CN108456457A - 3D direct write zirconia ceramics inks - Google Patents

3D direct write zirconia ceramics inks Download PDF

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Publication number
CN108456457A
CN108456457A CN201611141895.6A CN201611141895A CN108456457A CN 108456457 A CN108456457 A CN 108456457A CN 201611141895 A CN201611141895 A CN 201611141895A CN 108456457 A CN108456457 A CN 108456457A
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ink
chloride
ammonium
sodium
dispersant
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CN108456457B (en
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张斗
廖晶晶
陈何昊
周科朝
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Central South University
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Central South University
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • 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
    • C04B35/48—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 zirconium or hafnium oxides, zirconates, zircon or hafnates
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C09D11/38—Inkjet printing inks characterised by non-macromolecular additives other than solvents, pigments or dyes

Abstract

3D direct write zirconia ceramics inks, including zirconia particles, solvent, binder, dispersant and salt substance；Zirconia particles grain size is 0.1 2 μm, and solid concentration in the ink is 40 58vol%；Dispersant is polyacrylic acid, one or more of in acid polyethylene, ammonium polyacrylate, polyethylene hydrochlorate, polyacrylate, polycarboxylate, poly- acetimide, and dispersant is zirconia particles dry powder quality 0.1 2%；Salt substance is ammonium chloride, zinc acetate, sodium chloride, magnesium chloride, potassium chloride, barium chloride, ammonium hydrogen carbonate, anhydrous calcium chloride, potassium carbonate, sodium bicarbonate, sodium carbonate, natrium carbonicum calcinatum, anhydrous sodium acetate, anhydrous calcium chloride, copper sulphate, basic copper carbonate, ammonium sulfate, ammonium hydrogen carbonate, alum, one or more of in sodium citrate, salt substance is drop mass 0.001 0.1%.The present invention can print at room temperature, can be flowed out from fine nozzle while having higher solids content without blocking, and can be solidified into rapidly with some strength filament, have good rheological performance.

Description

3D direct write zirconia ceramics inks
Technical field
The present invention relates to a kind of zirconia ceramics inks for 3D direct writes, belong to 3D printing field of material technology.
Background technology
Modern micro-processing technology has the unrivaled advantage of traditional processing mode on micro-nano-scale.Micro-processing technology Including Soft lithograph technology, laser ablation technology, stereo lithography, two-photon polymerized technology, electrostatic discharged technology and 3D direct writes Technology etc..Wherein, 3D direct writing technologies (three dimensional direct-writing), also known as direct write package technique (Direct-writing Assembly) is a branch of 3D printing technique.The typical example of 3D printing manufacturing technology has light Curing molding, selective laser sintering and moulding and laminated solid body molding etc., but that there are formed precisions is low, subsequent processing is complicated, The disadvantages such as shaping strength is low are not suitable for preparing small-sized fine part.In recent years, the 3D direct write forming techniques based on rapid shaping (Direct ink writing, DIW) due to its can prepare it is fine with the complexity compared with large ratio of height to width and containing span feature Three-dimensional periodic structure and the extensive concern for causing researcher.
3D direct writes in broad terms, refer to a kind of mo(u)lding equipment using in computer control platform, will be special Determine the molding technology of precise structure that the material of ingredient is set according to computer software.Generally ink material (ink) is stored in In the barrel of one temperature-controllable, nozzle is connected with barrel and is mounted on a three axis CNC positioning tables, is controlled and is fed by pressure Mini sprinkler (micronozzle) material is sprayed, select different curing process by ejection according to the curing mode of material Ink material carries out curing molding.As long as having suitable rheological property and certain conformality, a variety of materials can design It is used for such sculpting method at marking ink, for the string diameter range printed from hundred nanometers to millimeter, filament can be horizontal Across larger gap, it might even be possible to which space free forming completes the processing tasks that other processing technologies are difficult to complete.
3D direct write forming techniques are a kind of novel mould-free forming technologies, and the technology is by CAD and precision Machinery, accurately controls the deposition of suspension, and simple three-dimensional periodic structure and (no branch containing span are prepared by way of being successively superimposed Support) or complex three-dimensional structure with very large ratio of height to width.Compared with other quick molding methods, direct write forming technique has aobvious Work advantage：1) forming process is not necessarily to mold, with short production cycle, efficient, at low cost；2) sample can easily be changed according to demand Shape and size, production is flexible, and control is accurate；3) raw material types diversification, there is inorganic non-metallic, metal and organic polymer Object etc.；4) functional material in the fields such as biology, optics, electronics, even active somatic cell can be prepared.
Entirely different with traditional materials processing technology, 3D direct writes are strong with simulation quality, speed is fast, cheap, Gao Yi The advantages that with property is that the subversiveness to traditional manufacture is changed.But as a kind of still immature technology, the section of 3D direct writes It learns technical research to be still in infancy, research and document report in relation to this respect are less, at home there is not yet related text Offer report.Moreover, 3D direct writes marking ink need to be flowed out from fine nozzle without blocking, and can be solidified into rapidly Filament with some strength is used for various moulding；Therefore, 3D direct writes marking ink must be provided simultaneously with shear thinning and glue Elasticity, if elasticity modulus is more than loss modulus.In general, it is 20- in shear rate for the ink of ultra-fine scale printing 200S-1When viscosity be about 10-100PaS.
Ceramic material causes ceramics as one of 3D printing material due to the structure and its keyness of ceramic material The sliding system of material itself is few, and dislocation generates and dyskinesia, is on the other hand exactly the tendency along boundary segregation, this is Row situation so that ceramic material is inherently a kind of fragile material；And the thermoplastic processing and mobility of fragile material are all difficult Therefore control for the 3D printing of ceramic material is compared to metal material, is more difficult to control.China Patent Publication No. is CN104108131A discloses a kind of 3D printing forming method of ceramic material, and this method is by the colloidal sol and pottery of cryogenic freezing characteristic The powders such as porcelain or metal are prepared by mixing into the slurry with freezing gel property, and slurry is injected in the printing of low temperature by print head Freezing, gel solidification on platform, successively printing obtain various types of materials and product.This method raw material preparation process is simple, fast Convenient feature, but freezing state is needed during 3D printing, cost is very high.In addition, 104877463 disclosure of Publication No. A kind of 3D inkjet printings zirconia ceramics ink and preparation method；But the ink is to be used for 3D inkjet printings after all, Solid content is of less demanding, also can not be under 3D direct write states, and effective curing molding is not suitable at all by the ink obtained by this scheme The requirement of 3D direct write inks.Therefore, for a person skilled in the art, it is relatively low how to obtain a kind of manufacturing cost, is suitble to It is still one in 3D direct writes printing ceramic ink and needs the technical barrier solved.
Invention content
In view of the deficiencies of the prior art, the present invention provides one kind being used for the molding zirconia ceramics ink of 3D direct writes, can be It prints, can be still flowed out from fine nozzle while there is higher solid content without blocking, and can at room temperature To be solidified into the filament with some strength rapidly for various moulding, there is good rheological performance.
The present invention provides a kind of zirconia ceramics ink of 3D direct writes, raw material includes zirconia particles, and solvent bonds Agent, dispersant and salt substance；The zirconia particles particle size range is 0.1-2 μm, solid concentration range in the ink For 40-58vol%；The dispersant is polyacrylic acid, acid polyethylene, ammonium polyacrylate, polyethylene hydrochlorate, polyacrylic acid The amount of one or more of salt, polycarboxylate, poly- acetimide, the dispersant is zirconia particles dry powder quality 0.1-2%；The salt substance is ammonium chloride, and zinc acetate, sodium chloride, magnesium chloride, potassium chloride, barium chloride, ammonium hydrogen carbonate is anhydrous Calcium chloride, potassium carbonate, sodium bicarbonate, sodium carbonate, natrium carbonicum calcinatum, anhydrous sodium acetate, anhydrous calcium chloride, copper sulphate, alkali formula carbon Sour copper, ammonium sulfate, ammonium hydrogen carbonate, alum, one or more of sodium citrate, the salt substance are drop mass 0.001-0.1%.
Inventor surprisingly has found that inventor passes through control point by the zirconium oxide ink in-depth study to 3D direct writes While the amount of powder is the 0.1-2% of zirconia particles dry powder quality, salt substance is added can consolidating in zirconium oxide ink Phase content is up in the range of 40-58vol% and under high shear forces, and the viscosity of ink suspension is still very low, ensures suspension Nozzle can be passed through without blocking, and the filament with some strength can be solidified into rapidly for various moulding, still With good rheological performance.In addition, inventor is found through experiments that if the amount of salt substance is more than the 0.1% of drop mass, can send out Raw serious agglomeration, can not prepare the ink of elasticity modulus and viscosity in claimed range.Very due to the solution of the present invention The case where spray nozzle clogging of good solution high solid loading, in the zirconia ceramics powder ink of high solid loading in forming process It can effectively avoid the case where molding structure cracks or deforms caused by contraction in dry and sintering process.
The preferred salt substance of the present invention is the 0.01-0.1% of drop mass.
The amount of presently preferred dispersing agent of the present invention is the 0.1-1.2% of zirconia particles dry powder quality.
The solvent is one or more of in deionized water, absolute ethyl alcohol, polyethylene glycol.
The binder is acrylamide, gelatin, agar, epoxy resin, cellulose, chitosan, gum arabic, fruit One or more of glue.
The binder is the 0.01-25wt% of solvent quality.
By raw material zirconia particles, binder, solvent, dispersant and salt substance, mixing forms slurry, and zirconium oxide mill is added Ball and antifoaming agent, after ball milling, sonic oscillation, you can prepare the zirconia ceramics ink.
Preferred zirconia ceramics ink in this programme, range of solid content 40-56vol%, the solvent are to go Ionized water, the dispersant are one or several in acid polyethylene, polyacrylic acid or ammonium polyacrylate, are zirconia particles The 0.2-1.0% of dry powder quality, the binder are the 0.01-2% of solvent quality；The salt substance is sodium chloride or chlorine It is 0.01-0.1% to change ammonium or zinc acetate, the content for being drop mass,.
The preferred technical solution of the zirconia ceramics ink for 3D direct writes one of the present invention：
Zirconia ceramics ink, range of solid content 40-56vol%, the solvent are deionized water, the dispersion Agent is one or several in acid polyethylene, Sodium Polyacrylate, polycarboxylate sodium or ammonium polyacrylate, is zirconia particles dry powder The 0.2-1.0% of quality, the binder are the 0.01-15% of solvent quality；The salt substance is sodium chloride or chlorination Ammonium or zinc acetate or copper sulphate, the content for being drop mass are 0.01-0.1%,.
The preferred technical solution of the zirconia ceramics ink for 3D direct writes two of the present invention：
It is 0.1-1 μm of zirconia particles by grain size, range of solid content 40-56vol%, solvent is deionized water, is glued Agent cellulose is tied, dispersant is acid polyethylene, and salt substance is that ammonium chloride is mixed to form slurry；In slurry：Zirconium oxide solid concentration Ranging from 40-56vol%, content of cellulose are the 0.002-0.01g/ml of solvent quality, and acid polyethylene is dry for zirconia particles The 0.4-1.2% of powder mass content；Ammonium chloride dosage is the 0.01-0.08% of drop mass.Further, it is also wrapped in this programme The step of acid-base modifier is added into ink is included, adjusting pH range is 7-9.
The sour agent is organic acid or inorganic acid.
The organic acid is formic acid, acetic acid, carboxylic acid, carboxylic acid, hydroxyacetic acid, oxalic acid, hexanedioic acid, succinic acid, benzene first Acid, salicylic acid, one or more of propionic acid, butyric acid, octanoic acid, acrylic acid.
The inorganic acid be hydrochloric acid, nitric acid, sulfuric acid, perchloric acid, hydrofluoric acid, boric acid, phosphoric acid, carbonic acid, chloric acid, mangaic acid, Chlorous acid, nitrous acid, peroxy acid, super oxygen acid, ozone acid, peroxide water, one or more of chloroazotic acid.
The alkaline agent is organic base or inorganic base.
The inorganic base is potassium hydroxide, calcium hydroxide, sodium hydroxide, ammonium hydrogen carbonate, ammonium hydroxide, hydrofluorination ammonium, hydrogen-oxygen Change aluminium, magnesium hydroxide, one or more of barium hydroxide.
The organic base is methylamine, urea (urea), ethamine, ethanol amine, one or more of ethylenediamine.
Further, preferred embodiment of the invention is：It is 0.1- μm of zirconia particles by grain size, solvent is deionization Water, binder, sour agent, alkaline agent, salt substance zinc acetate or copper sulphate, dispersant are poly- acetimide or ammonium polyacrylate or poly- third Olefin(e) acid sodium is mixed to form slurry；In slurry：Zirconium oxide solid concentration ranging from 40-56vol%, binder are solvent quality 0.01-15wt%, dispersant are the 0.4-1.2% of zirconia particles dry powder quality content；Zinc acetate or sulfuric acid copper content are ink The 0.01-0.06% of water quality.
The abrading-ball of zirconium oxide is added in the slurry, zirconium oxide is 1 with zirconium oxide balls mass ratio:(1-2) and defoaming Agent n-octyl alcohol, after 80-120rmp rotating speed ball millings 12-24h, to get the zirconia ceramics of 3D direct writes ink after sonic oscillation 1-12h Water.
The zirconia ceramics ink concrete application of the 3D direct writes is：The zirconia ceramics ink of 3D direct writes is packed into 3D In the spray canister of direct write equipment, nozzle diameter 0.5-400um sets the program of 3D direct write equipment, opens by being successively superimposed Mode print can be obtained three-dimensional structure in air, obtained three-dimensional structure is dried at room temperature for 6-12h After be put at 60 DEG C dry 12-24h and obtain the green compact of three-dimensional structure then as 80 DEG C of dry 12-24h, will then give birth to Base as ordinary sinter stove Program be warming up to 1300-1700 DEG C be sintered three-dimensional structure zirconia ceramic product.
Preferably, the sintering method can be ordinary sinter and microwave sintering, sintering procedure preferably 1 DEG C/min heatings 4h is kept the temperature to 500 DEG C, subsequent 10 DEG C/min is warming up to after 1000 DEG C of heat preservation 1h and is warming up to 1550 DEG C of heat preservation sinterings with phase same rate.
The solution of the present invention can prepare complicated fine minute yardstick three-dimensional structure.In forming process, ink of the invention The tiny cylindric nozzle that water slurry passes through micro/nano level forms the linear fluid of feature, and cures rapidly to keep shape Shape, or even keep its shape not cave in or phenomenon of rupture when molding is containing span or hanging beam (no support) structure.This The suspension ink of invention has following 3 advantages：1) under high shear forces, the viscosity of suspension ink of the invention is very It is low, ensure that suspension can pass through nozzle without blocking；2) cure rapidly when without shear action, and linear after solidification Fluid has preferable elastic property and intensity, and original shape can be kept under no supporting condition；3) suspension of the invention Liquid has solid volume fraction as high as possible, high solid volume fraction to can avoid molding structure in dry and sintering process because receiving Cracking caused by contracting or deformation
The suspension of the present invention is in forming process, and the radial shear stress suffered by the filament of nozzle interior is from center to side Edge linearly increases.Wherein, filament centres are not influenced substantially by shear stress, are in rigid gel state.And filament marginal portion There are larger frictions to generate shear stress with nozzle inner walls, and when the shear stress is more than τ y, filament surfaces viscosity drastically reduces In flow regime.Therefore, the filament in nozzle has rigidity (gel) core-shear flow solid shell structure, which can be well Play the role of keeping forming shape.In addition, the suspension ink of the present invention can smoothly micro-nano-scale be exported from nozzle, avoid Micro-nano-scale spray nozzle clogging caused by pressure filtration phenomenon occurs in suspension, due to there is not press filtration phenomenon, inventor It was found that being to meet to be more than as the shear stress acted on the linear fluid of filament shape needed for the molding ink molding of 3D direct writes Yield shear stress τ y and less than the compressive yield stress py of suspension this relationship.
The ink printed of the present invention is in 20-100S-1Viscosity is 2PaS under shear velocity, is had under direct write state good Rheological property.Ink printed using the present invention, does not need thermoplastic processing, because being near-net-shape, does not need Subsequent machining process, can be with straight forming.Green structure made from the ink printed of the present invention is with three-dimensional periodic The supporting structure aligned.
In addition, the ink printed of the present invention is also applicable to the nozzle that nozzle diameter is 50nm-1mm, the scope of application is very wide It is general.
A kind of 3D direct writes molding of the present invention prepares the application of zirconia ceramics, can be used for preparing various zirconia ceramics Shaped piece and structural member and customed product, including by the zirconia ceramics ink by 3D direct writes be prepared into medical implant and Tissue engineering bracket.
The zirconia ceramics ink that the present invention is developed can be directly used for the printing of 3D direct writes, be printed by 3D direct writes Zirconia ceramics support intensity is big, and porosity and support width can arbitrarily regulate and control, and preparation method is simply easily operated, preparation condition Mildly without particular/special requirement, it is easy to heavy industrialization application, zirconia ceramics ink of the invention compensates for the country and there is no correlation The deficiency of research.
Description of the drawings
Fig. 1 is the molding 8 layers of zirconia ceramics holder of zirconia ceramics ink 3D direct writes in embodiment 1, and nozzle diameter is 160um。
Fig. 2 is the molding 8 layers of zirconia ceramics holder cross-section diagram of zirconia ceramics ink 3D direct writes in embodiment 1.
Fig. 3 is the viscosity data of ceramic ink in embodiment 1, and abscissa is shear rate, and ordinate is viscosity, 10s-1Viscosity under shear velocity is 2Pas.
Fig. 4 is the elasticity modulus of ceramic ink in embodiment 1, and abscissa is concussion stress, and ordinate is elasticity modulus, Elasticity modulus is still up to 10 under 1Pa pressure3Pa。
Fig. 5 is the viscosity data of ceramic ink in embodiment 2, and abscissa is shear rate, and ordinate is viscosity, 10s-1Viscosity under shear velocity is 3Pas.
Fig. 6 is the elasticity modulus of ceramic ink in embodiment 2, and abscissa is concussion stress, and ordinate is elasticity modulus, Elasticity modulus is still up to 10 under 10Pa pressure3Pa。
Fig. 7 is the viscosity data of ceramic ink in embodiment 3, and abscissa is shear rate, and ordinate is viscosity, 10s-1Viscosity under shear velocity is 2Pas.
Fig. 8 is the elasticity modulus of ceramic ink in embodiment 3, and elasticity modulus is still up to 10 under 0.5Pa pressure3Pa。
Fig. 9 is that common slurry is molded zirconia particles deployment conditions comparison diagram in ink with 3D direct writes, wherein figure a is common The zirconia particles deployment conditions of slurry, for mutual independent dispersion in solvent, figure b is in this ink to zirconia particles to each other Grain deployment conditions, particle connects to each other to be formed network structure and is scattered in solvent.
Specific implementation mode
Embodiment 1
By zirconia particles (preferable particle size D50=0.8um), deionized water, cellulose, acid polyethylene, ammonium chloride mixing shape At slurry；Zirconium oxide solid concentration is 44%, content of cellulose 0.002g/ml, and acid polyethylene is that zirconia particles dry powder contains Amount 0.6%, ammonium chloride dosage be drop mass 0.06%, above-mentioned material is mixed in proportion be placed on ball mill with 90rmp rotating speed ball milling 12h have extraordinary shear thinning to get zirconia ceramics ink, the zirconia ceramics ink, In 10s-1Viscosity under shear velocity is 2Pas, and has extraordinary viscoplasticity, is up in 1pa elasticity modulus 103Pa has good conformality, can pass through needle mouth and block and keep three-dimensional shape, then be packed into the ink In the spray canister of 3D direct write equipment, nozzle diameter 100um sets the program of 3D direct write equipment, opens by being successively superimposed Mode prints can be obtained three-dimensional structure in air, is put in after obtained three-dimensional structure is dried at room temperature for 6h Dry 12h obtains the green compact of three-dimensional structure then as 80 DEG C of dry 12h at 60 DEG C, then burns green compact as common 500 DEG C being warming up to 1 DEG C/min in freezing of a furnace and keeping the temperature 4h, subsequent 10 DEG C/min is warming up to after 1000 DEG C of heat preservation 1h with phase same rate liter Temperature obtains the zirconia ceramic product of three-dimensional structure to 1550 DEG C of heat preservation sinterings.(referring to Fig. 1-4)
Embodiment 2
By 1 μm of zirconia particles, deionized water, zinc acetate, glycolylurea epoxide resin, ammonium polyacrylate；In slurry：Zirconium oxide Solid concentration ranging from 56vol%, the glycolylurea epoxide resin of content 15wt%, ammonium polyacrylate are zirconia particles dry powder content 0.8%, zinc acetate dosage be drop mass 0.05%, above-mentioned material is mixed in proportion be placed on ball mill with 100-140rmp rotating speed ball milling 12-24h, are removed, up to the zirconia ceramics ink of 3D direct writes after sonic oscillation 1-12h.Its 10s-1Viscosity under shear velocity is 3Pas, and has extraordinary viscoplasticity, is up in 10pa elasticity modulus 103Pa has good conformality, can pass through needle mouth and block and keep three-dimensional shape, (referring to Fig. 5-6)
The zirconia ceramics ink of the 3D direct writes is fitted into the spray canister of 3D direct write equipment, nozzle diameter 2um, setting The program of good 3D direct write equipment, printing can be obtained three-dimensional structure in air by way of being successively superimposed for unlatching, will Obtained three-dimensional structure is put at 60 DEG C dry 12-24h after being dried at room temperature for 6-12h, then as 80 DEG C of dry 12- For 24 hours, the green compact of three-dimensional structure are obtained, then by green compact as ordinary sinter stove Program be warming up to 1400 DEG C be sintered three Tie up the zirconia ceramic product of stereochemical structure.
Embodiment 3
By 0.5 μm of zirconia particles, deionized water, gum arabic, polycarboxylate sodium, sodium chloride is mixed to be uniformly mixed, oxygen Change zirconium solid concentration ranging from 40vol%, gum arabic content is 0.08g/ml, and polycarboxylate sodium is zirconia particles dry powder The 1% of content, sodium chloride dosage be drop mass 0.1%, above-mentioned material is mixed in proportion be placed on ball mill with 100-140rmp rotating speed ball milling 12-24h, are removed, up to the zirconia ceramics ink of 3D direct writes after sonic oscillation 1-12h.Its 10s-1Viscosity under shear velocity is 2Pas, and has extraordinary viscoplasticity, is up in 0.5pa elasticity modulus 103Pa has good conformality, can pass through needle mouth and block and keep three-dimensional shape, (referring to Fig. 7-8)
The zirconia ceramics ink of the 3D direct writes is fitted into the spray canister of 3D direct write equipment, nozzle diameter 10um, if The program of 3D direct write equipment has been set, printing can be obtained three-dimensional structure in air by way of being successively superimposed for unlatching, Obtained three-dimensional structure is dried at room temperature for being put at 60 DEG C dry 12-24h after 6-12h, then as 80 DEG C of dryings 12-24h obtains the green compact of three-dimensional structure, and green compact are then warming up to 1500 DEG C of sintering as ordinary sinter stove Program Obtain the zirconia ceramic product of three-dimensional structure.
Embodiment 4
By zirconia particles (preferable particle size D50=0.8um), deionized water, pectin, Sodium Polyacrylate, copper sulphate, soda acid Conditioning agent is mixed to form slurry；Zirconium oxide solid concentration is 40%, and pectin content 0.02g/ml, Sodium Polyacrylate is zirconium oxide The 0.6% of particle dry powder content, copper sulphate dosage are the 0.06% of drop mass, and sour dosage is sulfuric acid, and dosage is drop mass 0.05%, alkaline agent is sodium hydroxide, and dosage is the 0.01% of drop mass；Above-mentioned material is mixed in proportion and is placed on ball With 90rmp rotating speed ball milling 12h to get zirconia ceramics ink on grinding machine, which has extraordinary shearing Dilute property and viscoplasticity are caused, there is good conformality, needle mouth can be passed through and block and keep three-dimensional shape, it then should Ink is fitted into the spray canister of 3D direct write equipment, nozzle diameter 100um, sets the program of 3D direct write equipment, open by by The mode that stacking adds prints in air can be obtained three-dimensional structure, and obtained three-dimensional structure is dried at room temperature for It is put at 60 DEG C dry 12h after 6h and obtains the green compact of three-dimensional structure, then extremely by green compact then as 80 DEG C of dry 12h 500 DEG C being warming up to 1 DEG C/min in ordinary sinter stove and keeping the temperature 4h, subsequent 10 DEG C/min is warming up to after 1000 DEG C of heat preservation 1h with phase Same rate is warming up to the zirconia ceramic product that 1550 DEG C of heat preservation sinterings obtain three-dimensional structure.
Comparative example 1
By zirconia particles (preferable particle size D50=0.8um), deionized water, cellulose, polyethylene carboxylic acid, ammonium chloride, acid Alkali conditioning agent is mixed to form slurry；Zirconium oxide solid concentration is 44%, content of cellulose 0.002g/ml, and polyethylene carboxylic acid is The 0.6% of dry powder content, ammonium chloride dosage are 0.2%, and above-mentioned material is mixed in proportion and is placed on ball mill with 90rmp Rotating speed ball milling 12h has found that pulp particle is reunited seriously, can not be uniformly mixed that ink preparation process fails.
Comparative example 2
By zirconia particles (preferable particle size D50=0.8um), deionized water, cellulose, polyethylene carboxylic acid, acid-base modifier It is mixed to form slurry；Zirconium oxide solid concentration is 50%, content of cellulose 0.006g/ml, and polyethylene carboxylic acid is dry powder content 0.6%, salt substance is not added, above-mentioned material is mixed in proportion and is placed on ball mill with 90rmp rotating speed ball millings 12h, although it is in flowable state that pulp particle is well dispersed, particle do not form network, be completely dispersed but can not effectively direct write at Type, the failure of 3D structure preparation process.

Claims (10)

  1. The zirconia ceramics ink of 1.3D direct writes, which is characterized in that raw material includes zirconia particles, solvent, binder, dispersant With salt substance；The zirconia particles particle size range is 0.1-2 μm, solid concentration ranging from 40- in the ink 58vol%；The dispersant is polyacrylic acid, acid polyethylene, ammonium polyacrylate, polyethylene hydrochlorate, polyacrylate, poly- carboxylic One or more of hydrochlorate, poly- acetimide, the amount of the dispersant are the 0.1-2% of zirconia particles dry powder quality； The salt substance be ammonium chloride, zinc acetate, sodium chloride, magnesium chloride, potassium chloride, barium chloride, ammonium hydrogen carbonate, anhydrous calcium chloride, Potassium carbonate, sodium bicarbonate, sodium carbonate, natrium carbonicum calcinatum, anhydrous sodium acetate, anhydrous calcium chloride, copper sulphate, basic copper carbonate, sulphur Sour ammonium, ammonium hydrogen carbonate, alum, one or more of sodium citrate, the salt substance are the 0.001- of drop mass 0.1%.
  2. 2. the zirconia ceramics ink of 3D direct writes according to claim 1, which is characterized in that salt substance is drop mass 0.01-0.1%.
  3. 3. the zirconia ceramics ink of 3D direct writes according to claim 1, which is characterized in that the amount of dispersant is zirconium oxide The 0.1-1.2% of particle dry powder quality.
  4. 4. the zirconia ceramics ink of 3D direct writes according to claim 1, which is characterized in that the solvent is deionization It is one or more of in water, absolute ethyl alcohol, polyethylene glycol.
  5. 5. the zirconia ceramics ink of 3D direct writes according to claim 1, which is characterized in that the binder is propylene One or more of amide, gelatin, agar, epoxy resin, cellulose, chitosan, gum arabic, pectin.
  6. 6. the zirconia ceramics ink of 3D direct writes according to claim 1, which is characterized in that the binder is solvent The 0.01-25wt% of quality.
  7. 7. the zirconia ceramics ink of 3D direct writes according to claim 1, which is characterized in that
    Zirconia ceramics ink, range of solid content 40-56vol%, the solvent are deionized water, and the dispersant is One or more of acid polyethylene, Sodium Polyacrylate, polycarboxylate sodium or ammonium polyacrylate are zirconia particles dry powder quality 0.2-1.0%, the binder be solvent quality 0.01-15%；The salt substance be sodium chloride or ammonium chloride or Zinc acetate or copper sulphate, the content for being drop mass are 0.01-0.1%.
  8. 8. the zirconia ceramics ink of 3D direct writes according to claim 1, which is characterized in that by grain size be 0.1-1 μm of oxygen Change zirconium particle, range of solid content 40-56vol%, solvent is deionized water, and binder fiber element, dispersant is polyethylene Acid, salt substance are that ammonium chloride is mixed to form slurry；In slurry：Zirconium oxide solid concentration ranging from 40-56vol%, cellulose contain Amount is the 0.002-0.01g/ml of solvent quality, and acid polyethylene is the 0.4-1.2% of zirconia particles dry powder quality content；Chlorine Change the 0.01-0.08% that ammonium dosage is drop mass.
  9. 9. according to the zirconia ceramics ink of claim 1-8 any one of them 3D direct writes, which is characterized in that add into ink The step of entering acid-base modifier, adjusting pH range are 7-9.
  10. 10. the zirconia ceramics ink of 3D direct writes according to claim 9, which is characterized in that by grain size be 0.1- μm of oxygen Change zirconium particle, solvent is deionized water, binder, sour agent, alkaline agent, salt substance zinc acetate or copper sulphate, and dispersant is poly- acetyl Imines or ammonium polyacrylate or Sodium Polyacrylate are mixed to form slurry；In slurry：Zirconium oxide solid concentration ranging from 40- 56vol%, binder are the 0.01-15wt% of solvent quality, and dispersant is the 0.4- of zirconia particles dry powder quality content 1.2%；Zinc acetate or the 0.01-0.06% that sulfuric acid copper content is drop mass.
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CN110756804A (en) * 2019-10-30 2020-02-07 南方科技大学 3D printing method of metal material
CN111848141A (en) * 2020-07-24 2020-10-30 江苏师范大学 Preparation method of ceramic paste for 3D printing by direct-writing forming of slurry
CN112548114A (en) * 2020-11-09 2021-03-26 季华实验室 Method for directly printing metal part by adopting ink
CN112704767A (en) * 2021-02-05 2021-04-27 中南大学湘雅医院 Personalized customized bone organ manufactured accurately in 4D mode and preparation method thereof
CN112870450A (en) * 2021-01-28 2021-06-01 中南大学湘雅医院 Metformin-loaded artificial bone material and method for preparing artificial bone
CN112891620A (en) * 2021-01-28 2021-06-04 中南大学湘雅医院 Artificial bone material carrying anti-tumor medicine and method for preparing artificial bone
CN112891621A (en) * 2021-01-28 2021-06-04 中南大学湘雅医院 Artificial bone material carrying anti-osteoporosis medicine and method for preparing artificial bone
CN113476649A (en) * 2020-03-17 2021-10-08 中南大学湘雅医院 Hydroxyapatite bone-imitating material and preparation method thereof
CN113546614A (en) * 2020-04-16 2021-10-26 中国石油天然气股份有限公司 Catalyst alumina carrier material with gradient micro-morphology structure and preparation method thereof
CN115432998A (en) * 2021-06-03 2022-12-06 中国科学院上海硅酸盐研究所 Preparation method of transparent ceramic slurry for direct writing
CN115448734A (en) * 2022-10-21 2022-12-09 江南大学 3D printing ceramic composite material and preparation method and application thereof

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CN109111223A (en) * 2018-09-18 2019-01-01 中国科学院宁波材料技术与工程研究所 3D direct write printing titanium dioxide ceramic composition, slurry, preparation method and application
CN109400179A (en) * 2018-11-30 2019-03-01 中南大学 A method of preparing macroscopic view and all controllable material of microstructure
CN110756804A (en) * 2019-10-30 2020-02-07 南方科技大学 3D printing method of metal material
CN110756804B (en) * 2019-10-30 2022-06-14 南方科技大学 3D printing method of metal material
CN113476649A (en) * 2020-03-17 2021-10-08 中南大学湘雅医院 Hydroxyapatite bone-imitating material and preparation method thereof
CN113546614B (en) * 2020-04-16 2023-10-27 中国石油天然气股份有限公司 Catalyst alumina carrier material with gradient microstructure and preparation method thereof
CN113546614A (en) * 2020-04-16 2021-10-26 中国石油天然气股份有限公司 Catalyst alumina carrier material with gradient micro-morphology structure and preparation method thereof
CN111848141A (en) * 2020-07-24 2020-10-30 江苏师范大学 Preparation method of ceramic paste for 3D printing by direct-writing forming of slurry
CN112548114A (en) * 2020-11-09 2021-03-26 季华实验室 Method for directly printing metal part by adopting ink
CN112891621A (en) * 2021-01-28 2021-06-04 中南大学湘雅医院 Artificial bone material carrying anti-osteoporosis medicine and method for preparing artificial bone
CN112891620A (en) * 2021-01-28 2021-06-04 中南大学湘雅医院 Artificial bone material carrying anti-tumor medicine and method for preparing artificial bone
CN112870450A (en) * 2021-01-28 2021-06-01 中南大学湘雅医院 Metformin-loaded artificial bone material and method for preparing artificial bone
CN112704767A (en) * 2021-02-05 2021-04-27 中南大学湘雅医院 Personalized customized bone organ manufactured accurately in 4D mode and preparation method thereof
CN115432998A (en) * 2021-06-03 2022-12-06 中国科学院上海硅酸盐研究所 Preparation method of transparent ceramic slurry for direct writing
CN115448734A (en) * 2022-10-21 2022-12-09 江南大学 3D printing ceramic composite material and preparation method and application thereof

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