CN109809810A - A kind of bioactive ceramics bracket and preparation method thereof with heterogeneous porous bionical natural bony structure - Google Patents
A kind of bioactive ceramics bracket and preparation method thereof with heterogeneous porous bionical natural bony structure Download PDFInfo
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Abstract
The invention discloses a kind of bioactive ceramics brackets and preparation method thereof with heterogeneous porous bionical natural bony structure.This method, to the direct printing shaping of bioactive ceramics slurry, constructs the external fine and close porous structure to the variation of internal defect continuity, realizes to the bionical of natural bony structure by advanced direct extrusion molding technique.Preparation method is as follows: (1) preparation of 3D printing bioactive ceramics powder；(2) preparation of bioactive ceramics slurry；(3) printing of heterogeneous porous bionical natural bony structure bioceramic scaffold；(4) drying and sintering of bracket obtains the bioactive ceramics bracket with heterogeneous porous bionical natural bony structure.The present invention is realized the accurate control to ceramics bracket gradual-change bore diameter size, solves the problems, such as that inhomogeneous structure accurately constructs using self-control 3D printing dedicated ceramic powder in conjunction with the advantage of 3D printing technique, significant for bone defect Regeneration and Repair.
Description
Technical field
The present invention relates to 3D printing fields, and in particular to a kind of biology with heterogeneous porous bionical natural bony structure is living
Property ceramics bracket and preparation method thereof.
Background technique
Wound, disease and increasing aging of population in recent years make bone defect patient increasing.Bone tissue
The development of engineering provides new method for clinical bone defect healing.Calcium phosphate ceramic is because of the change with inorganic mineral in nature bone
It studies point similar with crystal structure and becomes most potential artificial bone substitute materials.Other than chemical constituent, one good
Bone tissue engineering scaffold should also imitate the structure of nature bone.Nature bone includes that external fine and close compact bone substance and internal defect are more
The cancellous bone in hole.Compact bone substance is made of the compact arranged bone plate of multilayer, maintains sclerotin hard, resistance to compression and buckling strong.Account for people
The cancellous bone of body bone amount 20% constitutes 80% bone surface.The porous structure being interconnected in cancellous bone gives birth to cell
Long, nutriment can exchange, and the physiological metabolism of bone can be gone on smoothly.Researcher develops various manufacturing technologies
Prepare this bioceramic scaffold with class bone structure.Traditional method such as gas foaming, mutually separation, salt leaching and freezing are dry
The porous structure parameter being difficult in accuracy controlling bracket such as dry.Fast-developing 3D printing technique is because of its pinpoint accuracy in recent years
And controllability, become the good selection that substitution conventional method prepares bioceramic scaffold.Such as about bracket mesoporous parameter: hole
Rate, aperture size, hole connectivity, the pattern in hole etc. were also once causing the extensive pass of scholars to the influence of osteanagenesis reparation
Note.However, most of research is built upon on the basis of bionical cancellous bone, the only homogeneous texture of internal stent or the office of concern
Inhomogeneous structure (He F, Qian G, Ren W, et al.Biofabrication, 2017,9 (2): 025005 in portion region；
Xu,Mengchi,et al.Journal of Materials Chemistry B 3.18(2015):3799-3809.；
Cordell,Jacqueline M.,Michelle L.Vogl,and Amy J.Wagoner Johnson.Journal of
The mechanical behavior of biomedical materials 2.5 (2009): 560-570.), day is had ignored
Right bone macroscopically from outside to inside heterogeneous porous structure the characteristics of.
So far, there are also scholar attempt to be prepared with the mode of (1) multistep working process it is this bionical natural
The heterogeneous porous structure of bone.Residual stress can be formed in later period sintering process at graded bedding, allows for stenter to implant in this way
It is easy to be formed in graded bedding interface to weight bearing area and be broken；(2) Tang, etal are attempted using centrifugal casting in combination with orientation
Freezing casting technology makes the alumina particle in slurry mobile from center to mold periphery under the influence of centrifugal force, finally by
The effect of ceramic viscosity and particle electrostatic repulsion itself obtain have the heterogeneous porous structure for stablizing gradient distribution (Tang,
Yufei,Cong Wu,and Kang Zhao.Ceramics International(2017)；In summary it can be found that utilizing
These traditional preparation processes have three: (1) aperture size of heterogeneous porous structure is unable to accurately control；(2) more
The connectivity in hole not can guarantee；(3) it is easy to appear fracture in the interface of graded bedding, substantially reduces the yield rate of burnt product.
Therefore, it is necessary to introduce a kind of more advanced bracket technology of preparing, realize to bioactive ceramics contoured cradle ruler
Very little and internal microstructure accurate control.Designing and preparing one kind to have heterogeneous porous bionical nature bone bracket is osteanagenesis
The problem of urgent need to resolve in reparation field.
Summary of the invention
It is an object of the invention to have heterogeneous porous bionical nature bone knot using a kind of advanced forming technique building
The bioactive ceramics bracket and its method of structure, realize the bionic structure of bone defect implant, which can accurately control
Porous structure parameter processed realizes that continuity changes bone bracket pore structure from outside to inside.
The present invention makes full use of the advantage of 3D printing technique, realizes the accurate control to gradual-change bore diameter size, solves
The problem that inhomogeneous structure accurately constructs is significant for bone defect Regeneration and Repair.
The purpose of the present invention is achieved through the following technical solutions.
A kind of preparation method of the bioactive ceramics bracket with heterogeneous porous bionical natural bony structure, including it is following
Step:
(1) synthesis of spherical shape or spherical bata-tricalcium phosphate powder: phosphorus source solution is added drop-wise in calcium source solution often dropwise
Tricalcium phosphate precipitating is formed under temperature, is centrifuged after ageing, is then freeze-dried again, and final high temperature is sintered to obtain spherical or spherical
Bata-tricalcium phosphate powder；
(2) preparation of bioactive ceramics slurry: the bata-tricalcium phosphate powder that polyacrylic acid ammonium salt solution and step (1) are synthesized
Body mixing, then ball milling, are then added hydroxypropyl methyl cellulose, ultrasonic vibration after ball milling mixing, then stand at low temperature, obtain life
Object active ceramic slurry；
(3) printing of heterogeneous porous bionical natural bony structure bioceramic scaffold: by the bioactive ceramics of step (2)
Slurry is placed in printing head, and calibrates the height of syringe needle；Then the round printer model of designing load, and the ruler of edit model
Very little, selective emission line fill pattern, the aperture file of load is TXT format；Extrusion printing is carried out again, is obtained heterogeneous porous bionical
Natural bony structure bioceramic scaffold；
(4) drying and sintering of bracket: the heterogeneous porous bionical natural bony structure bioceramic that will be printed in step (3)
Bracket is dry, is sintered, and finally obtains the bioactive ceramics bracket with heterogeneous porous bionical natural bony structure.
Preferably, the granularity of step (1) the spherical or spherical bata-tricalcium phosphate powder is 100nm-5 μm
Preferably, step (1) the bata-tricalcium phosphate powder is the spherical β-of nanoscale using chemical precipitation method synthesis
Tricalcium phosphate powder.Specific synthesis the following steps are included: a. by Ca (NO3)2·4H2O andPEG (6000) is dissolved in deionization
In water, stirring to obtain calcium source solution at normal temperature；B. by (NH4)2HPO4Solution is added drop-wise to dropwise in the calcium source solution, is used in combination
The pH value that ammonium hydroxide adjusts solution is that 6-8 forms precipitating；C. (NH is dripped4)2HPO4After solution, 8-12h is stirred, and be aged 1-3
It, is washed with deionized to neutrality；D. it is freeze-dried 1-4 days, 700-900 DEG C of heat preservation 2-4h, obtains spherical or spherical again
Bata-tricalcium phosphate powder；The calcium source solution and (NH4)2HPO4Ca:P molar ratio is 3:2 in solution.
It is further preferred that the calcium source solution and (NH4)2HPO4The concentration of solution is 0.3M, 0.2M respectively.
Preferably, the pH value of step (2) the polyacrylic acid ammonium salt solution is 7-10.
Preferably, the additional amount of step (2) described hydroxypropyl methyl cellulose is the 0.5wt%- of bata-tricalcium phosphate powder
3wt%.
Preferably, the solid content of step (2) the bioactive ceramics slurry is 30vt%-55vt%.
Preferably, the frequency of step (2) described ultrasonic vibration is 80-150Hz, time 10-30min, temperature 25-50
℃；The time of the stand at low temperature is 3-50h, and temperature is 4-30 DEG C.
Preferably, the equal score of ray of step (3) the radioactive ray fill pattern is 1-100.
Preferably, in step (3), squeezing out printing is at normal temperature, to select diameter for the TT inclined syringe needle of 0.16-1.2mm
Printing；Wherein, extrusion pressure 0.1-0.6MPa, print speed 4-30mm/s.
Preferably, step (4) sintering is that 1000-1200 DEG C of heat preservation 1-5h is risen to 2-6 DEG C/min, then again with 2-
6 DEG C/min is cooled to room temperature.
A kind of bioactivity with heterogeneous porous bionical natural bony structure as made from above-described preparation method
Ceramics bracket, continuity changes the bracket from outside to inside, and varying aperture range is 50 μm -3000 μm from outside to inside.
The present invention has the varying aperture range of the bioactive ceramics bracket of heterogeneous porous bionical natural bony structure
Determination is according to homogeneous porous structure in compact bone and spongy bone bone defect model Regeneration and Repair result of study.
Compared with prior art, the present invention has the following advantages and beneficial effects:
(1) present invention uses advanced extrusion molding process, passes through the matching of air exercise print size performance and print parameters
Regulation, can accurately control the outer dimension and internal microstructure of bracket.
(2) design of the heterogeneous porous structure of the present invention is with the research conclusion to the best pore structure of compact bone and spongy bone
Theoretical foundation can more reasonably set varying aperture range from outside to inside.
(3) present invention using improved printing fill software, it is ensured that pore structure completely through and realization aperture ruler
Very little consecutive variations from outside to inside.
Detailed description of the invention
Fig. 1 a, Fig. 1 b are that the aperture size of the embodiment of the present invention 1 is 50 μm -1200 μm and gradually changes heterogeneous porous knot
Structure design drawing and sterogram.
Fig. 2 a, Fig. 2 b are that the aperture of the embodiment of the present invention 2 is 80-1200 μm heterogeneous porous bionical natural from outside to inside
The bioactive ceramics support Design figure and sterogram of bone structure.
Specific embodiment
Below with reference to embodiment, the present invention is described in further detail, embodiments of the present invention are not limited thereto.
Embodiment 1
A kind of heterogeneous porous (aperture is 50-1200 μm from outside to inside) bionical natural bony structure bioactive ceramics bracket
Prepare it is as described below:
Step 1: the synthesis of 3D printing bata-tricalcium phosphate powder
(1) by 850.14g Ca (NO3)2·4H2O and 180g PEG (6000) dissolves in deionized water, stirs at normal temperature
It mixes and obtains 0.3M calcium source solution；
(2) by 316.944g, 0.2M (NH4)2HPO4Solution is added drop-wise to dropwise in (1) calcium source solution, and molten with ammonium hydroxide adjusting
The pH value of liquid is 6.5 formation precipitatings；
(3) 8h is stirred, and is aged 1 day, is washed with deionized to neutrality；
(4) it is freeze-dried 2 days, 700 DEG C of heat preservation 2h obtain spherical bata-tricalcium phosphate powder；
Step 2: the preparation (solid content 45vt%) of high solids content slurry
(1) 7ml deionized water is added in the ammonium polyacrylate of 0.268g and is used as solvent；
It (2) is 9 with the pH value that ammonium hydroxide adjusts polyacrylic acid ammonium salt solution；
(3) partial size for synthesizing polyacrylic acid ammonium salt solution with 17.886g step 1 is the spherical bata-tricalcium phosphate of 500nm
The mixing of (β-TCP) powder, using planetary ball mill ball milling 12h (frequency 30Hz), obtains slurry；
(4) hydroxypropyl methyl cellulose is added into slurry is auxiliary rheological agents, and additional amount is the 1.5wt% of β-TCP powder,
3h is mixed using planetary ball mill high speed ball milling (frequency 40Hz), then moves into slurry in barrel.Pass through ultrasonic vibration (frequency
100Hz, time 30min, 30 DEG C of temperature), the mode of stand at low temperature (time 12h, 4 DEG C of temperature), preparation can be used for three-dimensional beat
Print molding bioactive ceramics slurry；
Step 3: the printing of heterogeneous porous bionical natural bony structure bioceramic scaffold
(1) the bioactive ceramics slurry prepared in step 2 is placed in printing head, selects diameter for the TT of 0.21mm
Inclined syringe needle, and calibrate the height of syringe needle；
(2) the round printer model of designing load, and the size of edit model is 24*24*3mm, the filling of selective emission line
Mode；The equal score of ray is 24；The aperture file of load be TXT format (aperture be arranged 0.05,0.05,0.05,0.05,
0.07,0.07,0.07,0.09,0.09,0.09,0.1,0.1,0.2,0.2,0.3,0.3……1.2,1.2,1.2)；It clicks " raw
At path " figure of printing filling shown in Fig. 1 a is obtained, use extrusion pressure 0.35MPa；Print speed is 8mm/s, so that material
Reach extrusion-molding matching, carries out extrusion printing under room temperature.
Step 4: the later period of bracket is dry and is sintered
(1) bracket elder generation air drying 3 days will printed in step 3, then 50 DEG C of oven dryings are for 24 hours
(2) 1400 DEG C of high temperature furnaces are used, the sintering temperature of bracket is 1100 DEG C, soaking time 3h, heating rate 3
DEG C/min, rate of temperature fall is 3 DEG C/min, finally obtains the bioactive ceramics branch with heterogeneous porous bionical natural bony structure
Frame, as shown in Figure 1 b.
Embodiment 2
A kind of heterogeneous porous (aperture is 250-2000 μm from outside to inside) bionical natural bony structure bioactive ceramics branch
Preparing for frame is as described below:
Step 1: the synthesis of 3D printing bata-tricalcium phosphate powder
(1) by 1700.28g Ca (NO3)2·4H2O and 360g PEG (6000) dissolves in deionized water, at normal temperature
Stirring to obtain 0.6M calcium source solution；
(2) by 633.888g, 0.4M (NH4)2HPO4Solution is added drop-wise to dropwise in (1) calcium source solution, and molten with ammonium hydroxide adjusting
The pH value of liquid is 7 formation precipitatings；
(3) 10h is stirred, and is aged 2 days, is washed with deionized to neutrality；
(4) it is freeze-dried 3 days, 800 DEG C of heat preservation 3h obtain spherical bata-tricalcium phosphate powder；
Step 2: the preparation (solid content 48vt%) of high solids content slurry
(1) 9ml deionized water is added in the ammonium polyacrylate of 0.407g and is used as solvent；
It (2) is 8 with the pH value that ammonium hydroxide adjusts polyacrylic acid ammonium salt solution；
(3) the spherical bata-tricalcium phosphate (β-that the partial size for synthesizing polyacrylic acid ammonium salt solution with 27.12g step 1 is 1 μm
TCP) powder mixes, and using planetary ball mill ball milling 6h (frequency 35Hz), obtains slurry；
(4) hydroxypropyl methyl cellulose is added into slurry is auxiliary rheological agents, and additional amount is the 1.1wt% of β-TCP powder,
3h is mixed using planetary ball mill high speed ball milling (frequency 42Hz), then moves into slurry in barrel.Pass through ultrasonic vibration (frequency
120Hz, time 25min, 25 DEG C of temperature), the mode of stand at low temperature (time 6h, 25 DEG C of temperature), preparation can be used for three-dimensional beat
Print molding bioactive ceramics slurry；
Step 3: the printing of heterogeneous porous bionical natural bony structure bioceramic scaffold
(1) the bioactive ceramics slurry prepared in step 2 is placed in printing head, selects diameter for the TT of 0.25mm
Inclined syringe needle, and calibrate the height of syringe needle；
(2) the round printer model of designing load, and the size of edit model is 12*12*3mm, the filling of selective emission line
Mode；The equal score of ray is 23；The aperture file of load be TXT format (aperture be arranged 0.25,0.25,0.25,0.3,0.3,
0.3,0.5,0.5,0.5, ... ... 2,2,2)；It clicks " generating path " and obtains the figure of printing filling shown in Fig. 2 a, pressed using squeezing out
Power 0.28MPa；Print speed is 10mm/s, so that material reaches extrusion-molding matching, carries out extrusion printing under room temperature.
Step 4: the later period of bracket is dry and is sintered
(1) bracket elder generation air drying 2 days will printed in step 3, then 50 DEG C of oven drying 48h
(2) 1400 DEG C of high temperature furnaces are used, the sintering temperature of bracket is 1150 DEG C, soaking time 3h, heating rate 3
DEG C/min, rate of temperature fall is 3 DEG C/min, finally obtains the bioactive ceramics branch with heterogeneous porous bionical natural bony structure
Frame, as shown in Figure 2 b.
Embodiment 3
A kind of heterogeneous porous (aperture is 400-3000 μm from outside to inside) bionical natural bony structure bioactive ceramics branch
Preparing for frame is as described below:
Step 1: the synthesis of 3D printing bata-tricalcium phosphate powder
(1) by 8500.14g Ca (NO3)2·4H2O and 1800g PEG (6000) dissolves in deionized water, at normal temperature
Stirring to obtain 3M calcium source solution；
(2) by 3169.44g, 2M (NH4)2HPO4Solution is added drop-wise to dropwise in (1) calcium source solution, and adjusts solution with ammonium hydroxide
PH value be 6.8 formed precipitating；
(3) 12h is stirred, and is aged 3 days, is washed with deionized to neutrality；
(4) it is freeze-dried 4 days, 800 DEG C of heat preservation 3h obtain spherical bata-tricalcium phosphate powder；
Step 2: the preparation (solid content 55vt%) of high solids content slurry
(1) 9ml deionized water is added in the ammonium polyacrylate of 0.515g and is used as solvent；
It (2) is 8 with the pH value that ammonium hydroxide adjusts polyacrylic acid ammonium salt solution；
(3) the spherical bata-tricalcium phosphate for being 3 μm by one partial size synthesized the step of polyacrylic acid ammonium salt solution and 34.32g
The mixing of (β-TCP) powder, using planetary ball mill ball milling 6h (frequency 35Hz), obtains slurry；
(4) hydroxypropyl methyl cellulose is added into slurry is auxiliary rheological agents, and additional amount is the 1.0wt% of β-TCP powder,
3h is mixed using planetary ball mill high speed ball milling (frequency 42Hz), then moves into slurry in barrel.Pass through ultrasonic vibration (frequency
120Hz, time 25min, 25 DEG C of temperature), the mode of stand at low temperature (time 6h, 25 DEG C of temperature), preparation can be used for three-dimensional beat
Print molding bioactive ceramics slurry；
Step 3: the printing of heterogeneous porous bionical natural bony structure bioceramic scaffold
(1) the bioactive ceramics slurry prepared in step 2 is placed in printing head, selects diameter for the TT of 0.40mm
Inclined syringe needle, and calibrate the height of syringe needle；
(2) the round printer model of designing load, and the size of edit model is 24*24*3mm, the filling of selective emission line
Mode；The equal score of ray is 50；The aperture file of load be TXT format (aperture be arranged 0.4,0.4,0.4,0.5,0.5,
0.5,0.6,0.6,0.6, ... ... 3,3,3)；It clicks " generating path " and obtains printing filling figure, use extrusion pressure
0.56MPa；Print speed is 8mm/s, so that material reaches extrusion-molding matching, carries out extrusion printing under room temperature.
Step 4: the later period of bracket is dry and is sintered
(1) bracket elder generation air drying 3 days will printed in step 3, then 50 DEG C of oven drying 48h
(2) 1400 DEG C of high temperature furnaces are used, the sintering temperature of bracket is 1150 DEG C, soaking time 3h, heating rate 3
DEG C/min, rate of temperature fall is 3 DEG C/min, finally obtains the bioactive ceramics branch with heterogeneous porous bionical natural bony structure
Frame.
Claims (10)
1. a kind of preparation method of the bioactive ceramics bracket with heterogeneous porous bionical natural bony structure, feature exist
In, comprising the following steps:
(1) synthesis of spherical shape or spherical bata-tricalcium phosphate powder: phosphorus source solution is added drop-wise in calcium source solution dropwise under room temperature
Tricalcium phosphate precipitating is formed, is centrifuged after ageing, is then freeze-dried again, final high temperature is sintered to obtain spherical or spherical β-phosphorus
Sour tricalcium powder；
(2) preparation of bioactive ceramics slurry: the bata-tricalcium phosphate powder that will be synthesized in polyacrylic acid ammonium salt solution and step (1)
Mixing, then ball milling, are then added hydroxypropyl methyl cellulose, ultrasonic vibration after ball milling mixing, then stand at low temperature, obtain biological
Active ceramic slurry；
(3) printing of heterogeneous porous bionical natural bony structure bioceramic scaffold: by the bioactive ceramics slurry of step (2)
It is placed in printing head, and calibrates the height of syringe needle；Then the round printer model of designing load, and the size of edit model,
Selective emission line fill pattern, the aperture file of load are TXT format；Extrusion printing is carried out again, obtains heterogeneous porous bionical day
Right bone structure bioceramic scaffold；
(4) step (3) drying and sintering of bracket: are printed to obtained heterogeneous porous bionical natural bony structure bioceramic branch
Frame is dry, is sintered, and finally obtains the bioactive ceramics bracket with heterogeneous porous bionical natural bony structure.
2. preparation method according to claim 1, which is characterized in that step (1) the spherical or spherical β-tricresyl phosphate
The granularity of calcium powder body is 100 nm-5 μm；The synthesis of the spherical or spherical bata-tricalcium phosphate powder is the following steps are included: a.
By Ca (NO3)2·4H2O and PEG (6000) dissolves in deionized water, at normal temperature stirring to obtain calcium source solution；B. will
(NH4)2HPO4Solution is added drop-wise to dropwise in the calcium source solution, and is that 6-8 forms precipitating with the pH value that ammonium hydroxide adjusts solution；c.
Drip (NH4)2HPO4After solution, 8-12h is stirred, and be aged 1-3 days, be washed with deionized to neutrality；D. it freezes again dry
Dry 1-4 days, 700-900 DEG C of heat preservation 2-4h, obtain spherical or spherical bata-tricalcium phosphate powder.
3. preparation method according to claim 1, which is characterized in that the pH value of step (2) the polyacrylic acid ammonium salt solution
For 7-10.
4. preparation method according to claim 1, which is characterized in that step (2) described hydroxypropyl methyl cellulose adds
Enter the 0.5wt%-3wt% that amount is bata-tricalcium phosphate powder.
5. preparation method according to claim 1, which is characterized in that step (2) the bioactive ceramics slurry is consolidated
Content is 30vt%-55vt%.
6. preparation method according to claim 1, which is characterized in that the frequency of step (2) described ultrasonic vibration is 80-
150 Hz, time are 10-30 min, and temperature is 25 DEG C -50 DEG C；The time of the stand at low temperature be 3-50 h, temperature be 4 DEG C-
30℃。
7. preparation method according to claim 1, which is characterized in that the ray of step (3) the radioactive ray fill pattern
Equal score is 1-100.
8. preparation method according to claim 1, which is characterized in that in step (3), squeezing out printing is choosing at normal temperature
The TT inclined syringe needle that diameter is 0.16-1.2 mm is selected to print；Wherein, extrusion pressure 0.1-0.6MPa, print speed 4-30
mm/s。
9. preparation method according to claim 1, which is characterized in that step (4) sintering is risen to 2-6 DEG C/min
1000-1200 DEG C of heat preservation 1-5 h, is then cooled to room temperature again with 2-6 DEG C/min.
10. one kind as made from claim 1-9 described in any item preparation methods has heterogeneous porous bionical nature bone knot
The bioactive ceramics bracket of structure, which is characterized in that continuity changes gained bracket from outside to inside, from outside to inside varying aperture model
Enclose is 50 μm -3000 μm.
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| CN110624421A (en) * | 2019-09-20 | 2019-12-31 | 陕西国睿材料科技有限公司 | Al (aluminum)2O3-TiO2-Fe2O3Gradient porous structure ceramic ultrafiltration membrane and preparation method thereof |
| CN110833472A (en) * | 2019-11-22 | 2020-02-25 | 吉林大学 | Manufacturing method of 3D printing-based individual customized knee joint bionic prosthesis |
| CN112979303A (en) * | 2021-02-09 | 2021-06-18 | 浙江大学 | Bone tissue gradient scaffold with adjustable degradation speed and 3D printing-based forming method thereof |
| CN113292332A (en) * | 2021-06-11 | 2021-08-24 | 四川大学 | Calcium phosphate ceramic high-throughput screening model based on 3D printing, preparation method and application |
| CN115027052A (en) * | 2022-06-07 | 2022-09-09 | 上海大学 | Tibial bone support and 3D printing method thereof |
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