CN110092652A - Bioactivity, porous ceramic preparation based on the face DLP exposure forming technique - Google Patents

Bioactivity, porous ceramic preparation based on the face DLP exposure forming technique Download PDF

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Publication number
CN110092652A
CN110092652A CN201910326483.7A CN201910326483A CN110092652A CN 110092652 A CN110092652 A CN 110092652A CN 201910326483 A CN201910326483 A CN 201910326483A CN 110092652 A CN110092652 A CN 110092652A
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bioactivity
preparation
face
forming technique
calcium phosphate
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朱向东
魏怡航
胡可辉
李向锋
杨晓
张兴栋
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Beijing Ten Dimensions Technology Co Ltd
Sichuan University
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Beijing Ten Dimensions Technology Co Ltd
Sichuan University
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y10/00—Processes of additive manufacturing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y70/00—Materials specially adapted for additive manufacturing
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/447—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on phosphates, e.g. hydroxyapatite
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/64—Burning or sintering processes
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
    • C04B38/06—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof by burning-out added substances by burning natural expanding materials or by sublimating or melting out added substances
    • C04B38/0615—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof by burning-out added substances by burning natural expanding materials or by sublimating or melting out added substances the burned-out substance being a monolitic element having approximately the same dimensions as the final article, e.g. a porous polyurethane sheet or a prepreg obtained by bonding together resin particles
    • C04B38/062—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof by burning-out added substances by burning natural expanding materials or by sublimating or melting out added substances the burned-out substance being a monolitic element having approximately the same dimensions as the final article, e.g. a porous polyurethane sheet or a prepreg obtained by bonding together resin particles the burned-out substance being formed in situ, e.g. by polymerisation of a prepolymer composition containing ceramic powder
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
    • C04B2235/6562—Heating rate
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
    • C04B2235/6567—Treatment time
    • C—CHEMISTRY; METALLURGY
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
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Abstract

The invention belongs to biomedical materials fields, and in particular to a kind of bioactivity, porous ceramic preparation based on the face DLP exposure forming technique.Bioactivity, porous ceramic preparation provided by the invention based on the face DLP exposure forming technique is the following steps are included: the surface of the preparation of photosensitive resin, calcium phosphate powder is modified, preparation of photocuring ceramic slurry.Bioactivity, porous ceramic preparation provided by the invention based on the face DLP exposure forming technique, improve content of the calcium phosphate powder in photocuring ceramic slurry, simultaneously, the modified calcium phosphate powder in surface is added in photosensitive resin, so that ceramic ink also has good mobility in the case where possessing higher solids content, to improve the precision of final printed sample.Using the porous ceramics of bioactivity, porous ceramic preparation preparation provided by the invention, intensity and precision are improved and have excellent bioactivity, have a good application prospect.

Description

Bioactivity, porous ceramic preparation based on the face DLP exposure forming technique
Technical field
The invention belongs to biomedical materials fields, and in particular to a kind of biology based on the face DLP exposure forming technique is living Property porous ceramics preparation method.
Background technique
In recent years, calcium phosphate ceramic is because of its good biocompatibility, osteoconductive and osteoinductive, in orthopaedics biology material Material field is widely used.
The preparation method of conventional porous ceramics, such as slurry foaming, space occupy-place method, foam impregnation method, although can be real The Effective Regulation of existing porosity, but be difficult to realize contradictory problems of the ink for printing (slurry) between rheological characteristic and solid content, i.e., While meeting rheological characteristic, the addition of powder is restricted.
With the development of 3D printing technique, the porous material for being while realizing rheological characteristic and powder additional amount while being met Material preparation provides possibility.Relative to other rapid shaping techniques, photocuring 3D printing technique more can accurately control pore size, Pore size distribution and porosity gradient, shaping speed is fast, and accuracy is high, can effectively avoid step effect.However, the technology is used for Gao Sheng The preparation of object activity and high-precision porous calcium phosphate ceramic still lacks systematic research, how to improve calcium phosphate powder in photocuring Content in ceramic ink (slurry) simultaneously controls its rheological property, and the selection of the degreasing and sintering process adapted to therewith, is A technical problem to be solved urgently.
Summary of the invention
Aiming at the shortcomings in the prior art, the purpose of the present invention is to provide a kind of based on the face DLP exposure forming technique The preparation method of bioactivity, porous ceramics.Bioactivity, porous pottery provided by the invention based on the face DLP exposure forming technique The preparation method of porcelain improves content of the calcium phosphate powder in photocuring ceramic slurry (ink), meanwhile, in photosensitive resin The modified calcium phosphate powder in surface is added, so that photocuring ceramic slurry in the case where possessing higher solid content, also has excellent Rheological property.Using the bioactivity, porous ceramic preparation preparation provided by the invention based on the face DLP exposure forming technique Porous ceramics, intensity and precision are improved, have a good application prospect.
The invention is realized by the following technical scheme:
A kind of preparation method of the bioactivity, porous ceramics based on the face DLP exposure forming technique, steps are as follows:
The preparation of S1, photosensitive resin:
1) into acrylic ester monomer be added monomer mass 0.5-3wt% photoinitiator, ultrasonic disperse 3-10min, With the speed of 300-800r/min, 1-5h is stirred in magnetic stirring apparatus, dissolves photoinitiator sufficiently in monomer, is mixed Close solution；
2) auxiliary agent of monomer mass 0.2-1wt% is added, into the resulting mixed solution of step 1) with 800-1200r/min Speed 0.5-2h is stirred in mechanical agitator, make its be uniformly mixed, obtain photosensitive resin premixed liquid；
S2, the surface of calcium phosphate powder are modified:
1) surface modifier for the 1-6wt% that quality is calcium phosphate powder is weighed, it is monomer mass that quality, which is then added, 5-10 times of solvent, magnetic agitation 20-40min, then weighs calcium phosphate powder and is added in above-mentioned solution under room temperature, function Rate is 200-400W ultrasonic disperse 5-15min, obtains ultrasonic disperse liquid；
2) the ultrasonic disperse liquid that step 1) obtains is poured into agate jar, the revolving speed that ball mill is arranged is 300- 600r/min, Ball-milling Time are that 2-5h is uniformly mixed it, obtain ball milling slurry；
3) the resulting ball milling slurry of step 2) is dried into 60-80 DEG C of baking oven 12-24h, then crosses 250 meshes, obtains Modified calcium phosphate powder；
The preparation of S3, photocuring ceramic slurry: the photosensitive resin premixed liquid that step S1 is obtained is changed with what step S2 was obtained Calcium phosphate powder (65-40) in mass ratio after property: (35-60) are dispersed with stirring 1- with the revolving speed machinery of 800-1100r/min 2h, so that powder is uniformly mixed with resin；Then in a planetary ball mill with 200-600r/min revolving speed ball milling 3-6h, so that Powder is evenly dispersed in resin；Finally use vacuum defoamation blender with 600r/min- (800-1200) r/min-600r/ 2-6min is stirred in the revolving speed vacuum defoamation of min, obtains photocuring ceramic slurry；
The photocuring parameter for the photocuring ceramic slurry that S4, measuring process S3 are obtained, is arranged in DLP printing device and beats Parameter is printed, designed stent model is imported in 3D printer, then the photocuring ceramic slurry that step S3 is obtained is poured into In magazine, photocuring 3D printing molding is carried out；Biscuit is obtained after printing, and uncured with washes of absolute alcohol billet surface Ceramic slurry, carried out in Muffle furnace degreasing sintered after the biscuit after cleaning is dried, obtain ceramic body；
S5, the ceramic body progress for obtaining step S4 are degreasing sintered, and the degreasing sintered temperature control is as follows:
With the heating rate of 1-3 DEG C/min, 300 DEG C are warming up to from 25 DEG C, then keeps the temperature 0.5-1h；Again with 0.5-1 DEG C/ The heating rate of min is warming up to 500 DEG C from 300 DEG C, then keeps the temperature 1-3h；Again with the heating rate of 5-10 DEG C/min, from 500 DEG C it is warming up to 1000-1300 DEG C, then keeps the temperature 2-3h；Finally cool to the furnace room temperature to get.
Further, acrylic ester monomer described in the step S1 is trimethylolpropane trimethacrylate, 1,6- Hexanediyl ester, 1,6-HD dimethyl acrylate, ethoxyquin trimethylolpropane trimethacrylate, dipropylene glycol One or both of diacrylate, tripropylene glycol diacrylate, hydroxyethyl methacrylate mixture.
Further, photoinitiator is at least one of radical initiator in the step S1；The free radical draws Hair agent is 2,4,6- trimethylbenzoy-dipheny phosphine oxide, 1- hydroxyl-cyclohexyl-phenyl ketone, the bis- (2,4,6- of phenyl Trimethylbenzoyl) phosphine oxide, methyl benzoylformate, isopropyl thioxanthone green onion ketone, 2- hydroxy-2-methyl -1- [4- (2- hydroxyl At least one of base oxethyl) phenyl] -1- acetone.
Further, auxiliary agent described in the step S1 is BYK333, BYK-163, BYK-111, BYK-346, BYK- 378, at least one of UNIQJET9012, SP-890 auxiliary agent.
Further, the mass ratio of ultrasonic disperse liquid and agate ball is 1:1.5 in the step S2.
Further, the calcium-phosphorus ratio of calcium phosphate powder is 1.50-1.67, specific surface area 10- in the step S2 120m2/ g, partial size are 0.5-20 μm.
Further, in the step S2 surface modifier be higher fatty acids, it is advanced phosphate ester salt, unsaturated organic One of acid, unsaturated fatty acid.
Further, in the step S2 dissolve surface modifier solvent be petroleum ether, deionized water, dehydrated alcohol, One or both of acetone, butanone mixture.
Compared with prior art, beneficial effects of the present invention are as follows:
(1) the bioactivity, porous ceramic preparation provided by the invention based on the face DLP exposure forming technique, using table Face activating agent greatly improves content of the calcium phosphate powder in photosensitive resin, thus improve porous ceramics intensity and Precision.
(2) the bioactivity, porous ceramic preparation provided by the invention based on the face DLP exposure forming technique, to phosphoric acid Calcium powder body is modified, and modified calcium phosphate powder surface becomes hydrophobicity from hydrophily, so as to improve powder and organic matter Compatibility, improve its content in photosensitive resin.
(3) the bioactivity, porous ceramic preparation provided by the invention based on the face DLP exposure forming technique, using spy Different degreasing sintered technique greatly improves the intensity and precision of material.
Detailed description of the invention
Fig. 1 is that ceramics bracket prepared by the embodiment of the present invention 3 and the laser after mesenchymal stem cell co-cultivation 7 days are total to Focal imaging figure.
Fig. 2 is the digital photograph of ceramics bracket prepared by the embodiment of the present invention 3.
Fig. 3 is the digital photograph of the ceramics bracket of comparative example 3 of the present invention preparation.
The ceramics bracket SEM enlarged photograph that Fig. 4 is prepared for the embodiment of the present invention 3,30 times of amplification factor.
Fig. 5 is that H&E of the embodiment of the present invention 3 in implantation animal body after 12 weeks is sliced stained photographs.
Specific embodiment
The specific embodiment of form by the following examples makees further specifically above content of the invention It is bright.But the range that this should not be interpreted as to the above-mentioned theme of the present invention is only limitted to following embodiment.
Embodiment 1, a kind of bioactivity, porous ceramics based on the face DLP exposure forming technique
The bioactivity, porous ceramic preparation based on the face DLP exposure forming technique, steps are as follows:
The preparation of S1, photosensitive resin:
1) methyl benzoylformate 0.2g, isopropyl thioxanthone green onion ketone 0.6g, 2- hydroxy-2-methyl -1- [4- are weighed respectively (2- hydroxyl-oxethyl) phenyl] -1- acetone 0.4g is added to 25g dipropylene glycol diacrylate and tripropylene glycol diacrylate In mixture, ultrasonic disperse 3min, the moderate-speed mixer 1h under magnetic stirring apparatus, so that photoinitiator sufficiently dissolves in monomer, Obtain mixed solution；
2) 0.12g BYK333 is added in the resulting mixed solution of step 1), mechanical stirring 0.5h obtains photosensitive resin It is spare to be added to, 1.5h is stirred under the mechanical agitator of 800r/min, it is uniformly mixed, obtains photosensitive resin premixed liquid；
S2, the surface of calcium phosphate powder are modified:
1) weighing 0.8g palmitinic acid to be dissolved in 150mL volume ratio is the dehydrated alcohol of 5:2, butanone in the mixed solvent, at room temperature 20min is stirred in magnetic stirring apparatus, then weigh calcium phosphate powder (Ca/P=1.534, d50=0.5um) 80g be added to it is above-mentioned In solution, with the power ultrasonic disperse 5min of 200W, ultrasonic disperse liquid is obtained；
2) the ultrasonic disperse liquid that step 1) obtains is poured into agate jar (material ball ratio 1:1.5), ball mill is set Revolving speed be 300r/min, Ball-milling Time be 2h make its be uniformly mixed, obtain ball milling slurry；
3) the resulting ball milling slurry of step 2) is dried into 60 DEG C of baking ovens 12h, then crosses 250 meshes, obtains modified Calcium phosphate powder；
The preparation of S3, photocuring ceramic slurry: the modified calcium phosphate powder that 80g step S2 is obtained is in mechanical stirring In the case where, be added in the photosensitive resin premixed liquid that step S1 is obtained in three times, make photosensitive resin premixed liquid with it is modified Calcium phosphate powder quality ratio is 40:60, first passes through machine mixer with revolving speed 800r/min and is dispersed with stirring 1h, so that powder and tree Rouge is uniformly mixed；Then make powder evenly dispersed in resin with revolving speed 200r/min ball milling 3h in a planetary ball mill； It finally uses vacuum defoamation blender to stir 2min with 600r/min-800r/min-600r/min vacuum defoamation, obtains photocuring Ceramic slurry；
The photocuring parameter for the photocuring ceramic slurry that S4, measuring process S3 are obtained, is arranged in DLP printing device and beats It is 11552.5 μ w/cm that print parameter, which is optical power density,2, time for exposure 8s, 50 μm of slice thickness, by designed stent model Import in 3D printer, then the photocuring ceramic slurry that step S3 is obtained poured into magazine, carry out photocuring 3D printing at Type；Obtain biscuit after printing, and with the uncured ink of washes of absolute alcohol billet surface, by after gained biscuit airing It carries out degreasing sintered in Muffle furnace, obtains ceramic body；
S5, it the obtained ceramic body of step S4 is put into alumina crucible carries out degreasing sintered, the degreasing sintered temperature Degree control is as follows:
With the heating rate of 1 DEG C/min, 300 DEG C are warming up to from 25 DEG C, then keeps the temperature 0.5h；Again with the liter of 0.5 DEG C/min Warm rate is warming up to 500 DEG C from 300 DEG C, then keeps the temperature 1h；Again with the heating rate of 5 DEG C/min, 1300 are warming up to from 500 DEG C DEG C, then keep the temperature 2h；Finally cool to the furnace room temperature to get.
Embodiment 2, a kind of bioactivity, porous ceramics based on the face DLP exposure forming technique
The bioactivity, porous ceramic preparation based on the face DLP exposure forming technique, steps are as follows:
The preparation of S1, photosensitive resin:
1) the 1,6-HD dipropyl that 2,4,6- trimethylbenzoy-dipheny phosphine oxide 1.2g is added to 40g is weighed In olefin(e) acid ester and 20g trimethylolpropane trimethacrylate mixture, ultrasonic disperse 5min, the moderate-speed mixer under magnetic stirring apparatus 3h obtains mixed solution so that photoinitiator sufficiently dissolves in monomer；
2) 0.65g BYK111 levelling agent and 0.65g BYK163 levelling agent are added into the resulting mixed solution of step 1), Mechanical stirring 1h obtains photosensitive resin, spare, stirs 1h in the mechanical agitator that revolving speed is 1000r/min, keeps its mixing equal It is even, obtain photosensitive resin premixed liquid；
S2, the surface of calcium phosphate powder are modified:
1) it weighs 3.2g oleic acid to be dissolved in 300mL dehydrated alcohol, stirs 30min in magnetic stirring apparatus at room temperature, then claim Calcium phosphate powder (Ca/P=1.58, d50=4.62um) 80g is taken to be added in above-mentioned solution, with the power ultrasonic disperse of 300W 10min obtains ultrasonic disperse liquid；
2) the ultrasonic disperse liquid that step 1) obtains is poured into agate jar (material ball ratio 1:1.5), ball mill is set Revolving speed be 500r/min, Ball-milling Time be 5h make its be uniformly mixed, obtain ball milling slurry；
3) the resulting ball milling slurry of step 2) is dried into 75 DEG C of baking ovens 18h, then crosses 250 meshes, obtains modified Calcium phosphate powder；
The preparation of S3, photocuring ceramic slurry: the modified calcium phosphate powder that 80g step S2 is obtained is in mechanical stirring Under, it is added in the photosensitive resin premixed liquid that step S1 is obtained in three times, makes photosensitive resin premixed liquid and modified calcium phosphate Powder quality ratio is 55:45, first passes through machine mixer with revolving speed 900r/min and is dispersed with stirring 1h, so that powder is mixed with resin Uniformly；Then make powder evenly dispersed in resin with revolving speed 500r/min ball milling 6h in a planetary ball mill；Finally adopt 4min is stirred with 600r/min--900r/min-600r/min vacuum defoamation with vacuum defoamation blender, obtains photocuring ceramics Slurry；
The photocuring parameter for the photocuring ceramic slurry that S4, measuring process S3 are obtained, is arranged in DLP printing device and beats Print parameter is to be set as optical power density 20567.63uw/cm2, time for exposure 9s, slice thickness 100um, by designed branch Frame model imports in 3D printer, then the photocuring ceramic slurry that step S3 is obtained is poured into magazine, carries out photocuring 3D Printing shaping；Obtain biscuit after printing, and with the uncured ink of washes of absolute alcohol billet surface, gained biscuit is cool It is carried out in Muffle furnace degreasing sintered after dry, obtains ceramic body；
S5, it the obtained ceramic body of step S4 is put into alumina crucible carries out degreasing sintered, the degreasing sintered temperature Degree control is as follows:
With the heating rate of 1 DEG C/min, 300 DEG C are warming up to from 25 DEG C, then keeps the temperature 3h；Again with the heating speed of 1 DEG C/min Rate is warming up to 500 DEG C from 300 DEG C, then keeps the temperature 3h；Again with the heating rate of 5 DEG C/min, 1150 DEG C are warming up to from 500 DEG C, so After keep the temperature 2h；Finally cool to the furnace room temperature to get.
Embodiment 3, a kind of preparation method of the bioactivity, porous ceramics based on the face DLP exposure forming technique
The preparation method of the bioactivity, porous ceramics based on the face DLP exposure forming technique, steps are as follows:
The preparation of S1, photosensitive resin:
1) the 1,6-HD diformazan that bis- (2,4,6- trimethylbenzoyl) the phosphine oxide 1.2g of phenyl are added to 60g is weighed In acrylate, ultrasonic disperse 10min, with the speed of 300r/min, stirs 5h, so that photoinitiator in magnetic stirring apparatus It is sufficiently dissolved in monomer, obtains mixed solution；
2) 0.6g BYK111 levelling agent is added into the resulting mixed solution of step 1), mechanical stirring 2h obtains photosensitive tree Rouge, spare, then under the mixing speed of 1200r/min, mechanical stirring 2h is uniformly mixed it, obtains photosensitive resin premix Liquid；
S2, the surface of calcium phosphate powder are modified:
1) it weighs 4.8g decanedioic acid to be dissolved in 300mL dehydrated alcohol, stirs 40min in magnetic stirring apparatus at room temperature, claim 80g calcium phosphate powder (Ca/P=1.636, d50=20um) is taken to be added in above-mentioned solution, the ultrasonic disperse under the power of 400W 10min obtains ultrasonic disperse liquid；
2) the ultrasonic disperse liquid that step 1) obtains is poured into agate jar (material ball ratio 1:1.5), ball mill is set Revolving speed be 600r/min, Ball-milling Time be 5h make its be uniformly mixed, obtain ball milling slurry；
3) the resulting ball milling slurry of step 2) is dried for 24 hours in 80 DEG C of baking ovens, then crosses 250 meshes, obtains modified Calcium phosphate powder；
The preparation of S3, photocuring ceramic slurry: the modified calcium phosphate powder that 80g step S2 is obtained is in mechanical stirring In the case where, be added in the photosensitive resin premixed liquid that step S1 is obtained in three times, make photosensitive resin premixed liquid with it is modified Calcium phosphate powder quality ratio be 65:35, first pass through machine mixer with revolving speed 1100r/min and be dispersed with stirring 2h so that powder with Resin is uniformly mixed；Then with revolving speed 600r/min ball milling 6h powder is uniformly divided in resin in a planetary ball mill It dissipates；It finally uses vacuum defoamation blender to stir 6min with 600r/min-1200r/min-600r/min vacuum defoamation, obtains light Solidify ceramic slurry；
The photocuring parameter for the photocuring ceramic slurry that S4, measuring process S3 are obtained, is arranged in DLP printing device and beats It is 11552.5 μ w/cm that print parameter, which is optical power density,2, time for exposure 10s, 50 μm of slice thickness, by designed stent model Import in 3D printer, then the photocuring ceramic slurry that step S3 is obtained poured into magazine, carry out photocuring 3D printing at Type；Obtain biscuit after printing, and with the uncured ink of washes of absolute alcohol billet surface, by after gained biscuit airing It carries out degreasing sintered in Muffle furnace, obtains ceramic body；
S5, it the obtained ceramic body of step S4 is put into alumina crucible carries out degreasing sintered, the degreasing sintered temperature Degree control is as follows:
With the heating rate of 3 DEG C/min, 300 DEG C are warming up to from 25 DEG C, then keeps the temperature 1h；Again with the heating speed of 1 DEG C/min Rate is warming up to 500 DEG C from 300 DEG C, then keeps the temperature 3h；Again with the heating rate of 10 DEG C/min, 1300 DEG C are warming up to from 500 DEG C, Then 3h is kept the temperature；Finally cool to the furnace room temperature to get.
Comparative example 1, a kind of preparation method of the bioactivity, porous ceramics based on the face DLP exposure forming technique
The preparation method and the basic phase of embodiment 1 of the bioactivity, porous ceramics based on the face DLP exposure forming technique Together, difference is, is added without surfactant in the Process of Surface Modification of 1 calcium phosphate powder of comparative example.
Comparative example 2, a kind of preparation method of the bioactivity, porous ceramics based on the face DLP exposure forming technique
The preparation method and the basic phase of embodiment 1 of the bioactivity, porous ceramics based on the face DLP exposure forming technique Together, difference is, degreasing sintered temperature control is as follows in comparative example 2: 1150 DEG C are directly warming up to from 25 DEG C, heat up 4h, 1150 DEG C of heat preservation 2h, finally cool to the furnace room temperature to get.
A kind of preparation method of the bioactivity, porous ceramics based on the face DLP exposure forming technique of comparative example 3
The preparation method and the basic phase of embodiment 1 of the bioactivity, porous ceramics based on the face DLP exposure forming technique Together, difference is the unjustified improvement of photocuring parameter in comparative example 3: it is 35621.7 μ that setting print parameters, which are optical power density, w/cm2, time for exposure 12s, 100 μm of slice thickness.
Test example one, cell compatibility test
1, it subjects: chooses mesenchymal stem cell (BMSCs), is mentioned by Sichuan University's West China Experimental Animal Center For.
2, test material: the bioactivity, porous ceramics of embodiment 1-3 and comparative example 1-3 preparation.
3, test method:
The bioactivity, porous pottery based on the face DLP exposure forming technique respectively prepared by embodiment 1-3 and comparative example 1-3 Porcelain and BMSCs are co-cultured, and observe several groups of cell growth conditions.
4, test result:
CCK-8 testing result shows that is prepared with embodiment 1-3 and comparative example 1-3 exposes forming technique based on the face DLP The BMSCs proliferation activity no difference of science of statistics that bioactivity, porous ceramics co-culture, no obvious inhibiting effect.Test result table It is bright, it is raw made from the preparation method using the bioactivity, porous ceramics provided by the invention based on the face DLP exposure forming technique The active porous ceramics of object have no toxic side effect to normal cell.
And by the observation of the cellular morphology of Fig. 1 it can be seen that after cell culture 7 days, the cell quantity on material has apparent increasing Long, cell can be good at spreading on ceramics bracket, show that the present invention has good biocompatibility.
The osteoinductive of test example two, animal et al. Ke evaluation material
1, test material: the bioactivity, porous ceramics of embodiment 1-3.
2, experimental subjects: beasle dog 3.
3, test method: being implanted into sample 3 beasle dog muscle of back two sides, and every beasle dog back is implanted into 3 groups of samples, 3 Duplicate Samples are arranged in every group of sample, and sample uses the bioactivity, porous ceramics of embodiment 1-3 preparation.(sample is straight for intramuscular implantation Diameter is 0.7cm, a height of 0.7cm) select beasle dog muscle of back for material implant site, blunt separation muscle is in after pouch-shaped points Two sides Stent Implantation material, layer-by-layer suture muscle, fascia and skin.12 weeks after operation materials, sample is through fixation, dehydration, transparent, stone Wax embedding and etc. the paraffin section after 5um is made, using H&E dye investigate material osteoinductive.
4, test result is as shown in Figure 5.
It can be seen from Fig. 5 photo after being implanted into muscle 45D, there is newborn bone tissue to generate in material hole, illustrate this Material has preferable osteoinductive.
Test example three, printing precision test
1, test material: the bioactivity based on the face DLP exposure forming technique of embodiment 1-3 and comparative example 1-3 preparation Porous ceramics.
2. test method: on CAD modeling software design diameter be 12mm, be highly 6mm, aperture is 1000um porosity For 84.87% printer model, embodiment 1-3 and comparative example 1-3 is respectively adopted, each way printed material number is 10. Comparison different tests file printing after biscuit size and be finally sintered obtained ceramics sample and the difference to design a model.
3. test result is as shown in table 1.
1 printing precision test result of table
As shown in Table 1, the blank diameter of embodiment 1-3 printing and height model difference are no different, and show that printing precision is higher； And comparative example 1-3 and modelling dimensional discrepancy are larger, printing precision is lower than embodiment 1-3.Embodiment 1-3 and comparative example 1-3 It compares and green body aperture and is finally sintered obtained ceramic porosity and differs smaller with the porosity to design a model, wherein implementing The printing precision highest of example 1, is highly preferred embodiment of the present invention, and test result shows that embodiment 1-3 can be more accurate beats The hole cellular construction for printing off model, finally obtains more fine bioactive ceramics.
Test example four, measuring mechanical property
1, test material: the bioactivity, porous ceramics of embodiment 1-3 and comparative example 1-3 preparation.
2, compression strength performance test test method: is carried out to test material.
3, test result is as shown in table 2.
2 mechanical test data of table
Group Compression strength (MPa)
Embodiment 1 7.87±0.54
Embodiment 2 7.32±0.49
Embodiment 3 7.25±0.56
Comparative example 1 5.52±0.85
Comparative example 2 4.06±0.28
Comparative example 3 6.64±0.48
As shown in Table 2, the bioactivity, porous ceramics based on the face DLP exposure forming technique of embodiment 1-3 preparation have Higher compression strength, wherein the compression strength of embodiment 1 is best, is highly preferred embodiment of the present invention.In comparison, comparative example The compression strength of the bioactivity, porous ceramics based on the face DLP exposure forming technique of 1-3 preparation will be significantly lower than embodiment 1-3 The porous ceramics of preparation, although the porosity of comparative example 1-3 ceramics is ceramic (being shown in Table 1) lower than embodiment 1-3, it is however generally that, The compression strength and porosity of porous ceramics are negatively correlated relationship.But bioactivity, porous ceramic resistance to compression prepared by comparative example 1 Intensity is very low, reason be it is powder-modified during surfactant is not added it is final to burn so that printing slurry solid content is low It is poor to tie obtained ceramics strength.The bioactivity, porous ceramic compression strength of comparative example 2-3 preparation reduces, and reason is that degreasing is burnt Knot system and photocuring parameter and prepared photocuring slurry mismatch.The experimental results showed that using preparation of the invention The bioactivity, porous ceramics mechanical strength with higher based on the face DLP exposure forming technique of method preparation, has good Application value.
The above-described embodiments merely illustrate the principles and effects of the present invention, and is not intended to limit the present invention.It is any ripe The personage for knowing this technology all without departing from the spirit and scope of the present invention, carries out modifications and changes to above-described embodiment.Cause This, institute is complete without departing from the spirit and technical ideas disclosed in the present invention by those of ordinary skill in the art such as At all equivalent modifications or change, should be covered by the claims of the present invention.

Claims (8)

1. a kind of preparation method of the bioactivity, porous ceramics based on the face DLP exposure forming technique, which is characterized in that step is such as Under:
The preparation of S1, photosensitive resin:
1) into acrylic ester monomer be added monomer mass 0.5-3wt% photoinitiator, ultrasonic disperse 3-10min, with The speed of 300-800r/min, stirs 1-5h in magnetic stirring apparatus, dissolves photoinitiator sufficiently in monomer, is mixed Solution；
2) auxiliary agent of monomer mass 0.2-1wt% is added, into the resulting mixed solution of step 1) with the speed of 800-1200r/min Degree stirs 0.5-2h in mechanical agitator, is uniformly mixed it, obtains photosensitive resin premixed liquid；
S2, the surface of calcium phosphate powder are modified:
1) surface modifier for the 1-6wt% that quality is calcium phosphate powder is weighed, the 5-10 that quality is monomer mass is then added Solvent again, magnetic agitation 20-40min, then weighs calcium phosphate powder and is added in above-mentioned solution, power is under room temperature 200-400W ultrasonic disperse 5-15min, obtains ultrasonic disperse liquid；
2) the ultrasonic disperse liquid that step 1) obtains is poured into agate jar, the revolving speed that ball mill is arranged is 300-600r/ Min, Ball-milling Time are that 2-5h is uniformly mixed it, obtain ball milling slurry；
3) the resulting ball milling slurry of step 2) is dried into 60-80 DEG C of baking oven 12-24h, then crosses 250 meshes, is modified Calcium phosphate powder afterwards；
The preparation of S3, photocuring ceramic slurry: photosensitive resin premixed liquid and step S2 that step S1 is obtained are obtained modified Calcium phosphate powder (65-40) in mass ratio: (35-60) are dispersed with stirring 1-2h with the revolving speed machinery of 800-1100r/min, make Powder is obtained to be uniformly mixed with resin；Then in a planetary ball mill with 200-600r/min revolving speed ball milling 3-6h, so that powder It is evenly dispersed in resin；Finally use vacuum defoamation blender with 600r/min- (800-1200) r/min-600r/min's 2-6min is stirred in revolving speed vacuum defoamation, obtains photocuring ceramic slurry；
The photocuring parameter for the photocuring ceramic slurry that S4, measuring process S3 are obtained, the setting printing ginseng in DLP printing device Number imports designed stent model in 3D printer, then the photocuring ceramic slurry that step S3 is obtained is poured into magazine In, carry out photocuring 3D printing molding；Obtain biscuit after printing, and with the uncured pottery of washes of absolute alcohol billet surface Porcelain slurry, carries out degreasing sintered in Muffle furnace after the biscuit after cleaning is dried, obtain ceramic body；
S5, the ceramic body progress for obtaining step S4 are degreasing sintered, and the degreasing sintered temperature control is as follows:
With the heating rate of 1-3 DEG C/min, 300 DEG C are warming up to from 25 DEG C, then keeps the temperature 0.5-1h；Again with 0.5-1 DEG C/min's Heating rate is warming up to 500 DEG C from 300 DEG C, then keeps the temperature 1-3h；Again with the heating rate of 5-10 DEG C/min, heat up from 500 DEG C To 1000-1300 DEG C, 2-3h is then kept the temperature；Finally cool to the furnace room temperature to get.
2. the preparation method of the bioactivity, porous ceramics as described in claim 1 based on the face DLP exposure forming technique, special Sign is that acrylic ester monomer described in the step S1 is trimethylolpropane trimethacrylate, 1,6- hexylene glycol dipropyl Olefin(e) acid ester, 1,6-HD dimethyl acrylate, ethoxyquin trimethylolpropane trimethacrylate, dipropylene glycol diacrylate One or both of ester, tripropylene glycol diacrylate, hydroxyethyl methacrylate mixture.
3. the preparation method of the bioactivity, porous ceramics as described in claim 1 based on the face DLP exposure forming technique, special Sign is that photoinitiator is at least one of radical initiator in the step S1；The radical initiator is 2,4, 6- trimethylbenzoy-dipheny phosphine oxide, 1- hydroxyl-cyclohexyl-phenyl ketone, bis- (the 2,4,6- trimethylbenzene first of phenyl Acyl group) phosphine oxide, methyl benzoylformate, isopropyl thioxanthone green onion ketone, 2- hydroxy-2-methyl -1- [4- (2- hydroxyl-oxethyl) benzene At least one of base] -1- acetone.
4. the preparation method of the bioactivity, porous ceramics as described in claim 1 based on the face DLP exposure forming technique, special Sign is, auxiliary agent described in the step S1 is BYK333, BYK-163, BYK-111, BYK-346, BYK-378, At least one of UNIQJET9012, SP-890 auxiliary agent.
5. the preparation method of the bioactivity, porous ceramics as described in claim 1 based on the face DLP exposure forming technique, special Sign is that the mass ratio of ultrasonic disperse liquid and agate ball is 1:1.5 in the step S2.
6. the preparation method of the bioactivity, porous ceramics as described in claim 1 based on the face DLP exposure forming technique, special Sign is that the calcium-phosphorus ratio of calcium phosphate powder is 1.50-1.67, specific surface area 10-120m in the step S22/ g, partial size are 0.5-20μm。
7. the preparation method of the bioactivity, porous ceramics as described in claim 1 based on the face DLP exposure forming technique, special Sign is that surface modifier is higher fatty acids, advanced phosphate ester salt, unsaturated organic acid, unsaturated lipid in the step S2 One of fat acid.
8. the preparation method of the bioactivity, porous ceramics as described in claim 1 based on the face DLP exposure forming technique, special Sign is, the solvent of surface modifier is dissolved in the step S2 in petroleum ether, deionized water, dehydrated alcohol, acetone, butanone One or two kinds of mixtures.
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CN110946677A (en) * 2019-12-11 2020-04-03 南京中医药大学 Preparation method and application of 3D printing composite magnetic calcined native copper stent
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CN111960811A (en) * 2020-08-27 2020-11-20 广东工业大学 DLP (digital light processing) forming method for diamond/cubic boron nitride-ceramic composite material
CN112174657A (en) * 2020-09-29 2021-01-05 江西金石三维智能制造科技有限公司 Photocuring hydroxyl phosphorus lime ceramic slurry and preparation method and application thereof
WO2022174507A1 (en) * 2021-02-19 2022-08-25 南京航空航天大学 Method for preparing calcium silicate/magnesium oxide porous biological bone scaffold based on in-situ method
CN113387615A (en) * 2021-06-30 2021-09-14 成都百年贝雅医疗科技有限公司 DLP (digital light processing) biological ceramic printing slurry
CN113800940A (en) * 2021-09-22 2021-12-17 中国科学院金属研究所 Bionic light heat-insulation sandwich structure and preparation method thereof
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Application publication date: 20190806