CN110028335A - A kind of method of 3D printing porous ceramics organizational project product - Google Patents
A kind of method of 3D printing porous ceramics organizational project product Download PDFInfo
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- CN110028335A CN110028335A CN201910329144.4A CN201910329144A CN110028335A CN 110028335 A CN110028335 A CN 110028335A CN 201910329144 A CN201910329144 A CN 201910329144A CN 110028335 A CN110028335 A CN 110028335A
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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
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- 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
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
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- 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
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
- C04B35/632—Organic additives
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- 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
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
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- 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
- C04B38/063—Preparing or treating the raw materials individually or as batches
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3427—Silicates other than clay, e.g. water glass
- C04B2235/3436—Alkaline earth metal silicates, e.g. barium silicate
- C04B2235/3445—Magnesium silicates, e.g. forsterite
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/60—Aspects relating to the preparation, properties or mechanical treatment of green bodies or pre-forms
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- C04B2235/6026—Computer aided shaping, e.g. rapid prototyping
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- 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
Abstract
The present invention provides a kind of methods of 3D printing porous ceramics organizational project product, belong to the field of material preparation in increasing material manufacturing.The present invention is to be uniformly mixed two kinds of ceramic powders of bata-tricalcium phosphate and magnesium silicate and additive by rolling ball milling, obtains composite ceramic powder after mixed-powder is pre-sintered and is crushed.Ceramic composite powder and organic premixed liquid are hybridly prepared into solid content height, compared with low viscosity, the ceramic slurry of suitable printing, it is printed using 3D gel and carries out printing-forming, printing green body is passed through into drying, degreasing, sintering acquisition porous ceramics product sintered body, it is dipped in polycaprolactone (PCL) solution later, polycaprolactone (PCL) film layer is prepared in article surface, to overcome the brittleness and low-intensity of calcium phosphate ceramics bracket, and promote biocompatibility.
Description
Technical field
The present invention relates to a kind of methods of 3D printing porous ceramics organizational project product, belong to material increasing field, provide
A kind of method of 3D printing technique preparation ceramic structure engineering works, this method by the way that two kinds of ceramic powders are mixed,
Prepare that solid content is high, stability is good, the lower 3D gel printing slurry of viscosity carries out the printing of 3D gel, later by sintered pottery
Porcelain composite parts surface coats plastics polymer layer.
Background technique
3D printing technique, also known as " increasing material manufacturing " technology are on the basis of 2D printing, droplet ejection and modern materials science
The rapid shaping technique to grow up, basic principle be based on digital model file, can by powdery metal or ceramics etc.
Jointing material makes mutually to cohere between layers by successively printing, and constitutes a three-dimensional model in kind.3D gel prints skill
Art (3D gel-printing, 3DGP) is a kind of based on slurry printing technique (Slurry-based Three Dimensional
Printing, S-3DPTM) or directly inkjet printing technology (Direct Inkjet Printing, DIP) novel 3D printing at
Shape technology prints slurry by being formed compared with low-viscosity, the ceramics of higher solid volume fraction content or metal paste, and printer will
Slurry is ejected on print platform, while causing organic monomer in slurry in some way and free radical occurs in a very short period of time
Powder particle is carried out in-stiu coating by the tridimensional network macromolecule organic of polymerization reaction, formation, to realize that slurry is fast
Fast solidified forming, slurry form part blanks after printing solidified forming layer by layer, and green compact finally obtain after degreasing and sintering
Fine and close product.
Hydroxyapatite or bata-tricalcium phosphate or calcium silicates are similar with the inorganic constituents of bone tissue, in homeostasis
In the case where they and bone tissue have higher binding force, and material can be either logical by dissolving and absorbing step by step
This metabolic process is crossed to exclude in vitro, so that the position of bone defect is substituted by freshman bone tissue, and to degrade
Calcium, phosphonium ion is able to enter human recycle system and gradually forms area of new bone.And their biological safeties are good, Er Qiewu
Obvious rejection, new bone can smoothly realize the deposition and mass exchange of calcium salt while growing into bracket.But these
The poor ability of the external force resistance impact of ceramic material, degradation rate can not match with New born formation rate completely, magnesium silicate
In magnesium elements can improve the bioactivity of bata-tricalcium phosphate ceramics, can the outer osteoblast attachment of inductor, proliferation and raw
It is long, while can also be improved the intensity of these ceramic materials, and magnesium elements can activate the formation of skeletonization signal path promotion bone.
Pertinent literature retrieval is consulted it is found that the drop of hydroxyapatite or bata-tricalcium phosphate ingredient or calcium silicates in vivo
Solution property can by adjust the porosity of product, compactness extent and with other substances are compound is controlled.Now retrieve
CN201611110481.7 provides a kind of bone repairing support and its manufacturing method of the 3D printing containing multistage channel, uses 1300
DEG C calcined partial size, as raw material powder, part α-TCP generation, bracket drop is had since temperature is excessively high in 100 μm of TCP powder
It solves too fast, causes material that cannot play a role well, and when by β phase transition at α phase, volume increases, and can make material
Expansion, cracks, so the performance of its bracket can not show a candle to the lesser β-TCP powder of partial size.In addition, beating of using of such method
Print machine can not be beaten using the constant columnar ink for spraying 250 μm of diameter of cone cell spray head by adjusting nozzle to carry out accurate 3D
Print.
Ceramics, which are not only solved, using 3D gel printing technique molding composite ceramics product is difficult to the problem of forming, but also
The near-net-shape of complicated ceramic objects may be implemented, shorten the manufacturing cycle, reduce production cost.
Summary of the invention
The purpose of the present invention is to provide a kind of low cost, efficient manufacture complex-shaped, near-net-shape, more structures
The method of Ceramic Composite product, to obtain the biology implantation product that degradation property is good, mechanical property and biocompatibility are excellent.
The principle of the present invention is as follows: first by the bata-tricalcium phosphate of certain particle size (TCP) and silicic acid magnesium powder according to certain ratio
Example mixing, solid glucose progress rolling ball milling, which is added, makes the two uniformly mixing, is pre-sintered to obtain ceramics later again
Close powder.Ceramic composite powder is added in organic premixed liquid, the ceramic compound slurry of certain solid content is prepared, then by preparation
Ceramic compound slurry is packed into 3D gel printer and is printed, high, crowded by adjusting jet diameters, printable layer in print procedure
The print parameters such as rate, print speed, force of impression out, to obtain, surface quality is good, printing green body of complicated shape, will beat
Hand-pressing body obtains Ceramic Composite product by degreasing, sintering process.The Ceramic Composite product being sintered after printing is immersed later suitable
In polycaprolactone (PCL) solution of suitable concentration, single gather in oneself is prepared in Ceramic Composite article surface using dip-coating method
Ester (PCL) film layer improves its biocompatibility to overcome the brittleness and low-intensity of ceramics bracket.
Based on principles above and purpose, process of the invention include: composite ceramic mixing, print slurry preparation,
The printing of 3D gel, the degreasing of printing green body and sintering, coating of polycaprolactone (PCL) film layer etc..A kind of 3D provided by the invention
The method for printing porous ceramics organizational project product, includes the following steps:
(1) bata-tricalcium phosphate and silicic acid magnesium powder are weighed, solid glucose is added, is uniformly mixed, obtains mixed powder；
(2) mixed powder is pre-sintered, obtains composite ceramic powder；
(3) premixed liquid is prepared, the composite ceramic powder is uniformly mixed with premix, obtains ceramic compound slurry；
(4) ceramic compound slurry loading 3D gel printer is printed, obtains printing green body；
(5) the printing green body is passed through into degreasing, sintering process, obtains porous ceramics product；
(6) polycaprolactone film layer is prepared in the porous ceramics article surface, obtains porous ceramics organizational project product.
Preferably, above-mentioned steps (1)~(6) are implemented in the following way:
(1) bata-tricalcium phosphate (TCP) powder and silicic acid magnesium powder are weighed, wherein magnesium silicate accounts for 7~18wt.%, adds and accounts for pottery
The solid glucose of 1~3wt.% of porcelain silty amount, ball milling mixing are uniform；
(2) mixed powder of step (1) is packed into corundum crucible and is compacted to relative density 30-40%, it is pre- at 800~1000 DEG C
It is sintered 1~3h, powder ball mill crushing then will be pre-sintered and obtains 2~5 microns of average particle size of composite ceramic powder；
(3) 1~5wt% organic monomer, 0.1~0.6wt% crosslinking agent, 0.5~3wt% dispersing agent are dissolved in deionization
In water, lasting stirring obtains premixed liquid until dissolution completely, later presses step (2) obtained composite ceramic powder with premixed liquid
It is that 40~65vol% is stirred evenly according to ceramic, solid-phase content, obtains the ceramic compound slurry that viscosity is 50~300Pa.s；
(4) step (3) obtained ceramic compound slurry is fitted into the syringe of 3D gel printer, importing needs to print
Product figure printed, printing jet diameters used is 0.2~0.8mm, a height of 0.1~0.5mm of printable layer, printing pressure
Power be 0.2~0.6MPa, print speed be 5~25mm/s, 120~150 DEG C of baseplate temp；
(5) obtained green body dry 24~48h at 25~50 DEG C will be printed, later by dry green body 300~
600 DEG C of 3~6h of degreasing, in 1000~1200 DEG C of 1~3h of sintering, obtain porous ceramics system so that organic matter is completely decomposed of volatile
Part；
(6) the porous ceramics product for obtaining step (5) immerses in polycaprolactone (PCL) solution, using dip-coating method
Polycaprolactone (PCL) film layer is obtained in article surface, obtains porous ceramics organizational project product.
Further, the average particle size of ceramic powder described in step (1) is 3~20 μm.
Further, the organic monomer is acrylamide, acrylate, Methacrylamide, silicone-acrylate, gathers
At least one of urethane acrylate.
Further, the crosslinking agent is N-N'- methylene-bisacrylamide, 2,5- dimethyl -2,5 di-t-butyl peroxide
Change hexane, dimethylamine propylamine, at least one of trien；The dispersing agent is ammonium citrate, polyvinylpyrrolidine
At least one of ketone, polyethylene glycol, Sodium Polyacrylate, calgon, ester based quaternary ammonium salt, methylol tacryl element.
The present invention also provides the porous ceramics organizational project products using above method preparation.
The advantages of present invention process forming ceramic composite parts, is: on the one hand, by bata-tricalcium phosphate and two kinds of magnesium silicate
Ceramics progress is compound, not only remains the good degradability of bata-tricalcium phosphate ingredient and biocompatibility, but also due to magnesium silicate
Incorporation also improve its mechanical property, solve the disadvantage of bata-tricalcium phosphate external shock resistance ability difference, and by polycaprolactone
(PCL) it is coated in the surface of composite parts, further improves the biocompatibility of product；On the other hand, it is beaten by 3D gel
Print technology prepares organizational project Ceramic Composite product, solves the disadvantage that ceramics are difficult to form using conventional method, realizes multiple
The forming of the miscellaneous biological product of ceramics.
Specific embodiment
In order to make the foregoing objectives, features and advantages of the present invention clearer and more comprehensible, below by specific embodiment and
Attached drawing is described in further details the present invention.
The present invention provides a kind of method of 3D printing porous ceramics organizational project product, and process includes: composite ceramic
Mixing, the preparation of printing slurry, the printing of 3D gel, the degreasing and sintering, the coating of polycaprolactone (PCL) film layer of printing green body
Deng.Specifically comprise the following steps:
(1) bata-tricalcium phosphate (TCP) powder and silicic acid magnesium powder are weighed, wherein magnesium silicate accounts for 7~18wt.%, adds and accounts for pottery
The solid glucose of 1~3wt.% of porcelain silty amount, ball milling mixing are uniform.Two kinds of ceramics of bata-tricalcium phosphate and magnesium silicate are answered
It closes, not only remains the good degradability of bata-tricalcium phosphate ingredient and biocompatibility, but also since the incorporation of magnesium silicate also mentions
Its high mechanical property, solves the disadvantage of bata-tricalcium phosphate external shock resistance ability difference.The quantity of magnesium silicate influences whether to be sintered
Process, and the performance of material is finally influenced, it is including terms of mechanics and biology aspect.It needs to need to carry out according to different implantation
It adjusts.The average particle size of ceramic powder is 3~20 μm, and powder is too thin at high cost, and the too thick subsequent reactions of powder are incomplete, is sintered insufficient.
Solid glucose is added to make the powder after subsequent pre-sintering easily broken, and granularity can be readily controlled in 2~5
μm.It is to expand volatilization when mixed-powder is pre-sintered to form hole that it, which is acted on, keeps presintering powder more loose, easily broken.
The granularity of final ceramic composite powder, which is scheduled on 2~5 μm, to be determined according to the viscosity of slurry, solid content and stability.No
Solid glucose is selected, expects that block is finer and close after pre-sintering, partially firmly, 2 can be just crushed to by needing Ball-milling Time to be greater than 20 hours
~5 μm, and Ball-milling Time is long, and the impurity of introducing increases, and impurity content can increase to 0.6% or more.Select solid glucose
It is not react and be sintered between starting powder at this time because it can be expanded in a low temperature of 200 degree or less.In addition, solid
Glucose can decompose exclusion at 400 degree completely, will not remain.
(2) mixed powder of step (1) is packed into corundum crucible and is compacted to relative density 30-40%, it is pre- at 800~1000 DEG C
It is sintered 1~3h, powder ball mill crushing then will be pre-sintered and obtains 2~5 microns of average particle size of composite ceramic powder.This was pre-sintered
Journey is by the preparatory Composite of bata-tricalcium phosphate ingredient, first is that subsequent pulping process component segregation is avoided, second is that the viscosity of slurry
There is remarkable effect with stability, third is that reducing the deformation of product after sintering.It is packed into crucible and is compacted to relative density 30-40%,
On the one hand space is saved, on the other hand keeps of a relatively loose and is conducive to subsequent be crushed.
(3) 1~5wt% organic monomer, 0.1~0.6wt% crosslinking agent, 0.5~3wt% dispersing agent are dissolved in deionization
In water, lasting stirring obtains premixed liquid until dissolution completely, later by step (2) obtained ceramic composite powder and premixing
Liquid is that 40~65vol% is stirred evenly according to ceramic, solid-phase content, obtains the ceramic compound slurry that viscosity is 50~300Pa.s.
The organic monomer is acrylamide, acrylate, Methacrylamide, silicone-acrylate, urethane acrylate
At least one, the crosslinking agent be N-N'- methylene-bisacrylamide, 2,5- dimethyl -2,5 di-tert-butyl peroxide oneself
Alkane, dimethylamine propylamine, at least one of trien.Dispersing agent is also dissolved wherein, it is abundant to be conducive to dispersing agent
Powder particle surface is contacted, the effect of dispersing agent is preferably played.The dispersing agent be ammonium citrate, polyvinylpyrrolidone,
At least one of polyethylene glycol, Sodium Polyacrylate, calgon, ester based quaternary ammonium salt, methylol tacryl element.In premixed liquid
Organic monomer, crosslinking agent ratio according to the combined factors such as required solids in pulp amount, viscosity and powder size adjust, purpose
Reaching ceramic, solid-phase content is that 40~65vol% volume ratio stirs evenly, and obtains the Ceramic Composite that viscosity is 50~300Pa.s
Slurry.Solids in pulp amount is set according to the state of the indexs such as the porosity of final product and intensity and combining powder, viscosity
Numerical value is set according to print state.Therefore it needs to be reached according to various aspects integration requirement by the ratio that adjusting mixes pre- liquid
Desired indicator requirement can just obtain qualified slurry for 3D printing.
(4) step (3) obtained ceramic compound slurry is fitted into the syringe of 3D gel printer, importing needs to print
Product figure printed, printing jet diameters used is 0.2~0.8mm, a height of 0.1~0.5mm of printable layer, printing pressure
Power be 0.2~0.6MPa, print speed be 5~25mm/s, 120~150 DEG C of baseplate temp；The present invention is in this step by slurry
It is printed as required product, drawing is imported to the computer control system of 3D gel printer by processing first, according to material
Print parameters are arranged in the viscosity and article shape and dimension precision requirement of slurry, including nozzle diameter, printable layer are high, extrusion speed
Rate, print speed.Start print procedure after print parameters setting, printing successively carries out, and prints machine bottom board by control
Temperature fixes printing shape, realizes and solidifies in printing, successively stacks and obtain final product.
(5) obtained green body dry 24~48h at 25~50 DEG C will be printed, later by dry green body 300~
600 DEG C of 3~6h of degreasing, in 1000~1200 DEG C of 1~3h of sintering, obtain porous ceramics system so that organic matter is completely decomposed of volatile
Part.Printing green body is taken off part water and is further solidified by drying, carries out convenient for follow-up sintering process.Drying temperature should not mistake
Otherwise height will lead to cracking；Drying time wants long enough, otherwise can cause sintering crack.Sintering process cold stage early period is first
The organic-compound system of printing is decomposed into removing, the temperature and time in this removing stage will control proper, and temperature high de-agglomeration is fast
It will lead to cracking, the low decomposition of temperature not exclusively heats up also again will appear same problem.Removing the time is also as a same reason.Then rise
Temperature is densified to high temperature sintering, obtains final product.Sintering temperature depends on silicic acid content of magnesium, and silicic acid content of magnesium height is then sintered temperature
Degree is high.
(6) the porous ceramics product for obtaining step (5) immerses in polycaprolactone (PCL) solution, using dip-coating method
Polycaprolactone (PCL) film layer is obtained in article surface, obtains porous ceramics organizational project product.PCL layers are formed in article surface
It can be further improved the biocompatibility of product, guidance cambium is grown into after gradually degrading, and strengthens implantation effect.
In conclusion the present invention first mixes person's bata-tricalcium phosphate powder of certain particle size and silicic acid magnesium powder according to a certain percentage
It closes, solid glucose progress rolling ball milling, which is added, makes the two uniformly mixing, is pre-sintered to obtain composite ceramic powder later.
Ceramic composite powder is added in organic premixed liquid, the ceramic compound slurry of certain solid content is prepared, then by the ceramics of preparation
Slurry be packed into 3D gel printer printed, in print procedure by adjust jet diameters, printable layer height, rate of extrusion,
The print parameters such as print speed, force of impression, to obtain, surface quality is good, printing green body of complicated shape, will print green body
Ceramic Composite product is obtained by degreasing, sintering process.The Ceramic Composite product being sintered after printing is immersed into polycaprolactone later
(PCL) in solution, polycaprolactone (PCL) film layer is prepared in article surface.The invention has the advantages that: on the one hand, by β-tricresyl phosphate
Calcium and two kinds of ceramics progress of magnesium silicate are compound, not only remain the good degradability of bata-tricalcium phosphate ingredient and biocompatibility,
And since the incorporation of magnesium silicate also improves its mechanical property, solve the disadvantage of bata-tricalcium phosphate external shock resistance ability difference,
And polycaprolactone (PCL) is coated in the surface of composite parts, further improves the biocompatibility of product；Another party
Face, the organizational project Ceramic Composite product prepared by 3D gel printing technique are solved ceramics and are difficult into using conventional method
The shortcomings that type, realizes the forming of complicated ceramic structure engineering works.
Embodiment 1
(1) the silicic acid magnesium powder that the equal granularity of bata-tricalcium phosphate powder peace that average particle size is 3 μm is 5 μm is weighed, wherein silicic acid
Magnesium accounts for 7wt.%, adds the solid glucose for accounting for powder quality 1wt.%, and ball milling mixing is uniform；
(2) mixed powder of step (1) is packed into corundum crucible and is compacted to relative density 30%, in 800 DEG C of pre-sintering 1h, so
It will be pre-sintered powder ball mill crushing afterwards and obtain 2 microns of average particle size of composite ceramic powder；
(3) by 1wt% organic monomer acrylamide, 0.1wt% crosslinking agent N-N'- methylene-bisacrylamide, 0.5wt%
Dispersing agent ammonium citrate is dissolved in deionized water, and lasting stirring obtains premixed liquid until dissolution completely, later by step (2) institute
Obtained ceramic composite powder and premix is stirred evenly according to ceramic, solid-phase content for 40vol%, is obtained viscosity and is
The ceramic compound slurry of 50Pa.s；
(4) step (3) obtained ceramic compound slurry is fitted into the syringe of 3D gel printer, importing needs to print
Product figure printed, printing jet diameters used is 0.2mm, a height of 0.1mm of printable layer, and force of impression is
0.6MPa, print speed 25mm/s, 120 DEG C of baseplate temp；
(5) obtained green body dry 48h at 25 DEG C will be printed, will later make dry green body in 300 DEG C of degreasing 6h
It obtains organic matter to be completely decomposed of volatile, in 1000 DEG C of sintering 1h, obtains porous ceramics product；
(6) the porous ceramics product for obtaining step (5) immerses in polycaprolactone (PCL) solution, using dip-coating method
In single polycaprolactone (PCL) film layer that article surface obtains, porous ceramics organizational project product is obtained.
Embodiment 2
(1) it is 15 μm of silicic acid magnesium powders that weigh average particle size, which be 20 μm of equal granularities of bata-tricalcium phosphate powder peace, wherein magnesium silicate
18wt.% is accounted for, the solid glucose for accounting for powder 3wt.% is added, ball milling mixing is uniform；
(2) mixed powder of step (1) is packed into corundum crucible and is compacted to relative density 40%, in 1000 DEG C of pre-sintering 3h,
Then powder ball mill crushing will be pre-sintered and obtain 5 microns of average particle size of composite ceramic powder；
(3) by 5wt% organic monomer silicone-acrylate, 0.6wt% crosslinking agent dimethylamine propylamine, 3wt% dispersing agent
Polyvinylpyrrolidone is dissolved in deionized water, and lasting stirring obtains premixed liquid until dissolution completely, later by step (2) institute
Obtained ceramic composite powder and premix is stirred evenly according to ceramic, solid-phase content for 65vol%, is obtained viscosity and is
The ceramic compound slurry of 300Pa.s；
(4) step (3) obtained ceramic compound slurry is fitted into the syringe of 3D gel printer, importing needs to print
Product figure printed, printing jet diameters used is 0.8mm, a height of 0.5mm of printable layer, and force of impression is
0.2MPa, print speed 5mm/s, 150 DEG C of baseplate temp；
(5) will print the drying at 50 DEG C of obtained green body for 24 hours, later makes dry green body in 600 DEG C of degreasing 3h
It obtains organic matter to be completely decomposed of volatile, in 1200 DEG C of sintering 3h, obtains porous ceramics product；
(6) the porous ceramics product for obtaining step (5) immerses in polycaprolactone (PCL) solution, using dip-coating method
In single polycaprolactone (PCL) film layer that article surface obtains, porous ceramics organizational project product is obtained.
Embodiment 3
(1) it is 8 μm of silicic acid magnesium powders that weigh average particle size, which be 12 μm of equal granularities of bata-tricalcium phosphate powder peace, and wherein magnesium silicate accounts for
13wt.%, adds the solid glucose for accounting for powder 2wt.%, and ball milling mixing is uniform；
(2) mixed powder of step (1) is packed into corundum crucible and is compacted to relative density 35%, in 900 DEG C of pre-sintering 2h, so
It will be pre-sintered powder ball mill crushing afterwards and obtain 4 microns of average particle size of composite ceramic powder；
(3) by 3wt% organic monomer urethane acrylate, 0.4wt% crosslinking agent trien, 1.5wt% points
Powder Sodium Polyacrylate is dissolved in deionized water, and lasting stirring obtains premixed liquid until dissolution completely, later by step (2) institute
Obtained ceramic composite powder and premix is stirred evenly according to ceramic, solid-phase content for 55vol%, is obtained viscosity and is
The ceramic compound slurry of 160Pa.s；
(4) step (3) obtained ceramic compound slurry is fitted into the syringe of 3D gel printer, importing needs to print
Product figure printed, printing jet diameters used is 0.5mm, a height of 0.4mm of printable layer, and force of impression is
0.5MPa, print speed 15mm/s, 130 DEG C of baseplate temp；
(5) obtained green body dry 36h at 40 DEG C will be printed, will later make dry green body in 500 DEG C of degreasing 4h
It obtains organic matter to be completely decomposed of volatile, in 1100 DEG C of sintering 2h, obtains porous ceramics product；
(6) the porous ceramics product for obtaining step (5) immerses in polycaprolactone (PCL) solution, using dip-coating method
In single polycaprolactone (PCL) film layer that article surface obtains, porous ceramics organizational project product is obtained.
Embodiment 4
(1) weighing the equal granularity of bata-tricalcium phosphate powder peace that average particle size is 8 μm is 6 μm of silicic acid magnesium powders, wherein magnesium silicate
10wt.% is accounted for, the solid glucose for accounting for powder quality 2.5wt.% is added, ball milling mixing is uniform；
(2) mixed powder of step (1) is packed into corundum crucible and is compacted to relative density 35%, in 900 DEG C of pre-sintering 2h, so
It will be pre-sintered powder ball mill crushing afterwards and obtain 3.5 microns of average particle size of composite ceramic powder；
(3) by 3wt% organic monomer Methacrylamide, -2,5 di-t-butyl mistake of 0.3wt% crosslinking agent 2,5- dimethyl
Oxidation hexane, 1.2wt% dispersing agent methylol tacryl element are dissolved in deionized water, and lasting stirring obtains completely until dissolving
It is later 50vol% according to ceramic, solid-phase content by the obtained ceramic composite powder of step (2) and premix to premixed liquid
It stirs evenly, obtains the ceramic compound slurry that viscosity is 120Pa.s；
(4) step (3) obtained ceramic compound slurry is fitted into the syringe of 3D gel printer, importing needs to print
Product figure printed, printing jet diameters used is 0.6mm, a height of 0.5mm of printable layer, and force of impression is
0.5MPa, print speed 20mm/s, 140 DEG C of baseplate temp；
(5) obtained green body dry 48h at 40 DEG C will be printed, will later make dry green body in 450 DEG C of degreasing 5h
It obtains organic matter to be completely decomposed of volatile, in 1100 DEG C of sintering 2h, obtains porous ceramics product；
(6) the porous ceramics product for obtaining step (5) immerses in polycaprolactone (PCL) solution, using dip-coating method
In single polycaprolactone (PCL) film layer that article surface obtains, porous ceramics organizational project product is obtained.
The above embodiments are merely illustrative of the technical solutions of the present invention rather than is limited, the ordinary skill of this field
Personnel can be with modification or equivalent replacement of the technical solution of the present invention are made, without departing from the principle and scope of the present invention, originally
The protection scope of invention should be subject to described in claims.
Claims (10)
1. a kind of method of 3D printing porous ceramics organizational project product, which comprises the following steps:
(1) bata-tricalcium phosphate and silicic acid magnesium powder are weighed, solid glucose is added, is uniformly mixed, obtains mixed powder；
(2) mixed powder is pre-sintered, obtains composite ceramic powder；
(3) premixed liquid is prepared, the composite ceramic powder is uniformly mixed with premix, obtains ceramic compound slurry；
(4) ceramic compound slurry loading 3D gel printer is printed, obtains printing green body；
(5) the printing green body is passed through into degreasing, sintering process, obtains porous ceramics product；
(6) polycaprolactone film layer is prepared in the porous ceramics article surface, obtains porous ceramics organizational project product.
2. the method according to claim 1, wherein in the bata-tricalcium phosphate and silicic acid magnesium powder of step (1), silicic acid
Magnesium accounts for 7~18wt.%, and solid glucose accounts for 1~3wt.% of ceramic powder quality.
3. according to the method described in claim 2, it is characterized in that, the average particle size of ceramic powder is 3~20 μm in step (1).
4. being compacted the method according to claim 1, wherein the mixed powder is packed into corundum crucible by step (2)
To relative density 30-40%, in 800~1000 DEG C of 1~3h of pre-sintering, it then will be pre-sintered powder ball mill crushing and obtain average particle size
2~5 microns of composite ceramic powder.
5. the method according to claim 1, wherein step (3) by 1~5wt% organic monomer, 0.1~
0.6wt% crosslinking agent, 0.5~3wt% dispersing agent are dissolved in deionized water, and lasting stirring is premixed completely until dissolution
The ceramic composite powder and premixed liquid are later that 40~65vol% is stirred evenly according to ceramic, solid-phase content, are glued by liquid
Degree is the ceramic compound slurry of 50~300Pa.s.
6. according to the method described in claim 5, it is characterized in that, the organic monomer is acrylamide, acrylate, methyl
At least one of acrylamide, silicone-acrylate, urethane acrylate；The crosslinking agent is N-N'- di-2-ethylhexylphosphine oxide third
Acrylamide, -2,5 di-t-butyl hexane peroxide of 2,5- dimethyl, dimethylamine propylamine, at least one of trien；
The dispersing agent is ammonium citrate, polyvinylpyrrolidone, polyethylene glycol, Sodium Polyacrylate, calgon, ester group quaternary ammonium
At least one of salt, methylol tacryl element.
7. the method according to claim 1, wherein the ceramic compound slurry is packed into 3D gel by step (4)
In the syringe of printer, imports and the product figure printed is needed to be printed, printing jet diameters used is 0.2~0.8mm,
A height of 0.1~the 0.5mm of printable layer, force of impression be 0.2~0.6MPa, print speed be 5~25mm/s, baseplate temp 120~
150℃。
8. the method according to claim 1, wherein step (5) does the printing green body at 25~50 DEG C
Dry 24~48h, later by dry green body in 300~600 DEG C of 3~6h of degreasing, so that organic matter is completely decomposed of volatile, 1000
~1200 DEG C of 1~3h of sintering, obtain porous ceramics product.
9. the method according to claim 1, wherein step (6) gathers porous ceramics product immersion in oneself
In ester solution, polycaprolactone film layer is obtained in article surface using dip-coating method.
10. the porous ceramics organizational project product that according to claim 1~9 prepared by any claim the method.
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