CN105196398A - Preparation methods of ceramic slurry for air pressure extrusion type three-dimensional printing and biological ceramic bracket - Google Patents
Preparation methods of ceramic slurry for air pressure extrusion type three-dimensional printing and biological ceramic bracket Download PDFInfo
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- CN105196398A CN105196398A CN201510591180.XA CN201510591180A CN105196398A CN 105196398 A CN105196398 A CN 105196398A CN 201510591180 A CN201510591180 A CN 201510591180A CN 105196398 A CN105196398 A CN 105196398A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B28—WORKING CEMENT, CLAY, OR STONE
- B28B—SHAPING CLAY OR OTHER CERAMIC COMPOSITIONS; SHAPING SLAG; SHAPING MIXTURES CONTAINING CEMENTITIOUS MATERIAL, e.g. PLASTER
- B28B1/00—Producing shaped prefabricated articles from the material
- B28B1/001—Rapid manufacturing of 3D objects by additive depositing, agglomerating or laminating of material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B28—WORKING CEMENT, CLAY, OR STONE
- B28B—SHAPING CLAY OR OTHER CERAMIC COMPOSITIONS; SHAPING SLAG; SHAPING MIXTURES CONTAINING CEMENTITIOUS MATERIAL, e.g. PLASTER
- B28B11/00—Apparatus or processes for treating or working the shaped or preshaped articles
- B28B11/24—Apparatus or processes for treating or working the shaped or preshaped articles for curing, setting or hardening
- B28B11/243—Setting, e.g. drying, dehydrating or firing ceramic articles
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B28—WORKING CEMENT, CLAY, OR STONE
- B28C—PREPARING CLAY; PRODUCING MIXTURES CONTAINING CLAY OR CEMENTITIOUS MATERIAL, e.g. PLASTER
- B28C5/00—Apparatus or methods for producing mixtures of cement with other substances, e.g. slurries, mortars, porous or fibrous compositions
- B28C5/003—Methods for mixing
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- 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
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- Ceramic Engineering (AREA)
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Abstract
The invention discloses a preparation method of ceramic slurry for air pressure extrusion type three-dimensional printing. The preparation method comprises the following steps: (11) adding biological active ceramic powder into a solvent, performing ball grinding by a planetary ball grinder for 3 to 12 hours, and obtaining slurry, wherein the solid phase content of the slurry is 35 to 55 vol%; (12) adding a water-soluble rheological additive into the slurry obtained in the step (11), performing ball grinding by the planetary ball grinder for 0.5 to 3 hours, then transferring the slurry into a material feeding barrel, performing ultrasonic oscillation and low-temperature debubbling in sequence, and obtaining the ceramic slurry for air pressure extrusion type three-dimensional printing. The invention further discloses a preparation method of a biological active ceramic bracket by adopting an air pressure extrusion type three-dimensional printing forming technology. The ceramic slurry prepared by the preparation method disclosed by the invention is high in solid phase content and good in printing performance and coagulability; the prepared biological active ceramic bracket can be connected by 100 percent, and the appearance structure and the internal size of the biological active ceramic bracket can be controlled.
Description
Technical field
The present invention relates to the material preparation of rapid shaping technique, particularly a kind of for the ceramic size of air pressure extruded type 3 D-printing and the preparation method of bioceramic scaffold.
Background technology
Existing Bone Defect Repari technology mainly comprises autologous and allogenic bone transplantation technology: autologous bone contains Gegenbaur's cell alive and has the BMP of induced osteogenesis effect, and without immunological rejection, it is clinical bone defect healing " gold " standard, but limited source, can not be used for the treatment of large segmental defects; Homogeneous allogenic bone transplantation has advantage like biological characteristics and morphosis and autologous bone photo, but homogeneous allogenic bone limited source, and easily there is immunological rejection, there is the danger of propagating some disease.
In order to solve a reparation difficult problem for tissue and organ defect, the Chemical Engineer R.Langer of Massachusetts Institute Technology and the doctor J.P.Vacanti of medical college of Harvard University 20th century the mid-80 propose organizational project (Tissueengineering) this concept.Bone tissue engineer is exactly that the principle of utilizing works and life science and method regenerate new bone tissue, to repair and alternative pathology or defective bone tissue or promote the technology of its function, is the future thrust realizing Bone Defect Repari.The extracellular matrix substitute of timbering material in bone tissue engineer as seed cell and the framework of regenerating tissues, its characteristic directly affects the biological characteristics of seed cell, affect cells survival, migration, proliferation and function metabolism, finally affect the success or failure that bone tissue builds.
Along with people's improving constantly and the application of bioceramic in medical rehabilitation system biomaterial quality and security requirement, bioceramic, particularly bioactive ceramics become an important research field of material science and engineering in medicine.The preparation method of porous tissue engineering scaffold is a lot, and as foaming, Freeze Drying Technique, sintering process, but these methods are not only uncontrollable to the profile of support, aperture size and pattern, and can not realize the personalized customization of three-dimensional rack.3 D-printing forming technique integrates material science, CAD, Numeric Control Technology, adopts " increasing material " manufacturing process, accurately can copy the body with organism same shape.Rapid shaping technique can build the support that complete through hole, height rule, form and micro-structural have repeatability, and can design macrostructure and defective tissue almost identical three-dimensional structure.More ripe 3 D-printing material is resin and metal material at present, and the 3 D-printing of ceramic material is difficult to realize.Patent CN103707388A and patent CN103992088A discloses the method using powder bonding process to prepare gypsum 3 D workpiece, its existing problems are that the roughness of finished product is higher, mechanical property is poor, and prepared porous support pore size is generally more than 500 microns.Three-dimensional fiber deposition technique solves the shortcoming existed in powder bonding technology after being used for 3 D-printing, can prepare the porous support of pore size 100 microns to 1 millimeter, be expected to prepare the porous support materials closer to natural bony structure.Patent 201410840236.6 adopts electric motor boosted extruded type 3 D-printing formation system to carry out forming process of ceramics, but its organic additive addition reaches 30%, ceramic firing post-shrinkage ratio can be caused excessive, the problem that accuracy to size is not high.
Summary of the invention
In order to the above-mentioned shortcoming overcoming prior art is with not enough, the object of the present invention is to provide a kind of ceramic size for air pressure extruded type 3 D-printing, have high solid loading, good print performance and solidifiability.
Another object of the present invention is to provide and adopt air pressure extruded type 3 D-printing forming technique to prepare bioactive ceramics support, can obtain the three-dimensional rack that 100% connectedness, contour structures and inside dimension are controlled, can solve bioactive ceramics bone repair clinically can not the personalized problem accurately customized.
Object of the present invention is achieved through the following technical solutions:
For the preparation method of the ceramic size of air pressure extruded type 3 D-printing, comprise the following steps:
(11) add bioactive ceramics powder in a solvent, use planetary ball mill to be 20 ~ 30Hz ball milling, 3 ~ 12h with frequency, the solid concentration of the slurry obtained is 35 ~ 55vol%;
Described solvent is formed by deionized water and dispersant Homogeneous phase mixing; The addition of described dispersant is 0.5 ~ 2% of bioactive ceramics powder quality;
(12) water-soluble auxiliary rheological agents is added in the slurry obtained to step (11), planetary ball mill is used to be 20 ~ 30Hz ball milling mixing, 0.5 ~ 3h with frequency, then slurry is moved in barrel, carry out ultrasonic vibration, low temperature de-bubble successively, obtain the ceramic size for air pressure extruded type 3 D-printing;
The addition of described water-soluble auxiliary rheological agents is 0.5 ~ 2.5% of ceramic powder quality;
The frequency of described ultrasonic vibration is 100Hz, and the time is 15-60min, and temperature is 20 ~ 40 DEG C;
Described low temperature de-bubble is leave standstill 3 ~ 48h temperature 2 ~ 10 DEG C.
Dispersant described in step (11) is ammonium polyacrylate, Sodium Polyacrylate or stearic acid.
Step (12) water-soluble auxiliary rheological agents is xanthans, agarose, methylcellulose or polyvinyl alcohol.
Bioactive ceramics described in step (11) is hydroxyapatite, bata-tricalcium phosphate powder or bioactive glass powder.
The preparation method of bioceramic scaffold, adopts air pressure extruded type 3 D-printing legal system standby, specifically comprises the following steps:
(21) ceramic size being used for air pressure extruded type 3 D-printing that the described preparation method being used for the ceramic size of air pressure extruded type 3 D-printing prepares is placed in barrel, selects syringe needle, and calibrate the height of syringe needle;
(22) printer model of In-put design the size of edit model and form, carries out layering to model;
(23) set print parameters, slurry forms the three-dimensional ceramic support base substrate with different appearance and size and internal microstructure under the extruding of air pressure by 3 D-printing;
(24) step (23) is printed the three-dimensional ceramic support body drying obtained;
(25) dried three-dimensional ceramic support base substrate is sintered 1 ~ 5h at 1000 ~ 1200 DEG C.
Drying described in step (24), is specially:
First air drying 2 ~ 24h, then microwave drying, takes out samples weighing every 4h, until front and back quality no longer changes then completely dry.
Step (25) is described to be specially: with the ramp of 2 ~ 5 DEG C/min to 1000 ~ 1200 DEG C at 1000 ~ 1200 DEG C of sintering 1 ~ 5h, and insulation 1 ~ 5h, drops to room temperature with the speed of 2 ~ 6 DEG C/min.
Step (23) described print parameters comprises platform temperature, barrel temperature, atmospheric pressure, print speed.
The 3 D-printing that the three-dimensional fiber deposition technique of the employing air pressure extruded type of novelty of the present invention carries out porous ceramic film material is shaping, control compressed-air actuated pressure by barograph and extrude slurry, precision is higher, but pressure is the highest only has 0.6MPa, therefore to the mobility of slurry and the requirement of curing performance higher.The present invention is on the basis of system research, solve the rheological property regulation and control of slurry, the key technical problems such as solidifiability regulation and control, and control quantity of organic compounds lower than 3%, burn till and shrink lower than 10%, achieve the shaping controllable precise manufacture of 3 D-printing of bioceramic material.
Compared with prior art, the present invention has the following advantages and beneficial effect:
(1) slurry that the present invention prepares has good mobility, conformality and solidifiability.Be applicable to air pressure extruded type fiber laydown 3D print system (3D-Bioplotter
tMsystem or 3D-Bioprinter
tMsystem), printing precision reaches 0.001mm, is much higher than traditional electric motor boosted 3D print system.
(2) powder used in the present invention is bioactive ceramics powder, there is good biocompatibility, the organic reagent added is nontoxic, nuisanceless, only has bioactive ceramics phase, avoid organic additive to the bioactive impact of support after high temperature sintering in three-dimensional rack.
(3) the organic additive total amount of slurry prepared of the present invention is lower than 3wt%, burning till of Quality control can shrink lower than 10%, substantially increases the dimensional accuracy of material.
Accompanying drawing explanation
Fig. 1 is rheological property and the viscosity of slurry in embodiments of the invention 1.
Fig. 2 (a) is the three-dimensional microphoto of the top view of three-dimensional rack in embodiments of the invention 1.
Fig. 2 (b) is the three-dimensional microphoto of the side view of three-dimensional rack in embodiments of the invention 1.
Fig. 2 (c) is the sectional three-dimensional microphoto of three-dimensional rack in embodiments of the invention 1.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described in further detail, but embodiments of the present invention are not limited thereto.
Embodiment 1
Step one: the preparation of high solid loading slurry
(1) with the spherical bata-tricalcium phosphate of class (β-TCP) powder of micro/nano level of soluble calcium salt and the synthesis of phosphate reaction technique for raw material, with the mixed liquor of deionized water and ammonium polyacrylate for solvent, use planetary ball mill ball milling 8h (frequency 30Hz), preparation solid concentration is the slurry of 45vol%, and its rheological property and viscosity are shown in Fig. 1;
(2) methylcellulose adding high polymerization degree in slurry is auxiliary rheological agents, and addition is the 1wt% of β-TCP powder, uses planetary ball mill high speed ball milling mixing 2h, is then moved in barrel by slurry.By ultrasonic vibration (frequency 100Hz, time 30min, temperature 30 DEG C), low temperature de-bubble (time 12h, temperature 4 DEG C) mode, preparation may be used for the shaping bioactive ceramics slurry of 3 D-printing, the viscosity of slurry is lower than 100PaS, and aerial setting time is less than 1 minute.
Step 2: the preparation of three-dimensional controllable microstructure bioceramic scaffold base substrate
(1) slurry of preparation in step one is placed in shower nozzle, selection diameter is the TT inclined syringe needle of 0.41mm, and calibrates the height of syringe needle;
(2) the printer model cuboid of In-put design, and edit model is of a size of 20*20*5mm, carries out layering to model;
(3) arrange that platform temperature is 37 DEG C, barrel temperature is room temperature, air pressure is 0.23MPa, print speed is 6mm/s, make slurry have three-dimensional ceramic support by the formation of three-dimensional fiber deposition under the extruding of air pressure.
Step 3: the later stage of support is dry and sinter
(1) the first air drying 4h of support will printed in step 2, then takes out samples weighing every 4h after microwave drying 24h, until front and back quality no longer changes then completely dry;
(2) use 1400 DEG C of high temperature furnaces, the sintering temperature of support is 1120 DEG C, and temperature retention time is 3h, and heating rate is 3 DEG C/min, and rate of temperature fall is 3 DEG C/min, finally obtain having higher-strength, shrinkage factor be 5.7% bioactive ceramics three-dimensional rack.
Fig. 1 is viscosity and the rheological characteristic of slurry when not adding auxiliary rheological agents in this enforcement.Can find out, with the increase of shear rate, the viscosity of slurry is 0PaS, illustrates that its mobility is fabulous.
The top view of bioactive ceramics three-dimensional rack prepared by the present embodiment, side view and sectional three-dimensional microphoto are as shown in Fig. 2 (a) ~ (c).As seen from the figure, three-dimensional rack aperture rule ordered arrangement prepared by the present embodiment, and be evenly distributed, hole, horizontal and vertical direction connectedness reaches 100%.
Embodiment 2
Step one: the preparation of high solid loading slurry
(1) with ball shaped hydroxy-apatite (HA) powder of micro/nano level of soluble calcium salt and the synthesis of phosphate reaction technique for raw material, with the mixed liquor of deionized water and Sodium Polyacrylate for solvent, use planetary ball mill ball milling 8h (frequency 30Hz), preparation solid concentration is the slurry of 50vol%;
(2) in slurry, adding low melting-point agarose is auxiliary rheological agents, and addition is the 2.5wt% of HA powder, uses planetary ball mill high speed ball milling mixing 1h, is then moved in barrel by slurry.By ultrasonic vibration (frequency 100Hz, time 30min, temperature 30 DEG C), stand at low temperature (time 12h, temperature 4 DEG C) mode, preparation may be used for the shaping bioactive ceramics slurry of 3 D-printing, the viscosity of slurry is lower than 100PaS, and aerial setting time is less than 1 minute.
Step 2: the preparation of three-dimensional controllable microstructure bioceramic scaffold base substrate
(1) slurry of preparation in step one is placed in shower nozzle, selection diameter is the TT inclined syringe needle of 0.21mm, and calibrates the height of syringe needle;
(2) the printer model cuboid of In-put design, and edit model is of a size of 20*20*5mm, carries out layering to model;
(3) arrange that platform temperature is 0 DEG C, barrel temperature is 30 DEG C, air pressure is 0.30MPa, print speed is 13mm/s, make slurry have three-dimensional ceramic support by the formation of three-dimensional fiber deposition under the extruding of air pressure.
Step 3: the later stage of support is dry and sinter
(1) the first air drying 4h of support will printed in step 2, then takes out samples weighing every 4h after microwave drying 24h, until front and back quality no longer changes then completely dry;
(2) use 1400 DEG C of high temperature furnaces, the sintering temperature of support is 1200 DEG C, and temperature retention time is 3h, and heating rate is 3 DEG C/min, and rate of temperature fall is 3 DEG C/min, finally obtain having higher-strength, shrinkage factor be 4% bioactive ceramics three-dimensional rack.
Embodiment 3
Step one: the preparation of high solid loading slurry
(1) with sol-gel process synthesis nanometer level bioactive glass (BG) powder for raw material, with deionized water and stearic mixed liquor for solvent, use planetary ball mill ball milling 3h (frequency 30Hz), preparation solid concentration is the slurry of 40vol%;
(2) xanthans adding high polymerization degree in slurry is auxiliary rheological agents, and addition is the 2wt% of powder, uses planetary ball mill high speed ball milling mixing 1h, is then moved in barrel by slurry.By the mode of ultrasonic vibration (frequency 100Hz, time 30min, temperature 30 DEG C), stand at low temperature (time 12h, temperature 2 DEG C), for the preparation of the bioactive ceramics slurry that 3 D-printing is shaping; The viscosity of slurry is lower than 100PaS, and aerial setting time is less than 1 minute.
Step 2: the preparation of three-dimensional controllable microstructure bioceramic scaffold base substrate
(1) slurry of preparation in step one is placed in shower nozzle, selection diameter is the TT inclined syringe needle of 0.25mm, and calibrates the height of syringe needle;
(2) the printer model cuboid of In-put design, and edit model is of a size of 20*20*5mm, carries out layering to model;
(3) arrange that platform temperature is 0 DEG C, barrel temperature is 50 DEG C, air pressure is 0.17MPa, print speed is 5mm/s, make slurry have three-dimensional ceramic support by the formation of three-dimensional fiber deposition under the extruding of air pressure.
Step 3: the later stage of support is dry and sinter
(1) the first air drying 4h of support will printed in step 2, then takes out samples weighing every 4h after microwave drying 24h, until front and back quality no longer changes then completely dry;
(2) use 1400 DEG C of high temperature furnaces, the sintering temperature of support is 1000 DEG C, and temperature retention time is 3h, and heating rate is 3 DEG C/min, and rate of temperature fall is 3 DEG C/min, finally obtain having higher-strength, shrinkage factor be 10% bioactive ceramics three-dimensional rack.
Above-described embodiment is the present invention's preferably embodiment; but embodiments of the present invention are not limited by the examples; change, the modification done under other any does not deviate from Spirit Essence of the present invention and principle, substitute, combine, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (8)
1., for the preparation method of the ceramic size of air pressure extruded type 3 D-printing, it is characterized in that, comprise the following steps:
(11) add bioactive ceramics powder in a solvent, use planetary ball mill to be 20 ~ 30Hz ball milling, 3 ~ 12h with frequency, the solid concentration of the slurry obtained is 35 ~ 55vol%;
Described solvent is formed by deionized water and dispersant Homogeneous phase mixing; The addition of described dispersant is 0.5 ~ 2% of bioactive ceramics powder quality;
(12) water-soluble auxiliary rheological agents is added in the slurry obtained to step (11), planetary ball mill is used to be 20 ~ 30Hz ball milling mixing, 0.5 ~ 3h with frequency, then slurry is moved in barrel, carry out ultrasonic vibration, low temperature de-bubble successively, obtain the ceramic size for air pressure extruded type 3 D-printing;
The addition of described water-soluble auxiliary rheological agents is 0.5 ~ 2.5% of ceramic powder quality;
The frequency of described ultrasonic vibration is 100Hz, and the time is 15-60min, and temperature is 20 ~ 40 DEG C;
Described low temperature de-bubble is leave standstill 3 ~ 48h temperature 2 ~ 10 DEG C.
2. the preparation method of the ceramic size for air pressure extruded type 3 D-printing according to claim 1, is characterized in that, the dispersant described in step (11) is ammonium polyacrylate, Sodium Polyacrylate or stearic acid.
3. the preparation method of the ceramic size for air pressure extruded type 3 D-printing according to claim 1, is characterized in that, step (12) water-soluble auxiliary rheological agents is xanthans, agarose, methylcellulose or polyvinyl alcohol.
4. the preparation method of the ceramic size for air pressure extruded type 3 D-printing according to claim 1, is characterized in that, the bioactive ceramics described in step (11) is hydroxyapatite, bata-tricalcium phosphate powder or bioactive glass powder.
5. the preparation method of bioceramic scaffold, is characterized in that, adopts air pressure extruded type 3 D-printing legal system standby, specifically comprises the following steps:
(21) ceramic size being used for air pressure extruded type 3 D-printing that the preparation method being used for the ceramic size of air pressure extruded type 3 D-printing described in any one of Claims 1 to 4 prepares is placed in barrel, selects syringe needle, and calibrate the height of syringe needle;
(22) printer model of In-put design the size of edit model and form, carries out layering to model;
(23) set print parameters, slurry forms the three-dimensional ceramic support base substrate with different appearance and size and internal microstructure under the extruding of air pressure by 3 D-printing;
(24) step (23) is printed the three-dimensional ceramic support body drying obtained;
(25) dried three-dimensional ceramic support base substrate is sintered 1 ~ 5h at 1000 ~ 1200 DEG C.
6. the preparation method of bioceramic scaffold according to claim 5, is characterized in that, the drying described in step (24), is specially:
First air drying 2 ~ 24h, then microwave drying, takes out samples weighing every 4h, until front and back quality no longer changes then completely dry.
7. the preparation method of bioceramic scaffold according to claim 5, it is characterized in that, step (25) is described at 1000 ~ 1200 DEG C of sintering 1 ~ 5h, be specially: with the ramp of 2 ~ 5 DEG C/min to 1000 ~ 1200 DEG C, insulation 1 ~ 5h, drops to room temperature with the speed of 2 ~ 6 DEG C/min.
8. the preparation method of bioceramic scaffold according to claim 5, is characterized in that, step (23) described print parameters comprises platform temperature, barrel temperature, atmospheric pressure, print speed.
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| CN105439627A (en) * | 2015-12-31 | 2016-03-30 | 河北工业大学 | Production equipment and method for dental all-ceramic restoration |
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