CN110314250A - A kind of preparation method of PVDF/DBT Composite Bone bracket - Google Patents
A kind of preparation method of PVDF/DBT Composite Bone bracket Download PDFInfo
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- CN110314250A CN110314250A CN201910635513.2A CN201910635513A CN110314250A CN 110314250 A CN110314250 A CN 110314250A CN 201910635513 A CN201910635513 A CN 201910635513A CN 110314250 A CN110314250 A CN 110314250A
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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
- A61L27/44—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material having a macromolecular matrix
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- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
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- A61L2430/02—Materials or treatment for tissue regeneration for reconstruction of bones; weight-bearing implants
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Abstract
The invention discloses a kind of preparation method of PVDF/DBT Composite Bone bracket, this method is using situ aggregation method in BaTiO3Surface obtains coating BaTiO with poly-dopamine3The DBT powder of core-shell structure；The DBT powder is mixed by liquid phase with PVDF powder, ultrasound, stirring, is dispersed, dry and grinding, and PVDF/DBT composite granule is obtained；The PVDF/DBT composite granule obtains PVDF/DBT Composite Bone bracket: evenly dispersed BaTiO by selective laser sintering3Nano particle and PVDF have good interfacial combined function, assign the good piezoelectric property of bracket, mechanical property and biological property, the endogenous electricity microenvironment that bracket generates can generate electro photoluminescence to osteoblast, to promote adherency, proliferation and differentiation of the osteoblast on bone bracket.
Description
Technical field
The present invention relates to a kind of Composite Bone bracket, in particular to a kind of preparation method of PVDF/DBT Composite Bone bracket belongs to
In artificial bone scaffold preparation technical field.
Background technique
Currently, artificial bone scaffold is since cellular response is slow, to differentiation capability difference and subalimentation etc. self-bone grafting is presented in bone
The outstanding problems such as active low, osteanagenesis and Integrated implant speed are slow.Bone itself has piezoelectricity, and suitable electro photoluminescence can increase carefully
Free calcium ion concentration in cytosol promotes the orientated deposition of calcium Phosphate minerals, adjusts gene expression relevant to bone, improves alkaline phosphorus
Phytase activity and local blood supply etc., and then accelerate the regeneration and reparation of bone.Biological piezoelectric materials can be answered in exogenous machinery
Generation charge is deformed and induced under power effect, bionical building promotes the endogenous electricity microenvironment of bone tissue regeneration, is at present most
One of researching value and the electroactive bone alternate material of application prospect.
Kynoar (PVDF) piezoelectric polymeric materials are because it is with good piezoelectric property, biocompatibility and thermoplastic
Processability is widely used in field of biomedicine.However, Kynoar as bone holder material there are piezoelectric property, just
The problems such as degree and hardness are insufficient.Nano barium phthalate (BaTiO3) there is excellent piezoelectric property and good biocompatibility, if
It is combined in PVDF matrix, on the one hand can be superimposed and induce PVDF to generate more β by the piezoelectric property of the two brilliant
Carry out the piezoelectric property of reinforcing material；On the other hand, nanometer BaTiO3As a kind of rigid particles, can be improved PVDF rigidity and
Hardness.
The improvement of above-mentioned performance is built upon a nanometer BaTiO3The base of particle good dispersion and interface cohesion in PVDF
On plinth, however, nanometer BaTiO3Particle has high surface energy and surface lacks functional site, occurs that it easily in PVDF
Reunite, on the one hand will lead to the reduced capability even failure that nano particle induction PVDF generates β crystalline substance, the piezoelectricity of composite material in this way
Performance cannot enhance；On the other hand it will cause nano particle and the interface cohesion of polymeric matrix be poor, stress is in interface
It is difficult to effectively transmit, the stress-electric coupling of material, which acts on, to be weakened, it is difficult to realize that the piezoelectricity of material and mechanical property are strengthened, so limitation
Their applications in bone tissue engineer.
Summary of the invention
For the prior art in preparation PVDF/BaTiO3(BT) interface cohesion existing for Piezoelectric anisotropy bone bracket is weak, BaTiO3
Disperse phenomena such as uneven, easy to reunite in PVDF, the purpose of the present invention is to provide a kind of PVDF/DBT Composite Bone brackets
Preparation method, this method utilize the amine-modified barium titanate of DOPA, obtain poly-dopamine and coat BaTiO3Powder ((DBT powder), then with
PVDF is compound, it can be ensured that BaTiO3Disperse in PVDF matrix, and improves basal body interface binding ability, while improving bio-compatible
Property, to obtain the PVDF/DBT Piezoelectric anisotropy bone bracket with good piezoelectric property, mechanical property and biological property.
To achieve the goals above, the invention provides the following technical scheme:
A kind of preparation method of PVDF/DBT Composite Bone bracket of the present invention, by BaTiO3Powder is added to dopamine solution and obtains
Suspension is obtained, reaction obtains DBT powder, and DBT powder is mixed with PVDF powder then and obtains composite granule, composite granule warp
It crosses selective laser sintering and obtains PVDF/DBT Composite Bone bracket.
The present invention uses modification monomer of the dopamine as barium titanate, and dopamine itself is a kind of chemicals of human secretory
Matter has preferable biocompatibility and stronger reproducibility, can pass through oxidation autohemagglutination under certain reaction temperature and time
At poly-dopamine, poly-dopamine contains the functional groups such as a large amount of phenolic hydroxyl group and amino for symphysis, these groups can be by covalent
Key or non-covalent bond mode are in conjunction with barium titanate and Kynoar, to promote nano barium titanate titanate particle in Kynoar
It is evenly dispersed, while enhancing the interface compatibility between barium titanate and Kynoar and interface bond strength, assign PVDF/
The good piezoelectric property of DBT Piezoelectric anisotropy bone bracket, mechanical property and biological property, and then form uniform and stable endogenous electricity
Microenvironment generates electro photoluminescence to osteoblast, promotes adherency, proliferation and differentiation of the osteoblast on bone bracket.
Inventors have found that also being had a very big impact for final moulding process to Piezoelectric anisotropy bone bracket, such as at present
The preparation method of piezoelectric mounts for artificial bone mostly uses the methods of melt spinning, casting film-forming, particle leaching to prepare, this
The piezoelectricity bone bracket of a little method preparations is difficult to exactly match with bone defect position, is likely to result in inflammatory reaction.And the present invention adopts
It is that can match with bone defect position geometry with PVDF/DBT Piezoelectric anisotropy bone bracket prepared by selective laser sintering
Piezoelectricity bone bracket, avoid above-mentioned problem and exist, while inventor is also found surprisingly that, using selective laser sintering system
PVDF/DBT Piezoelectric anisotropy bone bracket that is standby, obtaining preferably defect can construct the electricity microenvironment for promoting osteanagenesis,
With more excellent rush osteogenic ability.
Preferred scheme, by BaTiO3Powder is added in dopamine solution and mixes, and suspension is formed, by suspension in 30
It~70 DEG C, reacts, is separated by solid-liquid separation, gained solid phase is DBT powder under stiring；The concentration of the dopamine solution be 0.5~
10mg/mL, the BaTiO3The mass ratio of dopamine is 1~5:1 in powder and dopamine solution.
As a further preference, the concentration of the dopamine solution is 0.5~2mg/mL.
As a further preference, the BaTiO3The mass ratio of dopamine is 1~3:1 in powder and dopamine solution.
Inventors have found that dopamine and BaTiO3Quality proportioning have a certain impact to the performance of material, dopamine mistake
It is unable to reach the purpose of sufficiently modification barium titanate less, and dopamine excessively will lead to the oxidation polymerization in air of extra dopamine
It is formed in poly-dopamine particle or poly-dopamine and coats more barium titanate particles, to influence the comprehensive of composite material bracket
Can, such as piezoelectricity, mechanics and homogeneity.
In addition, during the reaction, reaction temperature coats BaTiO to gained poly-dopamine3Powder also has certain shadow
It rings, if reaction temperature is too low, the reactivity of whole system can be made too low, the reaction time is longer；If reaction temperature is excessively high, can lead
The solvent evaporation rate of whole system is caused to accelerate, solution concentration steeply rises, to influence packet of the poly-dopamine on barium titanate
It covers.
It is further preferred, the BaTiO3Powder is tetragonal phase.
It is further preferred, the BaTiO3The partial size of powder is 100~1000nm.
Inventors have found that BaTiO3The crystal phase of powder, directly affects BaTiO3The piezoelectric property of powder, only tetragonal
The BaTiO of phase3Powder just has an excellent piezoelectric property, and BaTiO3The partial size of powder is too small, is often cubic phase, while grain
Diameter is too small, is also unfavorable for the dispersion during coating and easily occurs wrapping in poly-dopamine to influence the uniform cladding of poly-dopamine
The phenomenon that covering more barium titanate particles, and then piezoelectric property, bioactivity, the anti-microbial property etc. for influencing entire material, in addition
Partial size is excessive, will not have the effect of nano-particle reinforcement, and the mechanical property of bone bracket is caused to reduce.
It is further preferred, the BaTiO3The partial size of powder is 200~800nm.
Further preferred, matching for the dopamine solution takes process are as follows: dopamine powder is added to Tris-HCL and delays
In fliud flushing, mix to get dopamine solution.
It is further preferred, by BaTiO3Powder is added in dopamine solution, equal by mechanical stirring, ultrasonic mixing
It is even, form suspension.
It is further that preferably the pH of suspension is 6~10,
Further preferred, the time reacted under the stirring is 3~12 hours.
It after the completion of being stirred to react, is separated by solid-liquid separation, gained liquid phase is cleaned and removes the unreacted DOPA amine monomers in surface, 50
10~12h is dried in vacuo under the conditions of~70 DEG C, grinding finally obtains DBT powder.
Preferred scheme in the composite granule, is counted, DBT powder in mass ratio: powder=1 PVDF~40:60~99,
Further preferably 5~20:80~95.
Preferred scheme, the partial size of the PVDF powder are 20~100 μm, and fusing point is 150~180 DEG C.
Preferred scheme, the process that DBT powder is mixed with PVDF powder are as follows: the solution containing DBT is added in PVDF powder
In, mixed solution is obtained, successively obtains composite granule by mechanical stirring, ultrasonic disperse, drying, grinding；The mechanical stirring
Time be 30~120min, revolving speed is 500~1000r/min, and temperature is 30~60 DEG C, and time of the ultrasonic disperse is 30
~120min.
Further preferred, in the solution containing DBT, solvent is dehydrated alcohol.
Inventors have found that DBT is dispersed in dehydrated alcohol in advance, PVDF powder is added, while in liquid phase mixing,
Using strong mechanical stirring (mixing speed is fast) and ultrasonic disperse, it just can effectively realize DBT powder Uniform Doped in PVDF powder
In body, to provide good antecedent basis for barium titanate being uniformly distributed in PVDF matrix.
Preferred scheme, the process conditions of the selective laser sintering are as follows: laser power is 1.5~3W, scanning speed
For 400~700mm/min, sweep span is 2.5~4mm, and spot diameter is 0.6~1.0mm, powder layer thickness is 0.1~
0.2mm, powder bed preheating temperature are 140~170 DEG C.
Inventors have found that the working process parameter of selective laser sintering has very big shadow to the performance of composite material bracket
It rings.It needs controls such as the laser power of selective laser sintering, sweep span, scanning speeds in the reasonable scope, to pass through that
Effectively collaboration can just obtain the optimal sintered article of comprehensive performance for this.Wherein laser power, sweep span and sweep speed determine
Laser energy density in process, energy density is excessively high to be will lead to powder body material coking, vaporization and cracking etc. occur existing
As, and laser energy is too low, sintering is not fine and close, and the intensity that is bonded to each other between particle is low, and mechanical property is inadequate, while excessively high hole
Rate is also unfavorable for stress-electric coupling effect.The preheating temperature of powder bed will also control in the reasonable scope, and preheating temperature is excessively high, sintered
There is hardened or even thawing since thermal diffusion, heat radiation and heat exchange etc. make it exceed fusing point in un-sintered powder in journey；In advance
Hot temperature is too low, and there are the biggish temperature difference, sintering product is subcooled the powder of sintering part and un-sintered part, ties rapidly
Crystalline substance continue entire forming process can not, therefore, preheating temperature is too high or too low to phenomena such as warpage, deformation occur
It is all unfavorable to the sintering character of molded part and formed precision.
Make further preferred embodiment, the process conditions of the selective laser sintering are as follows: laser power be 1.5~
2.5W, scanning speed are 500~650mm/min, and sweep span is 2.5~3.0mm, and spot diameter is 0.6~1.0mm, bisque
With a thickness of 0.1~0.2mm, powder bed preheating temperature is 135~165 DEG C.
The specific technical solution of PVDF/DBT Composite Bone bracket of the present invention, comprising the following specific steps
(1) by dopamine powder, being added in Tris-HCL buffer and being equipped with concentration is that 0.5~10mg/mL dopamine is molten
Liquid.
(2) by BaTiO3Powder is added in above-mentioned dopamine solution, is uniformly dispersed, and obtains suspension, and control suspends
The pH of liquid is 6~10, and in 30~70 DEG C, 3~12h is reacted under the mixing speed of 50~100r/min, is stirred to react completion
Afterwards, it is separated by solid-liquid separation, cleaning, 10~12h is dried in vacuo under the conditions of 50~70 DEG C, grinding obtains DBT powder；The BaTiO3
The mass ratio of dopamine is 1~5:1 in powder and dopamine solution.
(3) DBT powder is added to absolute ethanol, is uniformly dispersed, obtain the solution containing DBT,
(4) it by PVDF powder, is added in the solution containing DBT, controls the mass ratio 1~40 of DBT powder and PVDF powder:
60~99, then by gained mixed solution in 30~60 DEG C, the first mechanical stirring 30 under the revolving speed of 500~1000r/min~
Then 120min carries out 30~120min of ultrasonic disperse again, be then filtered mixed solution and under the conditions of 50~70 DEG C
It is dried in vacuo 10~12h, grinding obtains composite granule.
(5) composite granule obtained above is placed in selective laser sintering system, is carried out layer by layer according to threedimensional model
Sintering removes unsintered powder after the completion of sintering to get PVDF/DBT Composite Bone bracket, selective laser sintering technological parameter
Are as follows: laser power is 1.5~3W, and scanning speed is 400~700mm/min, and sweep span is 2.5~4mm, and spot diameter is
0.6~1.0mm, powder layer thickness are 0.1~0.2mm, and powder bed preheating temperature is 140~170 DEG C.
Compared with the prior art, technical solution of the present invention bring good effect:
(1) present invention is using poly-dopamine to BaTiO3Surface is modified, and is formed poly-dopamine and is coated BaTiO3Nucleocapsid
Structure, can be in the form of covalent bond or non-covalent bond and BaTiO containing the functional groups such as phenolic hydroxyl group and amino in poly-dopamine3
It is combined with PVDF, to enhance BaTiO3Interface cohesion effect between PVDF, and promote BaTiO3Point in PVDF matrix
It dissipating, one side can promote the formation of β crystalline substance in PVDF in this way, it on the other hand can enhance stress in effective transmitting of interface,
Mechanical-electric coupling efficiency is improved, and then improves piezoelectricity, mechanical property and the biology performance of composite material bracket.
(2) present invention passes through poly-dopamine surface modification BaTiO3Promote its dispersion in PVDF, thus bionical structure
The endogenous electricity microenvironment of bone cell growth is built up, uniform and stable electro photoluminescence can adjust the function of cell membrane during Bone Defect Repari
Can, active cell signal path adjusts relevant to bone gene expression, thus promote adherency of the osteoblast on bone bracket,
Proliferation and differentiation, and then accelerate the regeneration and reconstruction of bone.
(3) present invention hydrophily and biocompatibility excellent using poly-dopamine, it is good to assign composite material bone bracket
Biocompatibility, be conducive to adherency, proliferation and the differentiation of cell.
(4) technical solution of the present invention, using situ aggregation method using dopamine to BaTiO3Surface is modified, and is obtained
Poly-dopamine coats BaTiO3Core-shell structure powder, and pass through the addition of parameter and raw material during effective controlled modification
Amount, partial size obtain the DBT powder that poly-dopamine is sufficiently modified, then by using strong mechanical stirring and ultrasonic disperse
Under collaboration, DBT powder and PVDF are sufficiently mixed uniformly, it is of the invention cooperateing with specific selective laser sintering to obtain
PVDF/DBT Piezoelectric anisotropy bone bracket.
(5) preparation method of the present invention, simply, controllably, resulting PVDF/BaTiO3Piezo-electricity composite material bone bracket has both good
Good piezoelectric property, mechanical property and biological property, is suitable for industrial application.
Detailed description of the invention
Cell adherence situation of the PVDF/DBT bone bracket when cultivating 7 days in Fig. 1 PVDF/BT and embodiment 1, wherein scheming
A is cell adherence situation of the PVDF/BT bone bracket when cultivating 7 days in 1, and Fig. 1 b is the PVDF/DBT bone bracket in embodiment 1
Cell adherence situation when cultivating 7 days.
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) 2g Dopamine hydrochloride powder is weighed using electronic balance, is added in the Tris-HCL buffer of 10mM and prepares
The dopamine solution 1L of 2.0mg/mL.
(2) BaTiO for being 200nm using electronic balance weighing 5g partial size3Powder is added to above-mentioned dopamine solution
In, main technologic parameters uniform through mechanical stirring and ultrasonic disperse are as follows: dopamine polymerization reaction time is 5h, mechanical stirring speed
Degree is 80r/min；Reaction temperature is 60 DEG C, pH 7, and resulting suspension is then carried out suction filtration cleaning using deionized water,
Remove the unreacted DOPA amine monomers in surface；It is dried in vacuo 12h under the conditions of 60 DEG C and obtains the barium titanate powder of poly-dopamine modification
Body.
(3) the DBT powder for utilizing electronic balance weighing 1g, is added in the three-necked flask for filling ethanol solution, leads to
It crosses mechanical stirring and ultrasonic disperse realizes that its is pre-dispersed.
(4) electronic balance weighing 9g is utilized, particle size is 40 μm, and the PVDF powder that fusing point is 170 DEG C is added to DBT
In suspension, then mixed solution is uniformly mixed through magnetic agitation and ultrasonic disperse, the time of mechanical stirring and ultrasonic disperse
For 60min, revolving speed 600r/min, temperature is 50 DEG C, and then uniformly mixed suspension is filtered and in 60 DEG C of conditions
Lower vacuum drying 12h, final grinding obtain uniform PVDF/DBT piezo-electricity composite material powder.
(5) 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
2W, scanning speed 500mm/min, sweep span 3mm, spot diameter 0.8mm, powder layer thickness 0.15mm, powder bed are pre-
Hot temperature is 160 DEG C.
(6) it is found through mechanical test, under the experiment condition of embodiment 1, adds BaTiO3With poly-dopamine modified lithium BaTiO3
The compressive strength of the PVDF/DBT Composite Bone bracket of preparation is respectively 30.2MPa and 38.9MPa, using poly-dopamine modification
BaTiO3(PVDF/DBT Composite Bone bracket) is with respect to BaTiO3The compressive strength of the compound rest of preparation improves 28.8%.
(7) it tests and finds through piezoelectricity, under the experiment condition of embodiment 1, add BaTiO3With poly-dopamine modified lithium BaTiO3
The output electric current of the compound rest of preparation is respectively 25nA and 80nA, the BaTiO modified using poly-dopamine3Opposite BaTiO3System
The output electric current of standby compound rest improves 220%.
(8) it is found through biological test, under the experiment condition of embodiment 1, adds BaTiO3With poly-dopamine modified lithium BaTiO3
Cell adherence, proliferation and the differentiation capability of the compound rest of preparation are remarkably reinforced, as shown in Figure 1.Wherein Fig. 1 a is more not carry out
The BaTiO of bar amine cladding3Cell adherence situation of the PVDF/BT bone bracket prepared by condition by embodiment when cultivating 7 days,
Fig. 1 b is cell adherence situation of the 1 gained PVDF/DBT bone bracket of embodiment when cultivating 7 days, it can be seen from the figure that PVDF/
Cell on DBT bone bracket is sprawled completely, and flanking cell is connected with each other, while occurring a large amount of pseudopodium and cell exocrine on cell
Matrix illustrates that PVDF/DBT bracket has and preferably promotes ability of cell proliferation.
Embodiment 2
(1) 2g Dopamine hydrochloride powder is weighed using electronic balance, is added in the Tris-HCL buffer of 10mM and prepares
The dopamine solution of 2.0mg/mL.
(2) BaTiO for being 400nm using the partial size of electronic balance weighing 5g3Powder is added to above-mentioned dopamine solution
In, main technologic parameters uniform through mechanical stirring and ultrasonic disperse are as follows: dopamine polymerization reaction time is 5h, mechanical stirring speed
Degree is 80r/min；Reaction temperature is 50 DEG C, pH 9, and resulting suspension is carried out suction filtration cleaning using deionized water, is removed
The unreacted DOPA amine monomers in surface；It is dried in vacuo 12h under the conditions of 60 DEG C and obtains the barium carbonate powder of poly-dopamine modification.
(3) the DBT powder for utilizing electronic balance weighing 2g, is added in the three-necked flask for filling ethanol solution, leads to
It crosses mechanical stirring and ultrasonic disperse realizes that its is pre-dispersed.
(4) electronic balance weighing 8g is utilized, particle size is 40 μm, and the PVDF powder that fusing point is 170 DEG C is added to DBT
In suspension, then mixed solution is uniformly mixed through magnetic agitation and ultrasonic disperse, the time of mechanical stirring and ultrasonic disperse
For 60min, revolving speed 600r/min, temperature is 50 DEG C, and then uniformly mixed suspension is filtered and in 60 DEG C of conditions
Lower vacuum drying 12h, final grinding obtain uniform PVDF/DBT piezo-electricity composite material powder.
(5) 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 PVDF/DBT Composite Bone bracket of threedimensional model, main sintering process
Parameter are as follows: laser power 2W, scanning speed 500mm/min, sweep span 3mm, spot diameter 0.8mm, bisque are thick
Degree is 0.15mm, and powder bed preheating temperature is 160 DEG C.
(6) it is found through mechanical test, under the experiment condition of embodiment 2, adds BaTiO3With poly-dopamine modified lithium BaTiO3
The compressive strength of the PVDF/DBT compound rest of preparation is respectively 30.1MPa and 31.6MPa, using poly-dopamine modification
BaTiO3Opposite BaTiO3The compressive strength of the compound rest of preparation improves 4.9%.
(7) it tests and finds through piezoelectricity, under the experiment condition of embodiment 2, add BaTiO3With poly-dopamine modified lithium BaTiO3
The output electric current of the PVDF/DBT compound rest of preparation is respectively 40nA and 78nA, the BaTiO modified using poly-dopamine3Preparation
PVDF/DBT compound rest with respect to BaTiO3The output electric current of the compound rest of preparation improves 95%.
(8) it is found through biological test, under the experiment condition of embodiment 2, adds BaTiO3With poly-dopamine modified lithium BaTiO3
Cell adherence, proliferation and the differentiation capability of the PVDF/DBT compound rest of preparation are remarkably reinforced.
Embodiment 3
(1) 2g Dopamine hydrochloride powder is weighed using electronic balance, is added in the Tris-HCL buffer of 10mM and prepares
The dopamine solution of 2.0mg/mL.
(2) powder for being 400nm using electronic balance weighing 5g partial size, is added in above-mentioned dopamine solution, through machine
Tool stirring and ultrasonic disperse are uniform, main technologic parameters are as follows: dopamine polymerization reaction time is 5h, and mechanical stirring speed is 80r/
min；Reaction temperature is 50 DEG C, pH 9, and resulting suspension is then carried out suction filtration cleaning using deionized water, removes surface
Unreacted DOPA amine monomers；It is dried in vacuo 12h under the conditions of 60 DEG C and obtains the barium carbonate powder of poly-dopamine modification.
(3) the DBT powder for utilizing electronic balance weighing 0.5g, is added in the three-necked flask for filling ethanol solution,
Realize that its is pre-dispersed by mechanical stirring and ultrasonic disperse.
(4) electronic balance weighing 9.5g is utilized, particle size is 40 μm, and the PVDF powder that fusing point is 170 DEG C is added to
In DBT suspension, then mixed solution is uniformly mixed through magnetic agitation and ultrasonic disperse, mechanical stirring and ultrasonic disperse when
Between be 60min, revolving speed 600r/min, temperature is 50 DEG C, and then uniformly mixed suspension is filtered and in 60 DEG C of items
12h is dried in vacuo under part, final grinding obtains uniform PVDF/DBT piezo-electricity composite material powder.
(5) 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 PVDF/DBT biology piezoelectricity bone bracket of threedimensional model, main sintering process parameter are as follows: laser
Power is 2W, scanning speed 500mm/min, sweep span 3mm, spot diameter 0.8mm, powder layer thickness 0.15mm,
Powder bed preheating temperature is 160 DEG C.
(6) it is found through mechanical test, under the experiment condition of embodiment 3, adds BaTiO3With poly-dopamine modified lithium BaTiO3
The compressive strength of the compound rest of preparation is respectively 29.2MPa and 36.9MPa, the BaTiO modified using poly-dopamine3Relatively
BaTiO3The compressive strength of the compound rest of preparation improves 26.4%.
(7) it tests and finds through piezoelectricity, under the experiment condition of embodiment 3, add BaTiO3With poly-dopamine modified lithium BaTiO3
The output electric current of the PVDF/DBT compound rest of preparation is respectively 20nA and 68nA, the BaTiO modified using poly-dopamine3Preparation
PVDF/DBT compound rest with respect to BaTiO3The output electric current of the compound rest of preparation improves 240%.
(8) it is found through biological test, under the experiment condition of embodiment 3, adds BaTiO3With poly-dopamine modified lithium BaTiO3
Cell adherence, proliferation and the differentiation capability of the PVDF/DBT compound rest of preparation are remarkably reinforced.
Embodiment 4
(1) 2g Dopamine hydrochloride powder is weighed using electronic balance, is added in the Tris-HCL buffer of 10mM and prepares
The dopamine solution 4L of 0.5mg/mL.
(2) BaTiO for being 500nm using electronic balance weighing 5g partial size3Powder is added to above-mentioned dopamine solution
In, main technologic parameters uniform through mechanical stirring and ultrasonic disperse are as follows: dopamine polymerization reaction time is 5h, mechanical stirring speed
Degree is 80r/min；Reaction temperature is 60 DEG C, pH 6, and resulting suspension is then carried out suction filtration cleaning using deionized water,
Remove the unreacted DOPA amine monomers in surface；It is dried in vacuo 12h under the conditions of 60 DEG C and obtains the barium titanate powder of poly-dopamine modification
Body.
(3) the DBT powder for utilizing electronic balance weighing 0.5g, is added in the three-necked flask for filling ethanol solution,
Realize that its is pre-dispersed by mechanical stirring and ultrasonic disperse.
(4) electronic balance weighing 9.5g is utilized, particle size is 40 μm, and the PVDF powder that fusing point is 170 DEG C is added to
In DBT suspension, then mixed solution is uniformly mixed through magnetic agitation and ultrasonic disperse, mechanical stirring and ultrasonic disperse when
Between be 60min, revolving speed 600r/min, temperature is 50 DEG C, and then uniformly mixed suspension is filtered and in 60 DEG C of items
12h is dried in vacuo under part, final grinding obtains uniform PVDF/DBT piezo-electricity composite material powder.
(5) 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
2W, scanning speed 500mm/min, sweep span 3mm, spot diameter 0.8mm, powder layer thickness 0.15mm, powder bed are pre-
Hot temperature is 160 DEG C.
(6) it is found through mechanical test, under the experiment condition of embodiment 4, adds BaTiO3With poly-dopamine modified lithium BaTiO3
The compressive strength of the PVDF/DBT compound rest of preparation is respectively 29.2MPa and 34.4MPa, using poly-dopamine modification
BaTiO3The PVDF/DBT compound rest of preparation is with respect to BaTiO3The compressive strength of the compound rest of preparation improves 17.8%.
(7) it tests and finds through piezoelectricity, under the experiment condition of embodiment 4, add BaTiO3With poly-dopamine modified lithium BaTiO3
The output electric current of the PVDF/DBT compound rest of preparation is respectively 20nA and 56nA, the BaTiO modified using poly-dopamine33Preparation
PVDF/DBT compound rest with respect to BaTiO3The output electric current of the compound rest of preparation improves 180%.
(8) it is found through biological test, under the experiment condition of embodiment 4, adds BaTiO3With poly-dopamine modified lithium BaTiO3
Cell adherence, proliferation and the differentiation capability of the PVDF/DBT compound rest of preparation are remarkably reinforced.
Embodiment 5
(1) 2g Dopamine hydrochloride powder is weighed using electronic balance, is added in the Tris-HCL buffer of 10mM and prepares
The dopamine solution of 2.0mg/mL.
(2) BaTiO for being 800nm using electronic balance weighing 5g partial size3Powder is added to above-mentioned dopamine solution
In, main technologic parameters uniform through mechanical stirring and ultrasonic disperse are as follows: dopamine polymerization reaction time is 5h, mechanical stirring speed
Degree is 80r/min；Reaction temperature is 70 DEG C, pH 6, and resulting suspension is then carried out suction filtration cleaning using deionized water,
Remove the unreacted DOPA amine monomers in surface；It is dried in vacuo 12h under the conditions of 60 DEG C and obtains the barium titanate powder of poly-dopamine modification
Body.
(3) the DBT powder for utilizing electronic balance weighing 0.5g, is added in the three-necked flask for filling ethanol solution,
Realize that its is pre-dispersed by mechanical stirring and ultrasonic disperse.
(4) electronic balance weighing 9.5g is utilized, particle size is 40 μm, and the PVDF powder that fusing point is 170 DEG C is added to
In DBT suspension, then mixed solution is uniformly mixed through magnetic agitation and ultrasonic disperse, mechanical stirring and ultrasonic disperse when
Between be 60min, revolving speed 600r/min, temperature is 50 DEG C, and then uniformly mixed suspension is filtered and in 60 DEG C of items
12h is dried in vacuo under part, final grinding obtains uniform PVDF/DBT piezo-electricity composite material powder.
(5) 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 PVDF/DBT piezoelectricity bone bracket of threedimensional model, main sintering process parameter are as follows: laser power
For 2.5W, scanning speed 600mm/min, sweep span 2.5mm, spot diameter 1.0mm, powder layer thickness 0.15mm,
Powder bed preheating temperature is 165 DEG C.
(6) it is found through mechanical test, under the experiment condition of embodiment 5, adds BaTiO3With poly-dopamine modified lithium BaTiO3
The compressive strength of the PVDF/DBT compound rest of preparation is respectively 31.6MPa and 37.9MPa, using poly-dopamine modification
BaTiO3The PVDF/DBT compound rest of preparation is with respect to BaTiO3The compressive strength of the compound rest of preparation improves 19.9%.
(7) it tests and finds through piezoelectricity, under the experiment condition of embodiment 5, add BaTiO3With poly-dopamine modified lithium BaTiO3
The output electric current of the PVDF/DBT compound rest of preparation is respectively 22nA and 64nA, the BaTiO modified using poly-dopamine3Preparation
PVDF/DBT compound rest with respect to BaTiO3The output electric current of the compound rest of preparation improves 191%.
(8) it is found through biological test, under the experiment condition of embodiment 5, adds BaTiO3With poly-dopamine modified lithium BaTiO3
Cell adherence, proliferation and the differentiation capability of the PVDF/DBT compound rest of preparation are remarkably reinforced.
Comparative example 1
(1) 2g Dopamine hydrochloride powder is weighed using electronic balance, is added in the Tris-HCL buffer of 10mM and prepares
The dopamine solution of 2.0mg/mL.
(2) BaTiO for being 200nm using electronic balance weighing 5g partial size3Powder is added to above-mentioned dopamine solution
In, main technologic parameters uniform through mechanical stirring and ultrasonic disperse are as follows: dopamine polymerization reaction time is 5h, mechanical stirring speed
Degree is 80r/min；Reaction temperature is 60 DEG C, pH 7, and resulting suspension is then carried out suction filtration cleaning using deionized water,
Remove the unreacted DOPA amine monomers in surface；It is dried in vacuo 12h under the conditions of 60 DEG C and obtains the barium titanate powder of poly-dopamine modification
Body.
(3) the DBT powder for utilizing electronic balance weighing 4g, is added in the three-necked flask for filling ethanol solution, leads to
It crosses mechanical stirring and ultrasonic disperse realizes that its is pre-dispersed.
(4) electronic balance weighing 4g is utilized, particle size is 40 μm, and the PVDF powder that fusing point is 170 DEG C is added to DBT
In suspension, then mixed solution is uniformly mixed through magnetic agitation and ultrasonic disperse, the time of mechanical stirring and ultrasonic disperse
For 60min, revolving speed 600r/min, temperature is 50 DEG C, and then uniformly mixed suspension is filtered and in 60 DEG C of conditions
Lower vacuum drying 12h, final grinding obtain uniform PVDF/DBT piezo-electricity composite material powder.
(5) 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 PVDF/DBT piezoelectricity bone bracket of threedimensional model, main sintering process parameter are as follows: laser power
For 2.5W, scanning speed 600mm/min, sweep span 2.5mm, spot diameter 1.0mm, powder layer thickness 0.15mm,
Powder bed preheating temperature is 165 DEG C.
(6) it is found in sintering, DBT too high levels, the melt viscosity that will lead to composite material is larger, and entire bracket can not be at
Type, follow-up test can not carry out.
Comparative example 2
(1) 2g Dopamine hydrochloride powder is weighed using electronic balance, is added in the Tris-HCL buffer of 10mM and prepares
The dopamine solution of 2.0mg/mL.
(2) BaTiO for being 50nm using electronic balance weighing 5g partial size3Powder is added in above-mentioned dopamine solution,
Uniform, the main technologic parameters through mechanical stirring and ultrasonic disperse are as follows: dopamine polymerization reaction time is 5h, and mechanical stirring speed is
80r/min；Reaction temperature is 60 DEG C, pH 7, and resulting suspension is then carried out suction filtration cleaning using deionized water, is removed
The unreacted DOPA amine monomers in surface；It is dried in vacuo 12h under the conditions of 60 DEG C and obtains the barium carbonate powder of poly-dopamine modification.
(3) the DBT powder for utilizing electronic balance weighing 1.0g, is added in the three-necked flask for filling ethanol solution,
Realize that its is pre-dispersed by mechanical stirring and ultrasonic disperse.
(4) electronic balance weighing 9.0g is utilized, particle size is 40 μm, and the PVDF powder that fusing point is 170 DEG C is added to
In DBT suspension, then mixed solution is uniformly mixed through magnetic agitation and ultrasonic disperse, mechanical stirring and ultrasonic disperse when
Between be 60min, revolving speed 600r/min, temperature is 50 DEG C, and then uniformly mixed suspension is filtered and in 60 DEG C of items
12h is dried in vacuo under part, final grinding obtains uniform PVDF/DBT piezo-electricity composite material powder.
(5) 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
2.5W, scanning speed 600mm/min, sweep span 2.5mm, spot diameter 1.0mm, powder layer thickness 0.15mm, powder
Bed preheating temperature is 165 DEG C.
(6) it is found through mechanical test, under the experiment condition of comparative example 2, adds BaTiO3And poly-dopamine modified lithium
BaTiO3The compressive strength of the compound rest of preparation is respectively 31.3MPa and 39.5MPa, the BaTiO modified using poly-dopamine3
Opposite BaTiO3The compressive strength of the compound rest of preparation improves 26.2%.
(7) it tests and finds through piezoelectricity, under the experiment condition of comparative example 2, add BaTiO3And poly-dopamine modified lithium
BaTiO3The output electric current of the compound rest of preparation is consistent substantially.
(8) it is found through biological test, under the experiment condition of comparative example 2, adds BaTiO3And poly-dopamine modified lithium
BaTiO3The compound rest of preparation is slightly improved compared to cell adherence, proliferation and the differentiation capability of PVDF bracket, but is not too bright
It is aobvious.
Comparative example 3
(1) 2g Dopamine hydrochloride powder is weighed using electronic balance, is added in the Tris-HCL buffer of 10mM and prepares
The dopamine solution of 2.0mg/mL.
(2) BaTiO for being 200nm using electronic balance weighing 5g partial size3Powder is added to above-mentioned dopamine solution
In, main technologic parameters uniform through mechanical stirring and ultrasonic disperse are as follows: dopamine polymerization reaction time is 5h, mechanical stirring speed
Degree is 80r/min；Reaction temperature is 120 DEG C, pH 7, causes solvent volatilization very fast as a result, it has been found that reaction temperature is excessively high, was modified
Journey can not be successfully progress.
Comparative example 4
(1) 2g Dopamine hydrochloride powder is weighed using electronic balance, is added in the Tris-HCL buffer of 10mM and prepares
The dopamine solution of 2.0mg/mL.
(2) BaTiO for being 200nm using electronic balance weighing 5g partial size3Powder is added to above-mentioned dopamine solution
In, main technologic parameters uniform through mechanical stirring and ultrasonic disperse are as follows: dopamine polymerization reaction time is 5h, mechanical stirring speed
Degree is 80r/min；Reaction temperature is 60 DEG C, pH 7, and resulting suspension is then carried out suction filtration cleaning using deionized water,
Remove the unreacted DOPA amine monomers in surface；It is dried in vacuo 12h under the conditions of 60 DEG C and obtains the barium titanate powder of poly-dopamine modification
Body.
(3) the DBT powder for utilizing electronic balance weighing 1.0g, is added in the three-necked flask for filling ethanol solution,
Realize that its is pre-dispersed by mechanical stirring and ultrasonic disperse.
(4) electronic balance weighing 9.0g is utilized, particle size is 40 μm, and the PVDF powder that fusing point is 170 DEG C is added to
In DBT suspension, then mixed solution is uniformly mixed through magnetic agitation and ultrasonic disperse, mechanical stirring and ultrasonic disperse when
Between be 60min, revolving speed 600r/min, temperature is 50 DEG C, and then uniformly mixed suspension is filtered and in 60 DEG C of items
12h is dried in vacuo under part, final grinding obtains uniform PVDF/DBT piezo-electricity composite material powder.
(5) 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 PVDF/DBT piezoelectricity bone bracket of threedimensional model, main sintering process parameter are as follows: laser power
For 2.5W, scanning speed 600mm/min, sweep span 2.5mm, spot diameter 1.0mm, powder layer thickness 0.15mm,
Powder bed preheating temperature is 130 DEG C.
(6) as a result, it has been found that, 4 preheating temperature of comparative example is too low, causes bracket warpage in sintering process serious, warpage
Bracket is dragged away by roller, can not be formed, and follow-up test can not also carry out.
Comparative example 5
(1) 2g Dopamine hydrochloride powder is weighed using electronic balance, is added in the Tris-HCL buffer of 10mM and prepares
The dopamine solution of 2.0mg/mL.
(2) BaTiO for being 200nm using electronic balance weighing 5g partial size3Powder is added to above-mentioned dopamine solution
In, main technologic parameters uniform through mechanical stirring and ultrasonic disperse are as follows: dopamine polymerization reaction time is 5h, mechanical stirring speed
Degree is 80r/min；Reaction temperature is 60 DEG C, pH 7, and resulting suspension is then carried out suction filtration cleaning using deionized water,
Remove the unreacted DOPA amine monomers in surface；It is dried in vacuo 12h under the conditions of 60 DEG C and obtains the barium titanate powder of poly-dopamine modification
Body.
(3) the DBT powder for utilizing electronic balance weighing 1.0g, is added in the three-necked flask for filling ethanol solution,
Realize that its is pre-dispersed by mechanical stirring and ultrasonic disperse.
(4) electronic balance weighing 9.0g is utilized, particle size is 40 μm, and the PVDF powder that fusing point is 170 DEG C is added to
In DBT suspension, then mixed solution is uniformly mixed through magnetic agitation and ultrasonic disperse, mechanical stirring and ultrasonic disperse when
Between be 60min, revolving speed 600r/min, temperature is 50 DEG C, and then uniformly mixed suspension is filtered and in 60 DEG C of items
12h is dried in vacuo under part, final grinding obtains uniform PVDF/DBT piezo-electricity composite material powder.
(5) 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 PVDF/DBT piezoelectricity bone bracket of threedimensional model, main sintering process parameter are as follows: laser power
For 0.5W, scanning speed 1200mm/min, sweep span 2.5mm, spot diameter 1.0mm, powder layer thickness 0.15mm,
Powder bed preheating temperature is 165 DEG C.
(6) it is found through mechanical test, under the experiment condition of comparative example 5, adds BaTiO3And poly-dopamine modified lithium
BaTiO3The compressive strength of the compound rest of preparation is respectively 20.1MPa and 22.3MPa, the BaTiO modified using poly-dopamine3
Opposite BaTiO3The compressive strength of the compound rest of preparation improves 10.9%.
(7) it tests and finds through piezoelectricity, under the experiment condition of embodiment 4, add BaTiO3With poly-dopamine modified lithium BaTiO3
The output electric current of the compound rest of preparation is respectively 13nA and 14nA, the BaTiO modified using poly-dopamine3Opposite BaTiO3System
The output electric current of standby compound rest improves 7.6%, and increase rate is little, this is because laser energy density is smaller, bracket
Internal voids are more, cause the power electrotransformation efficiency of bracket lower.
(8) it is found through biological test, under the experiment condition of comparative example 5, adds BaTiO3And poly-dopamine modified lithium
BaTiO3The compound rest of preparation is basically unchanged compared to cell adherence, proliferation and the differentiation capability of PVDF bracket.
Comparative example 6
(1) 2g Dopamine hydrochloride powder is weighed using electronic balance, is added in the Tris-HCL buffer of 10mM and prepares
The dopamine solution of 2.0mg/mL.
(2) BaTiO for being 400nm using the partial size of electronic balance weighing 5g3Powder is added to above-mentioned dopamine solution
In, main technologic parameters uniform through mechanical stirring and ultrasonic disperse are as follows: dopamine polymerization reaction time is 5h, mechanical stirring speed
Degree is 80r/min；Reaction temperature is 50 DEG C, pH 9, and resulting suspension is carried out suction filtration cleaning using deionized water, is removed
The unreacted DOPA amine monomers in surface；It is dried in vacuo 12h under the conditions of 60 DEG C and obtains the barium carbonate powder of poly-dopamine modification.
(3) electronic balance weighing 8g is utilized, particle size is 40 μm, and the PVDF powder that fusing point is 170 DEG C is added to DMF
It makes it completely dissolved to form uniform and stable solution in solvent, be then added to using the DBT powder of electronic balance weighing 2g
In PVDF solution, in order to construct porous structure, while the sodium chloride of weighing 0.5 is added in PVDF solution as pore-foaming agent, so
Mixed solution is uniformly mixed through magnetic agitation and ultrasonic disperse afterwards, the time of mechanical stirring and ultrasonic disperse is 60min, revolving speed
For 600r/min, temperature is 50 DEG C, then pours into culture dish uniformly mixed suspension and vacuum is done under the conditions of 60 DEG C
Dry 12h obtains uniform PVDF/DBT piezo-electricity composite material.
(5) composite material obtained above is placed in 80 DEG C of ultrapure water, stands 12h, the sodium chloride in composite material
It can be dissolved in water in the process, composite inner forms hole, and the final PVDF/DBT piezoelectricity for obtaining internal porous is multiple
Condensation material bracket.
(6) compared with the bracket that embodiment 2 is obtained by selective laser sintering method, what which obtained
The pore structure of PVDF/DBT piezo-electricity composite material internal stent is unordered in a jumble, and uniform pore diameter is poor.
(6) it is found through mechanical test, under the experiment condition of comparative example 6, adds poly-dopamine modified lithium BaTiO3System
The compressive strength of standby compound rest is 28.3MPa, and the compression performance compared to the bracket prepared by selective laser sintering drops
Low 11.7%.
(7) it tests and finds through piezoelectricity, under the experiment condition of comparative example 6, add poly-dopamine modified lithium BaTiO3System
The output electric current of standby PVDF/DBT Composite Bone bracket is 60nA, compared to the compression of the bracket prepared by selective laser sintering
Reduced performance 30%.
(8) it is found through biological test, under the experiment condition of comparative example 6, PVDF/DBT Composite Bone bracket cell is viscous
Attached, proliferation and differentiation capability weaken, and this aspect is attributed to the electro photoluminescence declines of composite material bracket, be on the other hand by
In the rack surface relative coarseness prepared by selective laser sintering, this is conducive to the adherency of cell, and then is the life of cell
Length provides good microenvironment.
Claims (10)
1. a kind of preparation method of PVDF/DBT Composite Bone bracket, it is characterised in that: by BaTiO3Powder is added to dopamine solution
Suspension is obtained, reaction obtains DBT powder, then mixes DBT powder with PVDF powder and obtains composite granule, composite granule
PVDF/DBT Composite Bone bracket is obtained by selective laser sintering.
2. a kind of preparation method of PVDF/DBT Composite Bone bracket according to claim 1, it is characterised in that: by BaTiO3
Powder is added in dopamine solution and mixes, and forms suspension and reacts under stiring by suspension in 30~70 DEG C, solid-liquid point
From gained solid phase is DBT powder；The concentration of the dopamine solution is 0.5~10mg/mL, the BaTiO3Powder and more
The mass ratio of dopamine is 1~5:1 in bar amine aqueous solution.
3. a kind of preparation method of PVDF/DBT Composite Bone bracket according to claim 2, it is characterised in that: described
BaTiO3Powder is tetragonal phase.
4. a kind of preparation method of PVDF/DBT Composite Bone bracket according to claim 2 or 3, it is characterised in that: described
BaTiO3The partial size of powder is 100~1000nm.
5. a kind of preparation method of PVDF/DBT Composite Bone bracket according to claim 2, it is characterised in that: the suspension
Liquid pH is 6~10, and the time reacted under the stirring is 3~12h.
6. a kind of preparation method of PVDF/DBT Composite Bone bracket according to claim 1, it is characterised in that: described compound
It in powder, counts in mass ratio, DBT powder: powder=1 PVDF~40:60~99.
7. a kind of preparation method of PVDF/DBT Composite Bone bracket according to claim 1, it is characterised in that: the PVDF
The partial size of powder is 20~100 μm, and fusing point is 150~180 DEG C.
8. a kind of preparation method of PVDF/DBT Composite Bone bracket according to claim 1, it is characterised in that: by DBT powder
The process that body is mixed with PVDF powder are as follows: PVDF powder is added in the solution containing DBT, obtains mixed solution, successively passes through machine
Tool stirring, ultrasonic disperse, drying, grinding obtain composite granule.
9. a kind of preparation method of PVDF/DBT Composite Bone bracket according to claim 8, it is characterised in that: the machinery
The time of stirring is 30~120min, and revolving speed is 500~1000r/min, and temperature is 30~60 DEG C, the time of the ultrasonic disperse
For 30~120min.
10. a kind of preparation method of PVDF/DBT Composite Bone bracket according to claim 1, it is characterised in that: the choosing
The laser sintered process conditions of selecting property are as follows: laser power is 1.5~3W, and scanning speed is 400~700mm/min, sweep span
For 2.5~4mm, spot diameter is 0.6~1.0mm, and powder layer thickness is 0.1~0.2mm, and powder bed preheating temperature is 140~170
℃。
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| CN113101410A (en) * | 2021-03-22 | 2021-07-13 | 华南理工大学 | Tricalcium phosphate support with uniform mesopore and three-dimensional communicated hierarchical pore structure as well as preparation method and application of tricalcium phosphate support |
| CN115025284A (en) * | 2022-05-11 | 2022-09-09 | 江西理工大学 | Graphene oxide improved barium titanate/poly (lactic acid-glycolic acid) biological scaffold and preparation method thereof |
| CN116605931A (en) * | 2023-05-18 | 2023-08-18 | 中南大学 | Method for jointly degrading water pollution by using bulk catalyst and powder catalyst |
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