CN111572021A - Preparation method of silane modified molybdenum disulfide/polycaprolactone composite bone scaffold - Google Patents

Preparation method of silane modified molybdenum disulfide/polycaprolactone composite bone scaffold Download PDF

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CN111572021A
CN111572021A CN202010423097.2A CN202010423097A CN111572021A CN 111572021 A CN111572021 A CN 111572021A CN 202010423097 A CN202010423097 A CN 202010423097A CN 111572021 A CN111572021 A CN 111572021A
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mos
pcl
powder
bone scaffold
silane
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帅词俊
冯佩
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Central South University
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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
    • 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
    • A61L27/40—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material
    • A61L27/44—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material having a macromolecular matrix
    • A61L27/446—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material having a macromolecular matrix with other specific inorganic fillers other than those covered by A61L27/443 or A61L27/46
    • 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
    • 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
    • B29C64/30—Auxiliary operations or equipment
    • B29C64/307—Handling of material to be used in additive manufacturing
    • B29C64/314—Preparation
    • 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
    • B29C64/30—Auxiliary operations or equipment
    • B29C64/386—Data acquisition or data processing for additive manufacturing
    • B29C64/393—Data acquisition or data processing for additive manufacturing for controlling or regulating additive manufacturing processes
    • 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
    • B33Y40/00—Auxiliary operations or equipment, e.g. for material handling
    • B33Y40/10—Pre-treatment
    • 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
    • B33Y50/00—Data acquisition or data processing for additive manufacturing
    • B33Y50/02—Data acquisition or data processing for additive manufacturing for controlling or regulating additive manufacturing processes
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2400/00—Materials characterised by their function or physical properties
    • A61L2400/12—Nanosized materials, e.g. nanofibres, nanoparticles, nanowires, nanotubes; Nanostructured surfaces
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2430/00—Materials or treatment for tissue regeneration
    • A61L2430/02—Materials or treatment for tissue regeneration for reconstruction of bones; weight-bearing implants
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2031/00—Other particular articles
    • B29L2031/753—Medical equipment; Accessories therefor
    • B29L2031/7532—Artificial members, protheses

Abstract

The invention discloses a preparation method of a silane modified molybdenum disulfide/polycaprolactone composite bone scaffold, which comprises the following steps: (1) MoS by silane pair2Modifying the nano sheet to obtain S-MoS2Powder; (2) adding S-MoS2Dispersing the powder and PCL powder into anhydrous ethanol to obtain S-MoS2The S-MoS is obtained by centrifugal separation and drying of the/PCL mixed suspension2a/PCL composite powder; (3) S-MoS2The S-MoS is prepared from the/PCL composite powder by a laser rapid prototyping technology2a/PCL composite bone scaffold. The invention modifies MoS through silane2The nanosheets promote the PCL bone scaffold to be uniformly dispersed in the PCL bone scaffold, and simultaneously improve the interface bonding capability of the PCL bone scaffold and improve the mechanical property of the PCL bone scaffold.

Description

Preparation method of silane modified molybdenum disulfide/polycaprolactone composite bone scaffold
Technical Field
The invention belongs to the technical field of preparation of high-molecular artificial bone scaffold materials, and particularly relates to a preparation method of a silane modified molybdenum disulfide/polycaprolactone composite bone scaffold.
Background
Polycaprolactone (PCL) is a bioabsorbable polyester approved by the U.S. food and drug administration and has potential bone and cartilage repair applications. It has lower melting point (55-60 ℃) and glass transition temperature (-60 ℃), higher thermal stability, and in addition, PCL has excellent viscoelasticity and rheological property and is easy to manufacture and process into the artificial bone scaffold. However, PCL, an artificial bone scaffold material, has a disadvantage of insufficient mechanical properties.
Molybdenum disulfide (MoS)2) The nano sheet not only has a unique two-dimensional layered nano structure and excellent mechanical properties, but also has better optical, thermal and chemical properties. But due to MoS2The large surface area of the nanosheets and the strong interaction force between the nanosheets easily cause agglomeration in a polymer matrix, so that the nanosheets are not uniformly dispersed, and the performance of the composite is affected by poor interface bonding performance of the molybdenum disulfide and the PCL matrix.
Disclosure of Invention
In order to solve the defect of insufficient mechanical property of polycaprolactone serving as an artificial bone scaffold, the invention aims to provide a preparation method of a silane modified molybdenum disulfide/polycaprolactone composite bone scaffold, wherein MoS is modified by silane2The nanosheets promote the PCL bone scaffold to be uniformly dispersed in the PCL bone scaffold, and improve the interface bonding capability of the PCL bone scaffold and the PCL, so that the mechanical property of the PCL bone scaffold is improved.
In order to achieve the technical purpose, the invention adopts the following technical scheme:
a preparation method of a silane modified molybdenum disulfide/polycaprolactone composite bone scaffold comprises the following steps:
(1) MoS by silane pair2Modifying the nano sheet to obtain S-MoS2Powder;
(2) mixing S-MoS2Dispersing the powder and PCL powder into absolute ethyl alcohol to obtain S-MoS2The S-MoS is obtained by centrifugal separation and drying of the/PCL mixed suspension2a/PCL composite powder;
(3)S-MoS2the S-MoS is prepared from the/PCL composite powder by a laser rapid prototyping technology2a/PCL composite bone scaffold.
Aiming at the defect of insufficient mechanical properties of PCL as an artificial bone scaffold, the invention uses MoS2Nanosheets being composited therewith, but MoS2The large surface area of the nanosheets and the strong interaction force between the nanosheets easily cause agglomeration in the PCL matrix, so that the dispersing is uneven; based on the above, the invention further adopts silane to firstly react on MoS2The nano-sheets are subjected to surface modification, then are compounded with PCL (polycaprolactone), and the S-MoS is prepared by utilizing a laser rapid prototyping technology2a/PCL composite bone scaffold. Siloxy in silane to MoS2The nano-sheet has reactivity, the organic functional group has reactivity and compatibility to a PCL matrix, and when silane is between MoS2And a bonding layer of an organic matrix-silane-inorganic matrix can be formed between the interfaces of the nanosheets and the PCL matrix. On the one hand, silane energy and MoS2The nanosheets react, thereby promoting MoS2And due to the dispersion of the nano-sheets, on the other hand, silane can react with or be compatible with a PCL matrix, so that the interface bonding capability is improved, and the mechanical property of the composite bone scaffold is further enhanced by combining the two aspects.
In the preferable scheme, in the step (1), silane powder is dispersed into absolute ethyl alcohol with the pH value of 4-5 to obtain a silane solution; then MoS2Adding the nanosheets into a silane solution, and obtaining S-MoS after centrifugal separation and drying2And (3) powder.
In a preferable scheme, the dispersion mode adopts a magnetic stirring mode and an ultrasonic dispersion mode, the magnetic stirring time is 10-30 min, and the speed is 100-500 r/min; the ultrasonic dispersion time is 5-10 min, and the temperature is 50-60 ℃; the concentration of silane in the silane solution is 1-10 g/mL, and the MoS2The solid-liquid ratio of the nanosheet to the silane solution is 1: 10-1: 15 g/ml.
Preferably, in the step (1), the silane is 3-aminopropyltriethoxysilane; MoS2The nanosheets having a particle size of0.2-5 μm, and the purity is more than 99%.
Preferably, in step (2), S-MoS2The mass ratio of the powder to the PCL powder is 0.5-2.5: 97.5 to 99.5. The inventors found that when S-MoS2When the content of (A) is too small, the effect of enhancing the mechanical property cannot be achieved; when S-MoS2When the content of (A) is excessive, MoS2The nano-sheets still agglomerate in the PCL matrix, thereby affecting the composite effect of the composite bone scaffold.
Preferably, in the step (2), the PCL powder has a particle size of 50-100 μm, a purity of more than 99% and a melting point of 55-65 ℃.
In the preferable scheme, in the step (2), a magnetic stirring mode and an ultrasonic dispersion mode are adopted as dispersion modes, the magnetic stirring time is 10-30 min, and the speed is 100-500 r/min; the ultrasonic dispersion time is 5-10 min, and the temperature is 50-60 ℃.
In the preferable scheme, in the step (2), the centrifugal separation time is 10-20 min, and the speed is 1000-5000 r/min; the drying temperature is 50-80 ℃, and the drying time is 12-24 h.
Preferably, in step (3), the S-MoS is added2Placing the PCL composite powder in a laser rapid prototyping system, sintering layer by layer according to a preset three-dimensional model, and removing unsintered powder by using compressed air after sintering to obtain S-MoS2a/PCL composite bone scaffold.
In a preferred scheme, the laser rapid prototyping technology has the following process parameters: the laser power is 2-3W, the scanning speed is 80-150 mm/min, the scanning interval is 1-2 mm, and the diameter of a light spot is 0.8-1.0 mm.
Compared with the prior art, the invention has the advantages that:
(1) the invention relates to MoS2The nanosheets are composited with PCL (polycaprolactone), and MoS is utilized2The mechanical property of the PCL bone scaffold is improved by the good mechanical property of the nano-sheets;
(2) the invention utilizes silane to MoS2Modification of nanosheets, siloxy and MoS2The nanosheets react, thereby promoting MoS2Dispersing the nanosheets in a PCL matrix;
(3) book (I)Invention modified MoS2The nano-sheet powder is mixed with PCL powder, and organic functional groups on silane can react or are compatible with PCL, so that interface bonding is improved;
(4) the invention utilizes the laser rapid prototyping technology to prepare the S-MoS2The PCL composite artificial bone scaffold realizes the integrated preparation of the complex appearance and the controllable internal hole structure of the bone scaffold.
Drawings
FIG. 1 is a surface topography of composite bone scaffolds prepared in examples 1-3 and comparative example 1, wherein (a) is a surface topography of a composite bone scaffold prepared in comparative example 1; (b) is a surface topography map of the composite bone scaffold prepared in example 2; (c) is a surface topography map of the composite bone scaffold prepared in example 1; (d) is a surface topography map of the composite bone scaffold prepared in example 3.
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) Weighing 20g of 3-aminopropyltriethoxysilane powder, dispersing the 3-aminopropyltriethoxysilane powder in 100ml of ethanol solution with the pH of 4-5, and performing magnetic stirring at the rotating speed of 500r/min for 30min and ultrasonic dispersion at the temperature of 50 ℃ for 10min to obtain a silane solution;
(2) weigh 10g of MoS2Adding the nano-sheet powder into a silane solution, and violently stirring for 30min at room temperature to obtain S-MoS2Centrifuging at 3000rpm for 15min, washing with deionized water, and vacuum drying to obtain S-MoS2Powder;
(3) 9.8g of PCL powder and 0.2g of S-MoS were weighed2Adding the powder into a beaker filled with anhydrous ethanol, sequentially magnetically stirring at 500r/min for 60min, ultrasonically dispersing at 50 deg.C for 10min to obtain uniform mixed solution, centrifuging at 3000rpm for 15min, placing the obtained solid in an electrothermal blowing dry box, and drying at 80 deg.C for 24h to obtain S-MoS2a/PCL composite powder;
(4) mixing S-MoS2Laser rapid prototyping system for placing/PCL composite powderIn the system, sintering layer by layer according to the three-dimensional model, and removing unsintered powder by using compressed air after sintering to obtain 2.0 wt% S-MoS2The PCL composite bone scaffold has the technical parameters of the laser rapid forming technology as follows: the laser power is 2.5W, the scanning speed is 100mm/min, the scanning interval is 1mm, and the diameter of a light spot is 1 mm.
Tensile Property testing found 2.0 wt% S-MoS2The tensile strength of the/PCL composite bone scaffold is 56.18 MPa.
As shown in FIG. 1, the scanning electron microscope revealed S-MoS2Uniformly dispersed in the PCL matrix.
Example 2
(1) Weighing 20g of 3-aminopropyltriethoxysilane powder, dispersing the 3-aminopropyltriethoxysilane powder in 100ml of ethanol solution with the pH of 4-5, and performing magnetic stirring at the rotating speed of 500r/min for 30min and ultrasonic dispersion at the temperature of 50 ℃ for 10min to obtain a silane solution;
(2) weigh 10g of MoS2Adding the nano-sheet powder into a silane solution, and violently stirring for 30min at room temperature to obtain S-MoS2Centrifuging at 3000rpm for 15min, washing with deionized water, and vacuum drying to obtain S-MoS2Powder;
(3) 9.95g of PCL powder and 0.05g of S-MoS powder were weighed2Adding the powder into a beaker filled with anhydrous ethanol, sequentially magnetically stirring at 500r/min for 60min, ultrasonically dispersing at 50 deg.C for 10min to obtain uniform mixed solution, centrifuging at 3000rpm for 15min, placing the obtained solid in an electrothermal blowing dry box, and drying at 80 deg.C for 24h to obtain S-MoS2a/PCL composite powder;
(4) mixing S-MoS2Placing the/PCL composite powder in a laser rapid prototyping system, sintering layer by layer according to a three-dimensional model, and removing unsintered powder by using compressed air after sintering to obtain 0.5 wt% S-MoS2The PCL composite bone scaffold has the technical parameters of the laser rapid forming technology as follows: the laser power is 2.5W, the scanning speed is 100mm/min, the scanning interval is 1mm, and the diameter of a light spot is 1 mm.
Tensile Property testing found 0.5 wt% S-MoS2The tensile strength of the/PCL composite bone scaffold is 40.78MPa。
As shown in FIG. 1, the scanning electron microscope revealed S-MoS2Uniformly dispersed in the PCL matrix.
Example 3
(1) Weighing 20g of 3-aminopropyltriethoxysilane powder, dispersing the 3-aminopropyltriethoxysilane powder in 100ml of ethanol solution with the pH of 4-5, and performing magnetic stirring at the rotating speed of 500r/min for 30min and ultrasonic dispersion at the temperature of 50 ℃ for 10min to obtain a silane solution;
(2) weigh 10g of MoS2Adding the nano-sheet powder into a silane solution, and violently stirring for 30min at room temperature to obtain S-MoS2Centrifuging at 3000rpm for 15min, washing with deionized water, and vacuum drying to obtain S-MoS2Powder;
(3) 9.75g of PCL powder and 0.25g of S-MoS were weighed2Adding the powder into a beaker filled with anhydrous ethanol, sequentially magnetically stirring at 500r/min for 60min, ultrasonically dispersing at 50 deg.C for 10min to obtain uniform mixed solution, centrifuging at 3000rpm for 15min, placing the obtained solid in an electrothermal blowing dry box, and drying at 80 deg.C for 24h to obtain S-MoS2a/PCL composite powder;
(4) mixing S-MoS2Placing the/PCL composite powder in a laser rapid prototyping system, sintering layer by layer according to a three-dimensional model, and removing unsintered powder by using compressed air after sintering to obtain 2.5 wt% S-MoS2The PCL composite bone scaffold has the technical parameters of the laser rapid forming technology as follows: the laser power is 2.5W, the scanning speed is 100mm/min, the scanning interval is 1mm, and the diameter of a light spot is 1 mm.
Tensile Property testing found 2.5 wt% S-MoS2The tensile strength of the/PCL composite bone scaffold is 53.21 MPa.
As shown in FIG. 1, the scanning electron microscope revealed S-MoS2Uniformly dispersed in the PCL matrix.
Comparative example 1
(1) Weigh 0.2g of MoS2Dispersing the nano-sheet powder in 100mL of ethanol solution, and sequentially magnetically stirring at a rotating speed of 500r/min for 30min and ultrasonically dispersing at 50 ℃ for 10min to obtain MoS2A solution;
(2) 9.8g of PCL powder are weighed and added to MoS2Sequentially performing magnetic stirring at 500r/min for 60min and ultrasonic dispersion at 50 deg.C for 10min to obtain mixed solution, centrifuging at 3000rpm for 15min, drying the obtained solid in electrothermal blowing dry box at 80 deg.C for 24h to obtain MoS2a/PCL composite powder;
(4) mixing MoS2Placing the/PCL composite powder in a laser rapid prototyping system, sintering layer by layer according to a three-dimensional model, and removing unsintered powder by using compressed air after sintering to obtain 2.0 wt% MoS2The PCL composite bone scaffold has the technical parameters of the laser rapid forming technology as follows: the laser power is 2.5W, the scanning speed is 100mm/min, the scanning interval is 1mm, and the diameter of a light spot is 1 mm.
Tensile Property testing found 2.0 wt% MoS2The tensile strength of the/PCL composite bone scaffold is 23.56 MPa.
As shown in FIG. 1, MoS was discovered by scanning electron microscopy2The nanosheets are agglomerated in the PCL matrix and even form defects.
Comparative example 2
(1) Weighing 20g of 3-aminopropyltriethoxysilane powder, dispersing the 3-aminopropyltriethoxysilane powder in 100ml of ethanol solution with the pH of 4-5, and performing magnetic stirring at the rotating speed of 500r/min for 30min and ultrasonic dispersion at the temperature of 50 ℃ for 10min to obtain a silane solution;
(2) weigh 10g of MoS2Adding the nano-sheet powder into a silane solution, and violently stirring for 30min at room temperature to obtain S-MoS2Centrifuging at 3000rpm for 15min, washing with deionized water, and vacuum drying to obtain S-MoS2Powder;
(3) 9.98g of PCL powder and 0.02g of S-MoS were weighed2Adding the powder into a beaker filled with anhydrous ethanol, sequentially magnetically stirring at 500r/min for 60min, ultrasonically dispersing at 50 deg.C for 10min to obtain uniform mixed solution, centrifuging at 3000rpm for 15min, placing the obtained solid in an electrothermal blowing dry box, and drying at 80 deg.C for 24h to obtain S-MoS2a/PCL composite powder;
(4) mixing S-MoS2placing/PCL composite powder in laser for rapid speedIn the forming system, sintering layer by layer according to the three-dimensional model, and removing unsintered powder by using compressed air after sintering to obtain 0.2 wt% S-MoS2The PCL composite bone scaffold has the technical parameters of the laser rapid forming technology as follows: the laser power is 2.5W, the scanning speed is 100mm/min, the scanning interval is 1mm, and the diameter of a light spot is 1 mm.
Tensile Property testing found 0.2 wt% S-MoS2The tensile strength of the/PCL composite bone scaffold is 26.43 MPa.
Scanning electron microscope discovery of S-MoS2Uniformly dispersed in the PCL matrix.
Comparative example 3
(1) Weighing 20g of 3-aminopropyltriethoxysilane powder, dispersing the 3-aminopropyltriethoxysilane powder in 100ml of ethanol solution with the pH of 4-5, and performing magnetic stirring at the rotating speed of 500r/min for 30min and ultrasonic dispersion at the temperature of 50 ℃ for 10min to obtain a silane solution;
(2) weigh 10g of MoS2Adding the nano-sheet powder into a silane solution, and violently stirring for 30min at room temperature to obtain S-MoS2Centrifuging at 3000rpm for 15min, washing with deionized water, and vacuum drying to obtain S-MoS2Powder;
(3) 9.7g of PCL powder and 0.3g of S-MoS were weighed2Adding the powder into a beaker filled with anhydrous ethanol, sequentially magnetically stirring at 500r/min for 60min, ultrasonically dispersing at 50 deg.C for 10min to obtain uniform mixed solution, centrifuging at 3000rpm for 15min, placing the obtained solid in an electrothermal blowing dry box, and drying at 80 deg.C for 24h to obtain S-MoS2a/PCL composite powder;
(4) mixing S-MoS2Placing the/PCL composite powder in a laser rapid prototyping system, sintering layer by layer according to a three-dimensional model, and removing unsintered powder by using compressed air after sintering to obtain 3.0 wt% S-MoS2The PCL composite bone scaffold has the technical parameters of the laser rapid forming technology as follows: the laser power is 2.5W, the scanning speed is 100mm/min, the scanning interval is 1mm, and the diameter of a light spot is 1 mm.
Tensile Property testing found 3.0 wt% S-MoS2The tensile strength of the/PCL composite bone scaffold is 42.31 MPa.
Scanning electron microscope discovery of S-MoS2Agglomeration occurs and even defects form in the PCL matrix.

Claims (10)

1. A preparation method of a silane modified molybdenum disulfide/polycaprolactone composite bone scaffold is characterized by comprising the following steps:
(1) MoS by silane pair2Modifying the nano sheet to obtain S-MoS2Powder;
(2) mixing S-MoS2Dispersing the powder and PCL powder into anhydrous ethanol to obtain S-MoS2The S-MoS is obtained by centrifugal separation and drying of the/PCL mixed suspension2a/PCL composite powder;
(3)S-MoS2the S-MoS is prepared from the/PCL composite powder by a laser rapid prototyping technology2a/PCL composite bone scaffold.
2. The preparation method of the silane modified molybdenum disulfide/polycaprolactone composite bone scaffold as claimed in claim 1, wherein: dispersing silane powder into absolute ethyl alcohol with the pH value of 4-5 to obtain a silane solution; then MoS2Adding the nanosheets into a silane solution, and obtaining S-MoS after centrifugal separation and drying2And (3) powder.
3. The preparation method of the silane modified molybdenum disulfide/polycaprolactone composite bone scaffold as claimed in claim 2, wherein: in a preferable scheme, the dispersion mode adopts a magnetic stirring mode and an ultrasonic dispersion mode, the magnetic stirring time is 10-30 min, and the speed is 100-500 r/min; the ultrasonic dispersion time is 5-10 min, and the temperature is 50-60 ℃; the concentration of silane in the silane solution is 1-10 g/mL, and the MoS2The solid-liquid ratio of the nanosheet to the silane solution is 1: 10-1: 15 g/ml.
4. The preparation method of the silane modified molybdenum disulfide/polycaprolactone composite bone scaffold as claimed in claim 1, wherein: in the step (1), the silane is 3-aminopropyltriethoxysilane; MoS2The particle size of the nano sheet is 0.2-5 mu m, and the purity is more than 99%.
5. The preparation method of the silane modified molybdenum disulfide/polycaprolactone composite bone scaffold as claimed in claim 1, wherein: in step (2), S-MoS2The mass ratio of the powder to the PCL powder is 0.5-2.5: 97.5 to 99.5.
6. The preparation method of the silane modified molybdenum disulfide/polycaprolactone composite bone scaffold as claimed in claim 1, wherein: in the step (2), the PCL powder has a particle size of 50-100 μm, a purity of more than 99% and a melting point of 55-65 ℃.
7. The preparation method of the silane modified molybdenum disulfide/polycaprolactone composite bone scaffold as claimed in claim 1, wherein: in the step (2), the dispersion mode adopts a magnetic stirring mode and an ultrasonic dispersion mode, the magnetic stirring time is 10-30 min, and the speed is 100-500 r/min; the ultrasonic dispersion time is 5-10 min, and the temperature is 50-60 ℃.
8. The preparation method of the silane modified molybdenum disulfide/polycaprolactone composite bone scaffold as claimed in claim 1, wherein: in the step (2), the centrifugal separation time is 10-20 min, and the speed is 1000-5000 r/min; the drying temperature is 50-80 ℃, and the drying time is 12-24 h.
9. The preparation method of the silane modified molybdenum disulfide/polycaprolactone composite bone scaffold as claimed in claim 1, wherein: in the step (3), the S-MoS is added2Placing the PCL composite powder in a laser rapid prototyping system, sintering layer by layer according to a preset three-dimensional model, and removing unsintered powder by using compressed air after sintering to obtain S-MoS2a/PCL composite bone scaffold.
10. The method for preparing the silane modified molybdenum disulfide/polycaprolactone composite bone scaffold as claimed in claim 9, wherein: the technological parameters of the laser rapid forming technology are as follows: the laser power is 2-3W, the scanning speed is 80-150 mm/min, the scanning interval is 1-2 mm, and the diameter of a light spot is 0.8-1.0 mm.
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