CN110327496A - A kind of Sr-GO/PCL Composite Bone bracket and preparation method thereof - Google Patents

A kind of Sr-GO/PCL Composite Bone bracket and preparation method thereof Download PDF

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CN110327496A
CN110327496A CN201910635515.1A CN201910635515A CN110327496A CN 110327496 A CN110327496 A CN 110327496A CN 201910635515 A CN201910635515 A CN 201910635515A CN 110327496 A CN110327496 A CN 110327496A
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pcl
composite
solution
powder
preparation
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戚方伟
帅词俊
彭淑平
杨友文
杨文静
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Jiangxi University of Science and Technology
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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
    • A61L27/40—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material
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    • 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
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    • 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
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    • A61L27/58—Materials at least partially resorbable by the body
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/002—Methods
    • 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
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    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
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    • A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
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Abstract

The present invention provides a kind of Sr-GO/PCL Composite Bone bracket and preparation method thereof, the compound multiple bracket is made of PCL matrix and the Sr-GO composite particles being scattered in PCL matrix, and the preparation method will contain Sr2+Solution be added drop-wise in the solution containing GO under stirring, then by mixed solution static reaction at room temperature, the oxygen-containing functional group on the surface GO will be anchored the Sr in solution2+Adventitious deposit and grow form strontium nano particle, obtain Sr-GO composite particles；After PCL powder is mixed with Sr-GO composite particles by liquid phase, it is separated by solid-liquid separation, obtains Sr-GO/PCL composite granule；Sr-GO/PCL composite granule obtains Sr-GO/PCL compound rest by selective laser sintering；This method using GO as Sr nano particle at paralinin and carrier, collaboration promotes dispersion of the GO and Sr nano particle in PCL matrix, assigns compound rest excellent bioactivity, hydrophily and mechanical property；Meanwhile Sr is realized using the degradation of PCL in vivo2+Slow release, achieve the purpose that promote vascularization, mineralising and skeletonization.

Description

A kind of Sr-GO/PCL Composite Bone bracket and preparation method thereof
Technical field
The present invention relates to a kind of preparation methods of Sr-GO/PCL Composite Bone bracket, belong to artificial bone supporting material technology neck Domain.
Background technique
Polycaprolactone (Polycaprolactone, PCL) is used as a kind of artificial synthesized high molecular material, because it has well Biocompatibility, biodegradability and lower fusing point (59~64 DEG C), field of biomedicine have huge application Potentiality.Especially the material is that can be applied to group by food and drug administration (FDA) and Europe unified (CE) certification After weaver's journey, the product of manufacture tends to the marketization.However, PCL itself does not have bioactivity and hydrophily is poor, cause It is lower to the affinity of cell, while the mechanical strength of PCL is relatively low, it is difficult to which the requirement for meeting compact bone is deposited above The problem of limit its application on bone graft.
Graphene oxide (Graphene oxide, GO) is a kind of derivative of graphene, and surface is connected with largely Oxygen-containing group, such as epoxy group, carboxyl and hydroxyl make it have excellent water-wet behavior and can provide for phosphatic deposition Nucleation site, while GO has excellent mechanical performance and good bioactivity, is that one kind can be used to improve bone bracket material Expect the ideal inorganic phase of mechanics, hydrophily and osteoinductive.However, GO has stronger polarity and higher specific surface energy, lead Cause is easily reunited in a polymer matrix, evenly dispersed difficulty, and enhancing is not achieved and improves the mesh of the other comprehensive performances of PCL 's.
Biologically active nanometer particle, such as copper (Cu), magnesium (Mg) and strontium (Sr) etc. can promote the formation of new bone and blood vessel. Among these, Sr2+It is the essential trace elements of the human body, plays an important role in maintaining tissue function, especially bone.Sr can Mesenchymal stem cell (MSCs) is adjusted to osteoblast differentiation, and promotes the synthesis and precipitating of bone matrix protein, and then is promoted Into osteoblast differentiation and New born formation.Meanwhile Sr can promote the growth of osteoblast and the generation of osteoclast, adjust bone It rebuilds, improves bone metabolism, maintain the stability and integrality of bone, improve the bone mass of sufferers of osteoporosis face.However, strontium nanometer Particle is also easy to reunite in PCL matrix, causes local Sr ion concentration excessively high, and then interferes the absorption and metabolism of calcium, when serious It can cause textured bone, fragility, muscular atrophy and anaemia etc..
Summary of the invention
For polycaprolactone bone bracket mechanical strength is low in the prior art, hydrophily is poor and bioactivity is low, and aoxidize Graphene, which is mutually introduced into polycaprolactone bone holder material with strontium nano particle as second, has bad dispersibility, easy to reunite etc. to ask Topic.
The first purpose of this invention be to provide a kind of graphene oxide be dispersed in strontium Nano composite granules it is poly- The Sr-GO/PCL Composite Bone bracket with high bioactivity and high intensity in caprolactone matrix.
Second object of the present invention is to provide a kind of preparation method of Sr-GO/PCL Composite Bone bracket, the preparation Method utilizes the high surface area of graphene oxide sheet, can be used as into paralinin, promotes strontium nano particle in graphene oxide Uniform adventitious deposit on edge and surface.Meanwhile strontium nano particle is clipped in formation " Sanming City between adjacent graphene oxide layer Control " structure, collaboration support can be played the role of.It on the one hand can pass through the collaboration between graphene oxide and strontium nano particle in this way Effect promotes dispersion of the two in PCL matrix, achievees the purpose that enhance its bioactivity, hydrophily and mechanics；On the other hand Sr can be realized by the degradation of polycaprolactone in vivo2+Slow release, reach and promote vascularization, mineralising and skeletonization Purpose.
In order to achieve the above technical purposes, the invention provides the following technical scheme:
A kind of Sr-GO/PCL Composite Bone bracket of the present invention, the compound multiple bracket by PCL matrix and are scattered in PCL matrix In graphene oxide and strontium nanometer (Sr-GO) composite particles form.
Preferred scheme, in the Composite Bone bracket, the mass fraction of Sr-GO composite particles is 0.5~5%.
Sr2+It is the essential trace elements of the human body, therefore its quality in Composite Bone bracket needs effectively control, content Influence facilitation to cell is weaker, and the excessive growth for then influencing whether cell instead.
A kind of preparation method of Sr-GO/PCL Composite Bone bracket of the present invention, will contain Sr2+Solution be added drop-wise to the solution containing GO In, static reaction is separated by solid-liquid separation to get Sr-GO composite particles, PCL powder is mixed with Sr-GO composite particles, obtains Sr- GO/PCL composite granule, the chosen property of Sr-GO/PCL composite granule is laser sintered to obtain Sr-GO/PCL Composite Bone bracket.
In the prior art, strontium nano particle and graphene oxide can not be dispersed in PCL matrix, and inventor is but It is found surprisingly that the composite particles by preparing strontium nano particle and graphene oxide, then compound with PCL matrix, not only realizes Strontium nano particle with it is evenly dispersed while graphene oxide, also collaboration obtains better reinforcing effect, this is mainly The Sr that surface of graphene oxide can be anchored in solution rich in a large amount of oxygen-containing group is cleverly utilized in the present invention2+, and have Big specific surface area can be used as into paralinin, promote strontium nano particle uniform on the edge and surface of graphene oxide Adventitious deposit.Inventors have found that after the static hair of certain time is answered, by the white of depositing dosed quantities in surface of graphene oxide Coloured particles are due to Sr2+When depositing on GO, the growth of meeting forming core, ultimately forms the strontium nano particle of amorphous state.Meanwhile strontium Nano particle is clipped in formation " sandwich " structure between adjacent graphene oxide layer, and collaboration support can be played to graphene sheet layer Effect, the dispersion in PCL matrix of graphene oxide and strontium nano particle is promoted by this synergistic effect, both is solved easily In reunion problem.
In the present invention, the solution containing GO is to add graphene oxide into pure water with method is taken, through ultrasonic agitation point It dissipates and obtains.
Preferred scheme, the partial size of the GO is 1~30 μm, with a thickness of 1~10nm.
Preferred scheme, in the solution containing GO, the concentration of GO is 0.1~3mg/mL,
Preferred scheme, it is described to contain Sr2+Solution in, Sr2+Concentration be 5~50mM.
In the present invention, contain Sr2+Solution use the soluble strontium salt without bio-toxicity.
Preferred scheme, the solution containing GO with contain Sr2+Solution volume ratio be 1:1~2:1.
In the present invention, GO and Sr2+Content than needing effective control, if Sr2+Content relative to graphene oxide Content is excessive, then strontium ion can have agglomeration traits on graphene oxide, and too small, and graphene oxide layer is difficult to be supportted It opens, equally exists agglomeration.
Preferred scheme will contain Sr2+Solution be added drop-wise in the solution containing GO dropwise under stiring, the revolving speed of the stirring For 1000~10000r/min.
Inventors have found that needing GO and Sr by way of being added dropwise under being vigorously stirred dropwise2+Carry out it is compound, otherwise still Can so there is a problem of that dispersion is bad.
Preferred scheme, the static reaction time are 5~72h.In the present invention, static reaction carries out at room temperature.
Preferred scheme, the process of the separation of solid and liquid are as follows: first filtering obtains solid phase powder, and solid phase fission is washed with water, It is centrifuged again, is drying to obtain Sr-GO composite particles, the speed of the centrifugation is 5000~10000rpm, and the time of the centrifugation is 10~20min.
Preferred scheme, in the Sr-GO/PCL composite granule, PCL powder and the mass ratio of Sr-GO composite particles are 0.5~5:95~99.5.
Preferred scheme, the partial size of the PCL powder are 20~100 μm.
Preferred scheme, the process that PCL powder is mixed with Sr-GO composite particles are as follows: contain the addition of Sr-GO composite particles In the solution of PCL, mixed solution is obtained, it is successively compound by mechanical stirring, ultrasonic disperse, drying, grinding acquisition Sr-GO/PCL Powder；The churned mechanically time is 30~120min, and revolving speed is 500~1000r/min, and temperature is 30~60 DEG C, described The time of ultrasonic disperse is 30~120min.
Further preferred, in the solution containing PCL, solvent is dehydrated alcohol.
Inventors have found that PCL is dispersed in dehydrated alcohol in advance, Sr-GO composite particles are added, while mixed in liquid phase When conjunction, using strong mechanical stirring (mixing speed is fast) and ultrasonic disperse, preferred scheme can be effectively realized, Uniform Doped exists In PCL powder.
It is further that preferably the temperature of the drying is 50~70 DEG C, the time is 12~for 24 hours.
Preferred scheme, the technological parameter of the selective laser sintering: laser power is 5~15W, and scanning speed is 500~1500mm/min, sweep span be 0.1~0.2mm, spot diameter be 0.6~1.0mm, powder layer thickness be 0.1~ 0.2mm, powder bed preheating temperature are 40~52 DEG C.
A kind of preparation method of Sr-GO/PCL Composite Bone bracket of the present invention, including following key step:
(1) it adds graphene oxide into pure water, disperses to obtain the solution containing GO, the solution containing GO through ultrasonic agitation In, the concentration of GO is 0.1~3mg/mL,
(2) by Sr2+Concentration is that the solution of 5~50mM is added drop-wise in graphene oxide solution under stirring, described to contain The solution of GO with contain Sr2+Solution volume ratio be 1:1~2:1, in a static condition react 5~72 hours, filtering, consolidate Phase powder, using ultrapure water clean solid phase powder, then at speed be 5000~10000rpm centrifugation apparatus on centrifugation 10~ 20min, then drying obtains Sr-GO composite particles for 24 hours at 60 DEG C；
(3) by PCL powder dehydrated alcohol, realize that its is pre-dispersed by mechanical stirring and ultrasonic disperse；It obtains containing PCL's Solution,
(4) it by gained Sr-GO composite granule, is added in the solution containing PCL and obtains mixed solution, guarantee mixed solution In, the mass ratio of Sr-GO composite particles and PCL powder is 0.5~5:95~99.5, and mixed solution is in 30~60 DEG C, first 500 30~120min of mechanical stirring under the revolving speed of~1000r/min, then carries out 30~120min of ultrasonic disperse again, then will mixing Solution is filtered and is dried in vacuo 10~12h under the conditions of 50~70 DEG C, obtains Sr-GO/PCL composite granule.
(5) Sr-GO/PCL composite granule is placed in selective laser sintering and moulding system, layer is carried out according to threedimensional model Layer sintering, removes unsintered powder after the completion of sintering to get Sr-GO/PCL Composite Bone bracket, selective laser sintering technique Parameter are as follows: laser power is 5~15W, and scanning speed is 500~1500mm/min, and sweep span is 0.1~0.2mm, and hot spot is straight Diameter is 0.6~1.0mm, and powder layer thickness is 0.1~0.2mm, and powder bed preheating temperature is 40~52 DEG C.
The advantages of invention and good effect:
(1) present invention can be anchored the Sr in solution rich in a large amount of oxygen-containing group using graphene oxide2+, and in its table Face and edge homoepitaxial form strontium nano particle, meanwhile, strontium nano particle is clipped between adjacent graphene oxide layer and is formed " sandwich " structure, can play the role of collaboration support to graphene sheet layer, promote graphene oxide by this synergistic effect With dispersion of the strontium nano particle in PCL matrix, solves the two and be easy to problem of reuniting；
(2) present invention is using the excellent mechanical performance and hydrophilicity of graphene oxide, can be improved PCL mechanical strength and Cell adherence ability；
(3) present invention can realize Sr by the degradation of polycaprolactone in vivo2+Slow release, fill between adjustable marrow Matter stem cell (MSCs) promotes the synthesis and precipitating of bone matrix protein to osteoblast differentiation, accelerates osteoblast differentiation, until New bone generates completely.
Specific embodiment
Further description of the specific embodiments of the present invention combined with specific embodiments below, but the content of the present invention is simultaneously It is not limited to this.
Embodiment 1
(1) 0.025mg graphene oxide powder is weighed using electronic balance, is added in 50mL ultrapure water, is stirred in ultrasound It is 0.5mg/mL suspension that concentration is formed under the effect of mixing.
(2) 100mL is contained into Sr2+Solution that concentration is 10mM (being added by strontium chloride to going in pure water with taking) is in stirring action Under be added drop-wise in 100mL graphene oxide solution dropwise, mixing speed 2000r/min, after being added dropwise to complete in a static condition Then reaction 72 hours cleans filtered composite granule using ultrapure water repeatedly, and in the centrifugation that revolving speed is 10000rpm 15min is centrifuged in equipment, then drying obtains Sr-GO composite granule for 24 hours at 60 DEG C；
(3) 9.95g is weighed, the PCL powder that particle size is 40 μm adds it to three mouthfuls for filling ethanol solution In flask, realize that its is pre-dispersed by mechanical stirring and ultrasonic disperse；
(4) it is added in PCL suspension using the Sr-GO powder of electronic balance weighing 0.05g, then passes through mixed solution Magnetic agitation and ultrasonic disperse are uniformly mixed, and the time of mechanical stirring and ultrasonic disperse is 60min, revolving speed 600r/min, temperature Degree is 50 DEG C, is then filtered uniformly mixed suspension and is dried in vacuo 12h under the conditions of 60 DEG C, final grinding obtains Uniform Sr-GO/PCL composite material powder；
(6) composite material powder obtained above is laid in selective laser sintering system, using laser according to setting Composite material powder is melted in fixed track, is layering, three-dimensionally shaped, after the completion of sintering, is removed using compressed air un-sintered Powder, final building and the consistent biological piezoelectricity bone bracket of threedimensional model, main sintering process parameter are as follows: laser power is 10W, scanning speed 800mm/min, sweep span 0.15mm, spot diameter 0.7mm, powder layer thickness 0.15mm, powder Bed preheating temperature is 51 DEG C.
(7) show under the experiment condition of embodiment 1 through mechanical test, the compression of Sr-GO/PCL composite material bracket and Tensile strength is respectively 11.26 and 13.66MPa, and 76% and 102% has been respectively increased compared to pure PCL bracket.Sr-GO/PCL is multiple The water contact angle of condensation material bracket is reduced to 42 ° from 81 °.Meanwhile showing Sr-GO/PCL composite wood by MTT and ALP test The proliferation of cell and differentiation capability significantly increase on material bracket, it was demonstrated that the material can effectively accelerate the regeneration and reconstruction of bone.
Embodiment 2
(1) 0.025mg graphene oxide powder is weighed using electronic balance, is added in 50mL ultrapure water, is stirred in ultrasound It is 0.5mg/mL suspension that concentration is formed under the effect of mixing.
(2) 100mL is contained into Sr2+Solution that concentration is 10mM (being added by strontium chloride to going in pure water with taking) is in stirring action Under be added drop-wise in 100mL graphene oxide solution dropwise, mixing speed 2000r/min, after being added dropwise to complete in a static condition Then reaction 72 hours cleans filtered composite granule using ultrapure water repeatedly, and in the centrifugation that revolving speed is 10000rpm 15min is centrifuged in equipment, then drying obtains Sr-GO composite granule for 24 hours at 60 DEG C；
(3) 9.9g is weighed, the PCL powder that particle size is 40 μm adds it to three mouthfuls for filling ethanol solution In flask, realize that its is pre-dispersed by mechanical stirring and ultrasonic disperse；
(4) it is added in PCL suspension using the Sr-GO powder of electronic balance weighing 0.1g, then passes through mixed solution Magnetic agitation and ultrasonic disperse are uniformly mixed, and the time of mechanical stirring and ultrasonic disperse is 60min, revolving speed 600r/min, temperature Degree is 50 DEG C, is then filtered uniformly mixed suspension and is dried in vacuo 12h under the conditions of 60 DEG C, final grinding obtains Uniform Sr-GO/PCL composite material powder；
(6) composite material powder obtained above is laid in selective laser sintering system, using laser according to setting Composite material powder is melted in fixed track, is layering, three-dimensionally shaped, after the completion of sintering, is removed using compressed air un-sintered Powder, final building and the consistent biological piezoelectricity bone bracket of threedimensional model, main sintering process parameter are as follows: laser power is 10W, scanning speed 800mm/min, sweep span 0.15mm, spot diameter 0.7mm, powder layer thickness 0.15mm, powder Bed preheating temperature is 51 DEG C.
(7) show under the experiment condition of embodiment 2 through mechanical test, the compression of Sr-GO/PCL composite material bracket and Stretch bending intensity is respectively 16.42 and 19.38MPa, and 157% and 187% has been respectively increased compared to pure PCL bracket.Sr-GO/ The water contact angle of PCL composite material bracket is reduced to 38 ° from 81 °.Meanwhile showing that Sr-GO/PCL is multiple by MTT and ALP test The proliferation of cell and differentiation capability significantly increase on condensation material bracket, it was demonstrated that the material can effectively accelerate the regeneration and reconstruction of bone.
Embodiment 3
(1) 0.025mg graphene oxide powder is weighed using electronic balance, is added in 50mL ultrapure water, is stirred in ultrasound It is 0.5mg/mL suspension that concentration is formed under the effect of mixing.
(2) 100mL is contained into Sr2+Solution that concentration is 10mM (being added by strontium chloride to going in pure water with taking) is in stirring action Under be added drop-wise in 100mL graphene oxide solution dropwise, mixing speed 2000r/min, after being added dropwise to complete in a static condition Then reaction 72 hours cleans filtered composite granule using ultrapure water repeatedly, and in the centrifugation that revolving speed is 10000rpm 15min is centrifuged in equipment, then drying obtains Sr-GO composite granule for 24 hours at 60 DEG C；
(3) 9.5g is weighed, the PCL powder that particle size is 40 μm adds it to three mouthfuls for filling ethanol solution In flask, realize that its is pre-dispersed by mechanical stirring and ultrasonic disperse；
(4) it is added in PCL suspension using the Sr-GO powder of electronic balance weighing 0.5g, then passes through mixed solution Magnetic agitation and ultrasonic disperse are uniformly mixed, and the time of mechanical stirring and ultrasonic disperse is 60min, revolving speed 600r/min, temperature Degree is 50 DEG C, is then filtered uniformly mixed suspension and is dried in vacuo 12h under the conditions of 60 DEG C, final grinding obtains Uniform Sr-GO/PCL composite material powder；
(6) composite material powder obtained above is laid in selective laser sintering system, using laser according to setting Composite material powder is melted in fixed track, is layering, three-dimensionally shaped, after the completion of sintering, is removed using compressed air un-sintered Powder, final building and the consistent biological piezoelectricity bone bracket of threedimensional model, main sintering process parameter are as follows: laser power is 10W, scanning speed 800mm/min, sweep span 0.15mm, spot diameter 0.7mm, powder layer thickness 0.15mm, powder Bed preheating temperature is 51 DEG C.
(7) show under the experiment condition of embodiment 3 through mechanical test, the compression of Sr-GO/PCL composite material bracket and Stretch bending intensity is respectively 13.11 and 15.26MPa, and 105% and 126% has been respectively increased compared to pure PCL bracket.Sr-GO/ The water contact angle of PCL composite material bracket is reduced to 34 ° from 81 °.Meanwhile showing that Sr-GO/PCL is multiple by MTT and ALP test The proliferation of cell and differentiation capability significantly increase on condensation material bracket, it was demonstrated that the material can effectively accelerate the regeneration and reconstruction of bone.
Comparative example 1
(1) 0.025mg graphene oxide powder is weighed using electronic balance, is added in 50mL ultrapure water, is stirred in ultrasound It is 0.5mg/mL suspension that concentration is formed under the effect of mixing.
(2) 100mL is contained into Sr2+Solution that concentration is 10mM (being added by strontium chloride to going in pure water with taking) is in stirring action Under be added drop-wise in 100mL graphene oxide solution dropwise, in a static condition react 72 hours, then using ultrapure water to filtering Composite granule afterwards cleans repeatedly, and is centrifuged 15min on the centrifugation apparatus that revolving speed is 10000rpm, then dry at 60 DEG C Sr-GO composite granule is obtained for 24 hours；
(3) 9g is weighed, the PCL powder that particle size is 40 μm adds it to three mouthfuls of burnings for filling ethanol solution In bottle, realize that its is pre-dispersed by mechanical stirring and ultrasonic disperse；
(4) it is added in PCL suspension using the Sr-GO powder of electronic balance weighing 1g, then by mixed solution through magnetic Power stirring and ultrasonic disperse are uniformly mixed, and the time of mechanical stirring and ultrasonic disperse is 60min, revolving speed 600r/min, temperature It is 50 DEG C, then uniformly mixed suspension is filtered and is dried in vacuo 12h under the conditions of 60 DEG C, final grinding obtains Even Sr-GO/PCL composite material powder；
(6) composite material powder obtained above is laid in selective laser sintering system, using laser according to setting Composite material powder is melted in fixed track, is layering, three-dimensionally shaped, after the completion of sintering, is removed using compressed air un-sintered Powder, final building and the consistent biological piezoelectricity bone bracket of threedimensional model, main sintering process parameter are as follows: laser power is 10W, scanning speed 800mm/min, sweep span 0.15mm, spot diameter 0.7mm, powder layer thickness 0.15mm, powder Bed preheating temperature is 51 DEG C.
(7) show under the experiment condition of comparative example 1 through mechanical test, the compression of Sr-GO/PCL composite material bracket and Stretch bending intensity is respectively 5.26 and 4.66MPa, is substantially reduced compared to pure PCL bracket, this is mainly that excessive graphene exists It is easy to reunite in PCL matrix, so that mechanical property be made to deteriorate.In addition, showing Sr-GO/PCL composite wood by MTT and ALP test Expect that the proliferation of cell and differentiation capability significantly reduce on bracket, a large amount of Cell deaths occur, this is mainly strontium ion concentration It is larger, it influences cell and normally grows, even result in its death.
Comparative example 2
(1) 0.025mg graphene oxide powder is weighed using electronic balance, is added in 50mL ultrapure water, is stirred in ultrasound It is 0.5mg/mL suspension that concentration is formed under the effect of mixing.
(2) 100mL is contained into Sr2+Solution that concentration is 10mM (being added by strontium chloride to going in pure water with taking) is in stirring action Under be added drop-wise in 100mL graphene oxide solution dropwise, in a static condition react 72 hours, then using ultrapure water to filtering Composite granule afterwards cleans repeatedly, and is centrifuged 15min on the centrifugation apparatus that revolving speed is 10000rpm, then dry at 60 DEG C Sr-GO composite granule is obtained for 24 hours；
(3) 9.99g is weighed, the PCL powder that particle size is 40 μm adds it to three mouthfuls for filling ethanol solution In flask, realize that its is pre-dispersed by mechanical stirring and ultrasonic disperse；
(4) it is added in PCL suspension using the Sr-GO powder of electronic balance weighing 0.01g, then passes through mixed solution Magnetic agitation and ultrasonic disperse are uniformly mixed, and the time of mechanical stirring and ultrasonic disperse is 60min, revolving speed 600r/min, temperature Degree is 50 DEG C, is then filtered uniformly mixed suspension and is dried in vacuo 12h under the conditions of 60 DEG C, final grinding obtains Uniform Sr-GO/PCL composite material powder；
(6) composite material powder obtained above is laid in selective laser sintering system, using laser according to setting Composite material powder is melted in fixed track, is layering, three-dimensionally shaped, after the completion of sintering, is removed using compressed air un-sintered Powder, final building and the consistent biological piezoelectricity bone bracket of threedimensional model, main sintering process parameter are as follows: laser power is 10W, scanning speed 800mm/min, sweep span 0.15mm, spot diameter 0.7mm, powder layer thickness 0.15mm, powder Bed preheating temperature is 51 DEG C.
(7) show under the experiment condition of comparative example 2 through mechanical test, the compression of Sr-GO/PCL composite material bracket and Stretch bending intensity is respectively 9.15 and 10.16MPa, is obviously improved compared to pure PCL bracket mechanical strength.Sr-GO/PCL is compound The water contact angle of stock support is reduced to 74 ° from 81 °.In addition, showing Sr-GO/PCL composite material by MTT and ALP test The proliferation of cell and differentiation capability slightly improve on bracket, this is mainly Sr in solution2+Concentration is lower, and the influence to cell promotes It acts on weaker.

Claims (10)

1. a kind of Sr-GO/PCL Composite Bone bracket, it is characterised in that: the compound multiple bracket by PCL matrix and is scattered in PCL base Sr-GO composite particles composition in body.
2. a kind of Sr-GO/PCL Composite Bone bracket according to claim 1, it is characterised in that: in the Composite Bone bracket, The mass fraction of Sr-GO composite particles is 0.5~5%.
3. preparing a kind of method of Sr-GO/PCL Composite Bone bracket as claimed in claim 1 or 2, it is characterised in that: Sr will be contained2 +Solution be added drop-wise in the solution containing GO, static reaction, be separated by solid-liquid separation to get Sr-GO composite particles, by PCL powder and Sr- The mixing of GO composite particles, obtains Sr-GO/PCL composite granule, the chosen property of Sr-GO/PCL composite granule is laser sintered to obtain Sr- GO/PCL Composite Bone bracket.
4. a kind of preparation method of Sr-GO/PCL Composite Bone bracket according to claim 3, it is characterised in that: the GO Partial size be 1~30 μm, with a thickness of 1~10nm.
5. a kind of preparation method of Sr-GO/PCL Composite Bone bracket according to claim 3, it is characterised in that: described to contain In the solution of GO, the concentration of GO is 0.1~3mg/mL, described to contain Sr2+Solution in, Sr2+Concentration be 5~50mM, it is described to contain The solution of GO with contain Sr2+Solution volume ratio be 1~2:1.
6. a kind of preparation method of Sr-GO/PCL Composite Bone bracket according to claim 3, it is characterised in that: Sr will be contained2+ Solution be added drop-wise in the solution containing GO dropwise under stiring, the revolving speed of the stirring is 1000~10000r/min.
7. a kind of preparation method of Sr-GO/PCL Composite Bone bracket according to claim 3, it is characterised in that: described quiet The state reaction time is 5~72h,
The process of the separation of solid and liquid are as follows: first filtering obtains solid phase powder, solid phase fission is washed with water, then be centrifuged, be drying to obtain Sr-GO composite particles, the speed of the centrifugation are 5000~10000rpm, and the time of the centrifugation is 10~20min.
8. a kind of preparation method of Sr-GO/PCL Composite Bone bracket according to claim 3, it is characterised in that: the Sr- In GO/PCL composite granule, the mass ratio of PCL powder and Sr-GO composite particles is 0.5~5:95~99.9, the PCL powder Partial size be 20~100 μm.
9. a kind of preparation method of Sr-GO/PCL Composite Bone bracket according to claim 3, it is characterised in that: by PCL powder The process that body is mixed with Sr-GO composite particles are as follows: Sr-GO composite particles are added in the solution containing PCL, mixed solution is obtained, Successively Sr-GO/PCL composite granule is obtained by mechanical stirring, ultrasonic disperse, drying, grinding；The churned mechanically time is 30~120min, revolving speed are 500~1000r/min, and temperature is 30~60 DEG C, time of the ultrasonic disperse is 30~ 120min。
10. a kind of preparation method of Sr-GO/PCL Composite Bone bracket according to claim 3, it is characterised in that: the choosing The laser sintered technological parameter of selecting property: laser power is 5~15W, and scanning speed is 500~1500mm/min, and sweep span is 0.1~0.2mm, spot diameter are 0.6~1.0mm, and powder layer thickness is 0.1~0.2mm, and powder bed preheating temperature is 40~52 DEG C.
CN201910635515.1A 2019-07-15 2019-07-15 A kind of Sr-GO/PCL Composite Bone bracket and preparation method thereof Pending CN110327496A (en)

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