulation on osteoblasts, thereby promoting the adhesion, proliferation and differentiation of osteoblasts on the bone scaffold.
The preparation method is simple and controllable, environment-friendly, and the obtained magnetic PLLA/Fe3O4 composite bone scaffold has excellent mechanical property and biological property, and is suitable for industrial popularization and application.
Detailed Description
The following further describes embodiments of the present invention with reference to specific examples, but the present invention is not limited thereto.
Example 1
1) Carrying out porous structure and individualized appearance design on the composite scaffold by utilizing SolidWorks three-dimensional design software, and introducing a designed three-dimensional data model into a computer for carrying out layered slicing processing to obtain the section profile information of each layer;
2) 3.9g of PLLA powder having a particle size of 80 μm and 20nm of Fe were weighed out by an electronic balance, respectively3O4Powder 0.1g, then adding into a beaker containing 50ml and 10ml ethanol, respectively, for PLLA-ethanol solution and Fe3O4Ultrasonic dispersion of an ethanol solution to prepare a solution having 2.5 wt% Fe3O4The composite powder of (1). The main technological parameters are as follows: ultrasonic dispersion time is 40min, and temperature is 50 ℃;
3) dispersing the Fe3O4-the ethanol solution is added into the PLLA-ethanol solution at a dropping speed of 1ml/s for mixing, and then the dispersion is carried out by utilizing ultrasonic and ball milling technologies, wherein the main technological parameters are as follows: the ultrasonic dispersion time is 40min, the temperature is 50 ℃, the ball milling time is 3h, and the ball milling speed is 300 r/min;
4) the mixed solution is dried in a drying oven after liquid-solid separation, and the main technological parameters are as follows: the drying temperature is 55 ℃, and the heat preservation time is 24 hours;
5) mechanically grinding the dried mixed powder to obtain PLLA-Fe3O4And (3) compounding the powder. Preparation of PLLA-Fe by using selective laser sintering system3O4And the system selectively sinters the powder material layer by layer according to the interface profile information of the three-dimensional data model, and removes unsintered powder after sintering is finished to obtain the required three-dimensional entity of the magnetic composite support. The main technological parameters in the sintering process are as follows: the laser power is 3W, the scanning speed is 120mm/min, the scanning interval is 1mm, the spot diameter is 0.3mm, and the preheating temperature of the powder bed is 200 DEG C
6) The mechanical property test shows that 2.5 wt.% of Fe is added3O4The compressive strength of the post composite scaffold was 30.1MPa, which was improved by 36% compared to the pure PLLA scaffold.
7) The addition of 2.5 wt.% Fe was found to be after cell compatibility testing3O4After 7 days of culture, the adhesion morphology, proliferation rate and differentiation capacity of the cells on the composite scaffold are superior to those of the cells cultured on a pure PLLA scaffold.
Example 2
1) Carrying out porous structure and individualized appearance design on the composite scaffold by utilizing SolidWorks three-dimensional design software, and introducing a designed three-dimensional data model into a computer for carrying out layered slicing processing to obtain the section profile information of each layer;
2) 3.8g of PLLA powder having a particle size of 80 μm and 20nm of Fe were weighed out by an electronic balance, respectively3O40.2g of the powder was added to a beaker containing 50ml and 10ml of ethanol for PLLA-ethanol solution and Fe3O4Ultrasonic dispersion of an ethanol solution to prepare a solution with 5 wt% Fe3O4The composite powder of (1). The main technological parameters are as follows: ultrasonic dispersion time is 40min, and temperature is 50 ℃;
3) dispersing the Fe3O4-the ethanol solution is added into the PLLA-ethanol solution at a dropping speed of 1.2ml/s for mixing, and then the dispersion is carried out by utilizing the ultrasonic and ball milling technologies, wherein the main technological parameters are as follows: the ultrasonic dispersion time is 40min, the temperature is 50 ℃, the ball milling time is 3h, and the ball milling speed is 300 r/min;
4) the mixed solution is dried in a drying oven after liquid-solid separation, and the main technological parameters are as follows: the drying temperature is 55 ℃, and the heat preservation time is 24 hours;
5) mechanically grinding the dried mixed powder to obtain PLLA-Fe3O4And (3) compounding the powder. Preparation of PLLA-Fe by using selective laser sintering system3O4And the system selectively sinters the powder material layer by layer according to the interface profile information of the three-dimensional data model, and removes unsintered powder after sintering is finished to obtain the required three-dimensional entity of the magnetic composite support. The main technological parameters in the sintering process are as follows: the laser power is 3W, the scanning speed is 120mm/min, the scanning interval is 1mm, the spot diameter is 0.3mm, and the preheating temperature of the powder bed is 200 ℃;
6) the mechanical property test shows that 5 wt.% of Fe is added3O4The compressive strength of the rear composite scaffold is 36.2MPa, which is improved by 60% compared with a pure PLLA scaffold;
7) after the addition of 7.5 wt.% Fe, the cell compatibility test shows that3O4After the cells on the composite scaffold are cultured for 7 days, the adhesion morphology, proliferation rate and differentiation capacity of the cells are obviously superior to those of the cells cultured on a pure PLLA scaffold.
Example 3
1) Carrying out porous structure and individualized appearance design on the composite scaffold by utilizing SolidWorks three-dimensional design software, and introducing a designed three-dimensional data model into a computer for carrying out layered slicing processing to obtain the section profile information of each layer;
2) 3.7g of PLLA powder having a particle size of 80 μm and 20nm of Fe were weighed out by an electronic balance, respectively3O40.3g of the powder was added to a beaker containing 50ml and 10ml of ethanol for PLLA-ethanol solution and Fe3O4Ultrasonic dispersion of an ethanol solution to prepare a solution with 7.5 wt% Fe3O4The composite powder of (1). The main technological parameters are as follows: ultrasonic dispersion time is 40min, and temperature is 50 ℃;
3) dispersing the Fe3O4-the ethanol solution is added into the PLLA-ethanol solution at a dropping speed of 1.5ml/s for mixing, and then the dispersion is carried out by utilizing the ultrasonic and ball milling technologies, wherein the main technological parameters are as follows: the ultrasonic dispersion time is 40min, the temperature is 50 ℃, the ball milling time is 3h, and the ball milling speed is 300 r/min;
4) the mixed solution is dried in a drying oven after liquid-solid separation, and the main technological parameters are as follows: the drying temperature is 55 ℃, and the heat preservation time is 24 hours;
5) mechanically grinding the dried mixed powder to obtain PLLA-Fe3O4And (3) compounding the powder. Preparation of PLLA-Fe by using selective laser sintering system3O4And the system selectively sinters the powder material layer by layer according to the interface profile information of the three-dimensional data model, and removes unsintered powder after sintering is finished to obtain the required three-dimensional entity of the magnetic composite support. The main technological parameters in the sintering process are as follows: the laser power is 3W, the scanning speed is 120mm/min, the scanning interval is 1mm, the spot diameter is 0.3mm, and the preheating temperature of the powder bed is 200 ℃;
6) the mechanical property test shows that 7.5 wt.% of Fe is added3O4The compressive strength of the post composite scaffold was 41.1MPa, which was 82% higher than that of the pure PLLA scaffold.
7) The addition of 7.5 wt.% F was found to be compatible with cellse3O4After the cells on the composite scaffold are cultured for 7 days, the adhesion morphology, proliferation rate and differentiation capacity of the cells are obviously superior to those of the cells cultured on a pure PLLA scaffold.
Comparative example 1
1) Carrying out porous structure and individualized appearance design on the composite scaffold by utilizing SolidWorks three-dimensional design software, and introducing a designed three-dimensional data model into a computer for carrying out layered slicing processing to obtain the section profile information of each layer;
2) 3.5g of PLLA powder having a particle size of 80 μm and 20nm of Fe were weighed out by an electronic balance, respectively3O40.5g of the powder was added to a beaker containing 50ml and 10ml of ethanol for PLLA-ethanol solution and Fe3O4Ultrasonic dispersion of ethanol solution to prepare a solution with 12.5 wt% Fe3O4The main technological parameters of the composite powder are as follows: ultrasonic dispersion time is 40min, and temperature is 50 ℃;
3) dispersing the Fe3O4-dripping the ethanol solution into the PLLA-ethanol solution for mixing, and then dispersing by using ultrasonic and ball milling technologies, wherein the main process parameters are as follows: the ultrasonic dispersion time is 40min, the temperature is 50 ℃, the ball milling time is 3h, and the ball milling speed is 300 r/min;
4) the mixed solution is dried in a drying oven after liquid-solid separation, and the main technological parameters are as follows: the drying temperature is 55 ℃, and the heat preservation time is 24 hours;
5) mechanically grinding the dried mixed powder to obtain PLLA-Fe3O4And (3) compounding the powder. Preparation of PLLA-Fe by using selective laser sintering system3O4And the system selectively sinters the powder material layer by layer according to the interface profile information of the three-dimensional data model, and removes unsintered powder after sintering is finished to obtain the required three-dimensional entity of the magnetic composite support. The main technological parameters in the sintering process are as follows: the laser power is 3W, the scanning speed is 120mm/min, the scanning interval is 1mm, the spot diameter is 0.3mm, and the preheating temperature of the powder bed is 200 ℃;
6) the mechanical property test shows that 12.5 wt.% of Fe is added3O4Rear composite supportHas a compressive strength of 32.3MPa, an improvement of 43% compared to a pure PLLA scaffold, but 7.5 wt.% Fe compared to the addition3O4The composite scaffold is reduced by 21%. The observation of a scanning electron microscope shows that a great amount of Fe appears on the surface of the composite scaffold3O4And (3) agglomeration.
7) The addition of 12.5 wt.% Fe was found to be after cell compatibility testing3O4After 7 days of culture, Fe3O4The morphology of cell adhesion at the uniformly dispersed sites was superior to cells cultured on pure PLLA scaffolds, but at Fe3O4Apoptosis appears at the site of aggregation.
Comparative example 2
1) Carrying out porous structure and individualized appearance design on the composite scaffold by utilizing SolidWorks three-dimensional design software, and introducing a designed three-dimensional data model into a computer for carrying out layered slicing processing to obtain the section profile information of each layer;
2) 3.7g of PLLA powder having a particle size of 80 μm and 20nm of Fe were weighed out by an electronic balance, respectively3O40.3g of the powder was added to a beaker containing 50ml and 10ml of ethanol for PLLA-ethanol solution and Fe3O4Ultrasonic dispersion of an ethanol solution to prepare a solution with 7.5 wt% Fe3O4The composite powder of (1). The main technological parameters are as follows: ultrasonic dispersion time is 40min, and temperature is 50 ℃;
3) dispersing the Fe3O4-dripping the ethanol solution into the PLLA-ethanol solution for mixing, and then dispersing by using an ultrasonic technology, wherein the main process parameters are as follows: ultrasonic dispersion time is 40min, and temperature is 50 ℃;
4) the mixed solution is dried in a drying oven after liquid-solid separation, and the main technological parameters are as follows: the drying temperature is 55 ℃, and the heat preservation time is 12 hours;
5) mechanically grinding the dried mixed powder to obtain PLLA-Fe3O4And (3) compounding the powder. Preparation of PLLA-Fe by using selective laser sintering system3O4Composite support, system for powder material according to interface contour information of three-dimensional data modelAnd (3) selectively sintering the material layer by layer, and removing unsintered powder after sintering to obtain the required three-dimensional entity of the magnetic composite bracket. The main technological parameters in the sintering process are as follows: the laser power is 3W, the scanning speed is 120mm/min, the scanning interval is 1mm, the spot diameter is 0.3mm, and the preheating temperature of the powder bed is 200 ℃;
6) the mechanical property test shows that 7.5 wt.% of Fe is added3O4The compressive strength of the rear composite scaffold is 36.6MPa, which is reduced by 11% compared with the compressive strength of the composite scaffold dispersed by using ultrasonic and ball milling technologies.
Comparative example 3
1) Carrying out porous structure and individualized appearance design on the composite scaffold by utilizing SolidWorks three-dimensional design software, and introducing a designed three-dimensional data model into a computer for carrying out layered slicing processing to obtain the section profile information of each layer;
2) 3.7g of PLLA powder having a particle size of 80 μm and 20nm of Fe were weighed out by an electronic balance, respectively3O40.3g of the powder was added to a beaker containing 50ml and 10ml of ethanol for PLLA-ethanol solution and Fe3O4Ultrasonic dispersion of an ethanol solution to prepare a solution with 7.5 wt% Fe3O4The composite powder of (1). The main technological parameters are as follows: ultrasonic dispersion time is 40min, and temperature is 50 ℃;
3) dispersing the Fe3O4-dripping the ethanol solution into the PLLA-ethanol solution for mixing, and then dispersing by using ultrasonic and ball milling technologies, wherein the main process parameters are as follows: the ultrasonic dispersion time is 40min, the temperature is 50 ℃, the ball milling time is 3h, and the ball milling speed is 300 r/min;
4) the mixed solution is dried in a drying oven after liquid-solid separation, and the main technological parameters are as follows: the drying temperature is 55 ℃, and the heat preservation time is 24 hours;
5) mechanically grinding the dried mixed powder to obtain PLLA-Fe3O4And (3) compounding the powder. Preparation of PLLA-Fe by using selective laser sintering system3O4Composite scaffolds with systems for selective powder material selection based on interface profile information from three-dimensional data modelsAnd (4) sintering the magnetic composite stent layer by layer, and removing unsintered powder after sintering to obtain the required three-dimensional entity of the magnetic composite stent. The main technological parameters in the sintering process are as follows: the laser power is 3W, the scanning speed is 40mm/min, the scanning interval is 1mm, the spot diameter is 0.3mm, and the preheating temperature of the powder bed is 200 ℃;
6) the aperture of the sintered composite stent is about 0.55mm through observation of a scanning electron microscope, while the aperture of the sintered stent is about 0.68mm at a scanning speed of 120mm/min, which shows that the aperture size of the stent is obviously reduced at a scanning speed of 40 mm/min.
7) Cell compatibility tests show that after the cells on the composite scaffold with the pore diameter of 0.68mm are cultured for 7 days, the adhesion morphology, proliferation rate and differentiation capacity of the cells are obviously higher than those of the cells cultured on the composite scaffold with the pore diameter of 0.55 mm.

Claims (9)

1. A preparation method of a poly-L-lactic acid/ferroferric oxide composite bone scaffold is characterized by comprising the following steps: will be dispersed with Fe3O4Dropwise adding the ethanol solution of the powder into the ethanol solution dispersed with PLLA powder, performing ultrasonic dispersion and ball milling to obtain a mixed solution, performing solid-liquid separation to obtain a solid phase, drying and grinding to obtain composite powder, and performing selective laser sintering on the composite powder to obtain PLLA/Fe3O4A composite bone support which is composed of a bone support body,
the parameters of the selective laser sintering process are as follows: the laser power is 2-5W, the scanning speed is 60-120 mm/min, the scanning interval is 0.8-1.5 mm, the spot diameter is 0.3-0.5 mm, and the preheating temperature of the powder bed is 200-220 ℃.
2. The preparation method of the poly-L-lactic acid/ferroferric oxide composite bone scaffold according to claim 1, characterized by comprising the following steps:
in the composite powder, the mass fraction of the PLLA powder is 90-97.5 wt%, and the weight fraction of the PLLA powder is Fe3O4The mass fraction of the powder is 2.5-10 wt%.
3. The preparation method of the poly-L-lactic acid/ferroferric oxide composite bone scaffold according to claim 1, characterized by comprising the following steps:
the particle size of the PLLA powder is 40-100 mu m, the viscosity is 0.3-5dl/g, the purity is more than or equal to 99%, and the melting point is 150-190 ℃;
said Fe3O4The particle size of the powder is 5-30 nm, and the purity is more than or equal to 99%.
4. The preparation method of the poly-L-lactic acid/ferroferric oxide composite bone scaffold according to claim 1, characterized by comprising the following steps: will be dispersed with Fe3O4And (3) dropwise adding the ethanol solution of the powder into the ethanol solution dispersed with the PLLA powder, wherein the dropwise adding speed is 1-1.5 ml/s.
5. The preparation method of the poly-L-lactic acid/ferroferric oxide composite bone scaffold according to claim 1, characterized by comprising the following steps:
the ultrasonic dispersion time is 20-40 min, and the ultrasonic dispersion temperature is 50-60 ℃.
6. The preparation method of the poly-L-lactic acid/ferroferric oxide composite bone scaffold according to claim 1, characterized by comprising the following steps:
the ball milling time is 1-4 h, and the ball milling speed is 100-300 r/min.
7. The preparation method of the poly-L-lactic acid/ferroferric oxide composite bone scaffold according to claim 1, characterized by comprising the following steps:
the temperature of the solid phase drying is 50-60 ℃, and the time is 10-24 hours.
8. The preparation method of the poly-L-lactic acid/ferroferric oxide composite bone scaffold according to claim 1, characterized by comprising the following steps:
dispersed with Fe3O4The preparation method of the ethanol solution of the powder comprises the following steps: mixing Fe3O4Adding the powder into ethanol, and performing ultrasonic dispersion to obtain Fe-dispersed powder3O4The ultrasonic dispersion time is 20-40 min, and the ultrasonic dispersion is carried outThe temperature is 50-60 ℃;
said dispersed with Fe3O4In ethanolic solution of the powder, Fe3O4The solid-liquid mass-volume ratio of the powder to the ethanol is 0.01-0.04 (g/ml).
9. The preparation method of the poly-L-lactic acid/ferroferric oxide composite bone scaffold according to claim 1, characterized by comprising the following steps:
the preparation method of the PLLA powder dispersed ethanol solution comprises the following steps: adding PLLA powder into ethanol, and ultrasonically dispersing to obtain Fe-dispersed powder3O4The ultrasonic dispersion time is 20-40 min, and the ultrasonic dispersion temperature is 50-60 ℃;
in the ethanol solution in which the PLLA powder is dispersed, the solid-liquid mass-volume ratio of the PLLA powder to ethanol is 0.072-0.078 (g/ml).
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