CN105384449B - A kind of ceramic ink and preparation method and application - Google Patents

A kind of ceramic ink and preparation method and application Download PDF

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Publication number
CN105384449B
CN105384449B CN201510764977.5A CN201510764977A CN105384449B CN 105384449 B CN105384449 B CN 105384449B CN 201510764977 A CN201510764977 A CN 201510764977A CN 105384449 B CN105384449 B CN 105384449B
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ceramic
ink
ceramic ink
dispersant
powder
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CN105384449A (en
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肖建中
徐坦
田思宇
刘璐
刘文燕
李向东
王超
王兵
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Huazhong University of Science and Technology
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Huazhong University of Science and Technology
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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
    • 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
    • C04B35/62605—Treating the starting powders individually or as mixtures
    • C04B35/62625—Wet mixtures
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K6/00—Preparations for dentistry
    • A61K6/80—Preparations for artificial teeth, for filling teeth or for capping teeth
    • A61K6/802—Preparations for artificial teeth, for filling teeth or for capping teeth comprising ceramics
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K6/00—Preparations for dentistry
    • A61K6/80—Preparations for artificial teeth, for filling teeth or for capping teeth
    • A61K6/802—Preparations for artificial teeth, for filling teeth or for capping teeth comprising ceramics
    • A61K6/818—Preparations for artificial teeth, for filling teeth or for capping teeth comprising ceramics comprising zirconium oxide
    • 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
    • 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
    • C04B35/10—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 aluminium oxide
    • C04B35/111—Fine ceramics
    • 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
    • C04B35/10—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 aluminium oxide
    • C04B35/111—Fine ceramics
    • C04B35/117—Composites
    • C04B35/119—Composites with zirconium oxide
    • 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
    • C04B35/486—Fine ceramics
    • 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
    • C04B35/486—Fine ceramics
    • C04B35/488—Composites
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626—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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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance

Abstract

The invention discloses a kind of ceramic ink, including the ceramic powder that mass fraction is 57%~70%, 1%~5% dispersant, 8%~30% glycerine, 8%~35% water and 5%~20% organic solvent；The pH value of the ceramic ink is 8~12, and the dispersant is 1 by mass ratio:5~5:1 ammonium polyacrylate and polyvinylpyrrolidone composition.The invention also discloses the preparation method of the ceramic ink and the application in the inkjet printing of artificial tooth.The present invention improves the dispersiveness and stability of ink of ceramic ink by binary dispersant, and then the solid concentration of ceramic ink is improved to 20vol.%~40vol.%, so as to go out the ceramics such as artificial tooth using the direct inkjet printing of the ceramic ink, and ceramic relative density is more than 98%.

Description

A kind of ceramic ink and preparation method and application
Technical field
The invention belongs to rapid three dimensional printing forming field, more particularly, to a kind of ceramic ink and preparation method thereof With application.
Background technology
Direct inkjet printing shaping belongs to a kind of rapid three dimensional printing forming method, and stock utilization is high, is formed without mould Tool, the manufacturing cycle is shortened, manufacture efficiency is high, and cost is low, and the droplet size of particularly direct inkjet printing shaping injection is skin Rise (10-12L) rank, thus printed product form accuracy is high, without post processing.The viscosity of ink-jet printing ink typically requires small In 30cP, and for ceramic ink jet printing ink, that is, need to ensure its low viscosity to meet the requirement of inkjet printing, again It is required that there is high solid content to obtain high sintered density, therefore, the direct inkjet printing of ceramic such as artificial tooth at present Shaping is limited to the preparation of ceramic ink, and there has been no the ceramic ink that can conform to requirement.
The performance of ceramic ink jet printing ink depends mainly on the dispersiveness and its suspension stability of ceramic phase (solid phase), and one As more high then its stably dispersing of solid concentration it is more difficult, and ink viscosity is bigger.Scientific worker has carried out numerous studies work, Wang Ruigang, as dispersant, is matched somebody with somebody from sodium pyrophosphate, polyethylene glycol, ammonium polyacrylate, sodium alginate using Orthogonal Experiment and Design Oxygenerating zircon ceramic ink, by the result of settling test, it is prepared for the zirconia ceramics ink that solid concentration is 2vol.% and reaches To the process conditions of fine dispersion.Fourth Hunan is attempted using sodium alginate or polyacrylic acid 3000 as dispersant, has prepared maximum Solid concentration is 15vol.% zirconia ceramics ink, still, because its solid concentration is relatively low, it is difficult to obtains height by sintering The ceramic of density.
The content of the invention
For the disadvantages described above or Improvement requirement of prior art, the invention provides a kind of ceramic ink for inkjet printing Water, its object is to by optimizing the proportioning of composition and the formula of dispersant, so as to improve the solid concentration of ceramic ink, from And increase the firmware intensity of inkjet printing shaping, to meet the needs of ceramics such as artificial tooth.
To achieve the above object, the invention provides a kind of ceramic ink, including the pottery that mass fraction is 57%~70% Porcelain powder, 1%~5% dispersant, 8%~30% glycerine, 8%~35% water and 5%~20% organic solvent；Institute The pH value for stating ceramic ink is 8~12, and the dispersant is 1 by mass ratio:5~5:1 ammonium polyacrylate and polyvinyl pyrrole Alkanone forms.
Preferably, the ceramic powder is zirconia ceramics powder, yttrium stable zirconium oxide ceramic powder, aluminium oxide ceramics powder or oxidation One or more in zirconium reinforced alumina ceramic powder.
Preferably, the water-soluble defrother is in n-butanol, n-octyl alcohol, tributyl phosphate, hexadecanol, the ester of tricresyl phosphate ten One or more.
Preferably, the pH value of the ceramic ink is 9~11.
Preferably, the organic solvent is ethanol, isopropanol, cyclohexyl pyrrolidone, acetone, cyclohexanone, ethyl acetate With the one or more in butyl acetate,
Preferably, the ceramic ink also includes the binding agent and 0.2%~1% that mass fraction is 0.1%~2% Water-soluble defrother, the binding agent are in polyvinyl alcohol, polyethylene glycol, Ludox, polyvinyl butyral resin and acrylate One or more.
Preferably, the mass fraction of the glycerine is 10%~20%.
Preferably, the mass fraction of the dispersant is 2%~4%, and the dispersant is 1 by mass ratio:2~2:1 Ammonium polyacrylate and polyvinylpyrrolidone composition.
Another aspect of the present invention additionally provides a kind of preparation method of the ceramic ink, comprises the following steps：
(1) according to quality proportioning, 100 parts of ceramic powders, 11 parts~50 parts water and 11 parts~50 parts glycerine, mixing are turned into Mixed slurry, 1.4 parts~9 parts dispersants are then added into the mixed slurry and are well mixed；The particle diameter of the ceramic powder is small In 1000nm, the dispersant is 1 by mass ratio:5~5:1 ammonium polyacrylate and polyvinylpyrrolidone composition；
(2) to step (1) obtain mixed slurry in add 0.3 part~2 parts water-soluble defrothers, and with 100rpm~ 300rpm rotating speed ball milling makes the component in mixed slurry be uniformly dispersed；
(3) 7 parts~35 parts organic solvents are added to the mixed slurry that step (2) obtains, and pH is adjusted with acid-base modifier It is worth for 8~12, obtains the ceramic ink.
Preferably, the step (2) is：0.3 part~2 parts water solubilitys are added in the mixed slurry obtained to step (1) to remove Infusion and 0.15 part~3.5 parts of binding agent, and make with 100rpm~300rpm rotating speed ball milling the component in mixed slurry It is uniformly dispersed；
Preferably, acid-base modifier is in ammoniacal liquor, dimethylamine, triethanolamine, hydrochloric acid and sulfate in the step (3) One or more.
Preferably, the ceramic ink is used to 3 μm~10 μm of bore filter again, with removing after the step (3) Insoluble solid particle in ink, the ceramic ink after being filtered.
It is another aspect of this invention to provide that a kind of ceramic ink is additionally provided applied to the inkjet printing of ceramic Method.
Preferably, the ceramic is artificial tooth, and this method comprises the following steps that：
(1) by the oral cavity data of patient, the threedimensional model of artificial tooth needed for foundation；
(2) by after the model conversion file format in step (1), three-dimensional inkjet printer fabrication schedule is imported；
(3) the ceramic ink printing shaping artificial tooth biscuit is utilized；
(4) by the artificial tooth biscuit drying, degreasing, sintering.
In general, by the contemplated above technical scheme of the present invention compared with prior art, due to optimizing ceramics The formula of composition and dispersant used in ink, can obtain following beneficial effect：
1st, the mixture that have chosen ammonium polyacrylate and polyvinylpyrrolidone is inhaled as dispersant, polyvinylpyrrolidone While investing ceramic grain surface, it is connected with ammonium polyacrylate by hydrogen bond, adds the steric hindrance between ceramic particle Effect, prevents ceramic particle from reuniting so that the ceramic ink stability and dispersiveness prepared is more preferable；
2nd, glycerine is added in ceramic ink as wetting agent, wetting nozzle is not only contributed to, improves the printing stream of ink Smooth performance, while glycerol molecule can be connected with hydrogen bond with ceramic powder, so as to further increase the steric hindrance of ceramic particle, be carried The stability of high ceramic ink；
3rd, in the ceramic ink prepared, the mass fraction of ceramic powder has reached 57%~70% and (contained equivalent to solid phase Measure as 20vol.%~40vol.%), it is adapted to direct inkjet printing shaping, the raising of solid concentration, is advantageous to satisfaction and is printed as Intensity and the consistency requirement of type product, so as to meet the needs of artificial tooth inkjet printing；
4th, the ceramic powder raw material average grain diameter selected is less than 1000nm；And disperse the component in ceramic ink using ball milling Uniformly, the average grain diameter of ceramic powder further reduces, and is advantageous to improve the dispersion stabilization and printing fluency of ceramic ink；
5th, can be prepared using the ceramic ink without the ceramic such as mould, direct inkjet printing shaping artificial tooth Artificial tooth product precision it is high, good compactness.
Embodiment
In order to make the purpose , technical scheme and advantage of the present invention be clearer, with reference to embodiments, to the present invention It is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, it is not used to Limit the present invention.As long as in addition, technical characteristic involved in each embodiment of invention described below each other it Between do not form conflict can be mutually combined.
The ceramic ink that one aspect of the present invention provides has following components：Mass fraction is 57%~70% ceramics Powder, 1%~5% dispersant, 8%~30% glycerine, 8%~35% water and 5%~20% organic solvent；It is described The pH value of ceramic ink is 8~12, and the dispersant is 1 by mass ratio:5~5:1 ammonium polyacrylate and polyvinylpyrrolidine Ketone forms, and the particle diameter of the ceramic powder is less than 1000nm.
Wherein, ceramic powder is preferably zirconia ceramics powder, yttrium stable zirconium oxide ceramic powder, aluminium oxide ceramics powder or zirconium oxide One or more in reinforced alumina ceramic powder, for the main component of the artificial tooth in inkjet printing shaping；Water-soluble defrother One or more preferably in n-butanol, n-octyl alcohol, tributyl phosphate, hexadecanol, the ester of tricresyl phosphate ten；Organic solvent is ceramics Commonly use the liquid flux such as alcohol, ketone or ester in ink, preferably ethanol, isopropanol, cyclohexyl pyrrolidone, acetone, cyclohexanone, One or more in ethyl acetate and butyl acetate, add and be used to prevent shower nozzle from blocking in ceramic ink, and accelerate system The drying of product；The ceramic ink can also include the binding agent and 0.2%~1% water that mass fraction is 0.1%~2% Dissolubility defrother, the binding agent are preferably polyvinyl alcohol, polyethylene glycol, Ludox, polyvinyl butyral resin and acrylate In one or more, for strengthening the cohesive force between ceramic powder, so as to improve the mechanical strength of artificial tooth product；Glycerine is used for Wetting nozzle, improves the printing smoothness performance of ink, while improves the stability of ceramic ink, and its preferred mass proportioning is 10% ~20%；Dispersant is used to be adsorbed in ceramic powder surface, so as to increase the effect of the steric hindrance of ceramic particle, improves ceramic ink Dispersiveness, dispersant preferably by mass ratio be 1:2~2:1 ammonium polyacrylate and polyvinylpyrrolidone composition, its is preferred Mass fraction be 2%~4%.
The preparation method of the ceramic ink comprises the following steps：
(1) according to quality proportioning, 100 parts of ceramic powders, 11 parts~50 parts water and 11 parts~50 parts glycerine, mixing are turned into Mixed slurry, 1.4 parts~9 parts dispersants are then added into the mixed slurry and are well mixed；The particle diameter of the ceramic powder is small In 1000nm, the dispersant is 1 by mass ratio:5~5:1 ammonium polyacrylate and polyvinylpyrrolidone composition；It is wherein poly- Ammonium acrylate is anionic dispersing agent, and polyvinylpyrrolidone is non-ionic dispersing agent；
(2) 0.3 part~2 parts water-soluble defrothers and 0 part~3.5 parts of binding agent are added in mixed slurry again, and It is allowed to be uniformly dispersed with 100rpm~300rpm speed ball milling, because dispersant also has bond effect in itself, so can also It is added without binding agent；Ball-milling Time is related to ball milling speed to inventory, preferably 8h~30h, and the ratio of grinding media to material of ball milling is 2:1~ 5:1。
(3) 7 parts~35 parts organic solvents are added to the mixed slurry that step (2) obtains, and is adjusted and mixed with acid-base modifier The pH value for closing slurry is 8~12 (being preferably 9~11) so that mixed slurry keeps its stability in the basic conditions, obtains institute State ceramic ink；Acid-base modifier is preferably the one or more in ammoniacal liquor, dimethylamine, triethanolamine, hydrochloric acid and sulfate, More preferably ammoniacal liquor and hydrochloric acid.
Wherein, after the step (3), mixed slurry can also be filtered, to remove 3 μm~more than 10 μm insoluble Property solid.
It is applied to the method for the inkjet printing of the ceramics such as artificial tooth present invention also offers the ceramic ink, including it is following Step：
(1) threedimensional model of ceramic is established；
(2) model layers are cut into slices, is converted into STL forms, import three-dimensional inkjet printer fabrication schedule；
(3) ceramic ink is injected into print cartridge, printing shaping artificial tooth biscuit；
(4) by the drying of artificial tooth biscuit, degreasing, sintering, ceramic is obtained.
Herein below is embodiment：
Embodiment 1
(1) 3YSZ ceramic powders (yttrium stable zirconium oxide ceramic powders) 242g, deionized water 80g, glycerine 63g is weighed, is fallen Enter beaker, mix, stir；Then the dispersant for adding 4.84g thereto (is 1 by mass ratio:1 ammonium polyacrylate and Polyvinylpyrrolidone forms)；
(2) 1.21g polyvinyl alcohol is added into beaker to stir, obtain as defrother as binding agent, 2g n-octyl alcohols To slurry；Then slurry is poured into ball grinder, adds zirconium oxide ball milling pearl, 250rpm planetary ball mills 24h；
(3) 20g ethanol is added into ceramic slurry as organic solvent, stirs, adds 5g ammoniacal liquor (traditional Chinese medicines, NH4OH Mass fraction be 26% ± 2%) regulation pH be 10；
(4) slurry is filtered by 5 μm of spray drawing machine butterfly filter, stable ceramic ink is obtained, by ceramic ink Pour into suspension bottle, room temperature standstill seal preserves.
This 3YSZ ceramic inks solid concentration (volume fraction of ceramic powder) 20vol.%, viscosity at ambient temperature 23cP, except ceramics The gross mass of other components is about 176g beyond powder：Its reclaimed water 84g, glycerine 63g, the common 4.84g of dispersant, defrother n-butanol 2g, polyvinyl alcohol 1.21g, ethanol 20g, NH4OH 1g。
Embodiment 2
(1) aluminium oxide ceramics powder 200g, glycerine 60g, deionized water 60g are weighed respectively, pours into beaker, is mixed, and stirring is equal Even, the dispersant for then adding 7g thereto (is 3 by mass ratio:4 ammonium polyacrylate and polyvinylpyrrolidone composition)；
(2) 4g polyvinyl alcohol is added into beaker to stir, obtain as defrother as binding agent, 2g n-octyl alcohols Slurry；Then slurry is poured into ball grinder, adds aluminum oxide ball milling pearl, 300rpm planetary ball mills 16h；
(3) 20g ethanol is added into ceramic slurry as organic solvent, stirs, adds 4g dimethylamine solution (diformazans The mass fraction of amine is 10 40%) to adjust pH；
(4) slurry is filtered by 10 μm of spray drawing machine butterfly filter, stable ceramic ink is obtained, by ceramic ink Pour into suspension bottle, room temperature standstill seal preserves.
This aluminium oxide ceramics ink solid concentration (volume fraction of ceramic powder) 25vol.%, viscosity 36cP, except ceramic powder In addition, the gross mass of other components is about 187g in addition to ceramic powders：Deionized water 62g, glycerine 60g, the common 7g of dispersant, are removed Infusion n-butanol 2g, polyethylene glycol 4g, ethanol 25g, diformazan ammonia 2g.
Embodiment 3
Embodiment 2 is repeated with described same steps, difference is, the quality of deionized water is 100g, the quality of glycerine For 100g, dispersant is made up of 6g ammonium polyacrylate and 3g polyvinylpyrrolidone, regulation pH value in the step (4) For 11.
Embodiment 4
(1) 3YSZ ceramic powders 200g are weighed, deionized water 22g, glycerine 22g, pour into beaker, mixes, stirs；So The dispersant for adding 2.8g thereto afterwards (is 1 by mass ratio:5 ammonium polyacrylate and polyvinylpyrrolidone composition)；
(2) 0.6g tributyl phosphates are added into beaker as defrother, stirs, obtains slurry；Then by slurry Ball grinder is poured into, adds zirconium oxide ball milling pearl, 100rpm planetary ball mills 30h (ratios of grinding media to material 5:1)；
(3) 70g cyclohexanone is added into ceramic slurry as organic solvent, stirs, pH is adjusted with dimethylamine solution For 10；Ceramic slurry is not filtered and directly poured into suspension bottle, room temperature standstill seal preserves.
Embodiment 5
(1) zirconia ceramics powder 200g is weighed, deionized water 85g, glycerine 36g, pours into beaker, mixes, stirs； Then the dispersant for adding 18g thereto (is 5 by mass ratio:1 ammonium polyacrylate and polyvinylpyrrolidone composition), magnetic force 10min is stirred, it is preliminary scattered；
(2) 4g tributyl phosphates are added into beaker as defrother and 0.36g acrylate as binding agent, stirring Uniformly, slurry is obtained；Then the slurry system prepared is poured into ball grinder, adds zirconium oxide ball milling pearl, 300rpm planetary ball mills 6h (ratios of grinding media to material 2:1)；
(3) 14g cyclohexanone is added into ceramic slurry as organic solvent, stirs, is adjusted with triethanolamine and hydrochloric acid It is 12 to save pH；Ceramic slurry is not filtered and directly poured into suspension bottle, room temperature standstill seal preserves.
Embodiment 6
(1) zirconia ceramics powder 200g is weighed, deionized water 30g, glycerine 80g, pours into beaker, mixes, stirs； Then the dispersant for adding 8g thereto (is 1 by mass ratio:2 ammonium polyacrylate and polyvinylpyrrolidone composition), magnetic force 10min is stirred, it is preliminary scattered；
(2) it is equal as binding agent, stirring as defrother and 8g acrylate that 2g tributyl phosphates are added into beaker It is even, obtain slurry；Then the slurry system prepared is poured into ball grinder, adds zirconium oxide ball milling pearl, 250rpm planetary ball mills 16h (ratio of grinding media to material 3:1)；
(3) 70g cyclohexanone is added into ceramic slurry as organic solvent, is stirred, to adjust the property of ceramic slurry Can, it is 9 with ammoniacal liquor and salt acid for adjusting pH；Ceramic slurry is not filtered and directly poured into suspension bottle, room temperature standstill seal preserves.
Embodiment 7
(1) alumina ceramic powder 320g is weighed, deionized water 50g, glycerine 40g, pours into beaker, mixes, stirs； Then the dispersant for adding 4.8g thereto (is 2 by mass ratio:1 ammonium polyacrylate and polyvinylpyrrolidone composition), magnetic Power stirs 10min, preliminary scattered；
(2) polyethylene glycol 3.2g and polyvinyl alcohol 1.6g is added into beaker as binding agent, addition 3.2g octanol conducts Defrother, stir, obtain slurry；Then slurry pours into ball grinder, adds zirconium oxide ball milling pearl, 250rpm planetary ball mills (ratio of grinding media to material 3 after 20h:1)；
(3) 30g butanone is added into ceramic slurry as organic solvent, stirs, adds triethanolamine 4g regulation potteries The pH of ceramic ink water is 9；Ceramic slurry is not filtered and directly poured into suspension bottle, room temperature standstill seal preserves.
This aluminium oxide ceramics ink solid concentration 40vol.% (equivalent to mass fraction 70%), viscosity 50cP, except ceramics The gross mass of other components is about 136.8g beyond powder：Including deionized water 50g, glycerine 40g, the common 4.8g of dispersant, Defrother octanol 3.2g, triethanolamine 4g, polyethylene glycol 3.2g, polyvinyl alcohol 1.6g, butanone 30g.
Embodiment 8
By aluminium oxide ceramics ink in 3YSZ ceramic inks in example 1 and example 2 by mass percentage 2：3 is well mixed, Hybrid ceramic ink is made, ceramic ink is poured into suspension bottle, room temperature standstill seal preserves.
This ink 324.4g is taken, including 3YSZ ceramic powder 96.8g, aluminium oxide ceramics powder 60g, deionized water 70.4g, Glycerine 61.2g, the common 6.1g of dispersant, defrother n-butanol 2g, polyethylene glycol 2.4g, polyvinyl alcohol 0.5g, ethanol 23g, NH4OH1g, diformazan ammonia 1g, the solid concentration of this ink is 23vol.% (equivalent to mass fraction 48%), viscosity 30cP.
Embodiment 9
The composition of ceramic ink to being prepared in embodiment 1- embodiments 8 is analyzed, wherein the quality of ceramic powder Fraction is 57%~70%, and solid concentration is 20vol.%~40vol.%, and the mass fraction of dispersant is 1%~5%, water-soluble Property defrother mass fraction be 0.2%~1%, the mass fraction of binding agent is 0%~2%, and the mass fraction of glycerine is 8% ~30%, the mass fraction of water is 8%~35%, and the mass fraction of organic solvent is 5%~20%.
The step of using above-mentioned ceramic ink inkjet printing artificial tooth, is as follows：
(1) oral cavity data are gathered, establish the threedimensional model of artificial tooth；
(2) model layers are cut into slices, is converted into STL forms, import three-dimensional inkjet printer fabrication schedule；
(3) ceramic ink is injected into print cartridge, printing shaping artificial tooth biscuit；
(4) by the drying of artificial tooth biscuit, degreasing, sintering, artificial tooth is obtained.
Wherein, the justice being prepared using the ceramic ink of embodiment 1, embodiment 2 and embodiment 9 by above step Tooth, test consistency have respectively reached 99.1%, 96.3% and the 97.8% of theoretical value.Prepared with embodiment 1- embodiments 9 Obtained other ceramics also have similar effect.
As it will be easily appreciated by one skilled in the art that the foregoing is merely illustrative of the preferred embodiments of the present invention, not to The limitation present invention, all any modification, equivalent and improvement made within the spirit and principles of the invention etc., all should be included Within protection scope of the present invention.

Claims (7)

  1. A kind of 1. ceramic ink, it is characterised in that including the ceramic powder that mass fraction is 57%~70%, 1%~5% it is scattered Agent, 8%~30% glycerine, 8%~35% water and 5%~20% organic solvent；The pH value of the ceramic ink is 8 ~12, the dispersant is 1 by mass ratio:5~5:1 ammonium polyacrylate and polyvinylpyrrolidone composition.
  2. 2. ceramic ink as claimed in claim 1, it is characterised in that the ceramic powder is zirconia ceramics powder, yttrium Stable Oxygen Change the one or more in zircon ceramic powder, aluminium oxide ceramics powder or Zirconia reinforced alumina ceramic powder.
  3. 3. ceramic ink as claimed in claim 1, it is characterised in that the pH value of the ceramic ink is 9~11.
  4. 4. ceramic ink as claimed in claim 1, it is characterised in that the organic solvent is ethanol, isopropanol, cyclohexyl pyrrole One or more in pyrrolidone, acetone, cyclohexanone, ethyl acetate and butyl acetate.
  5. 5. ceramic ink as claimed in claim 1, it is characterised in that also including mass fraction be 0.1%~2% binding agent And 0.2%~1% water-soluble defrother, the binding agent be polyvinyl alcohol, polyethylene glycol, Ludox, polyvinyl alcohol contracting One or more in butyraldehyde and acrylate, the water-soluble defrother are n-butanol, n-octyl alcohol, tributyl phosphate, 16 One or more in alcohol, the ester of tricresyl phosphate ten.
  6. 6. ceramic ink as claimed in claim 1, it is characterised in that the mass fraction of the dispersant is 2%~4%, institute It is 1 that dispersant, which is stated, by mass ratio:2~2:1 ammonium polyacrylate and polyvinylpyrrolidone composition.
  7. 7. the ceramic ink as described in any one in claim 1-6 is applied to the inkjet printing of ceramic.
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CN106045503A (en) * 2016-05-27 2016-10-26 北京科技大学 Oral porcelain tooth 3D gel printing preparation method
CN108456456B (en) * 2016-12-12 2021-06-22 中南大学 3D direct-writing zirconia colloidal ink
CN108610044B (en) * 2016-12-12 2021-06-25 中南大学 Zirconia ink for 3D direct writing
CN108456457B (en) * 2016-12-12 2021-06-18 中南大学 3D direct-writing zirconia ceramic ink
WO2019051748A1 (en) * 2017-09-14 2019-03-21 熊建平 Method for preparing cobalt blue ceramic glaze ink
CN108249890B (en) * 2018-01-17 2021-03-30 龙泉市金宏瓷业有限公司 High-density 3D printing ceramic material and preparation method thereof
ES2906273T3 (en) * 2018-11-29 2022-04-18 Ivoclar Vivadent Ag Procedure and use of slip for the manufacture of ceramic molded bodies from zirconium oxide by 3D inkjet printing
CN112390651A (en) * 2020-11-16 2021-02-23 中国工程物理研究院材料研究所 AlN ceramic powder preparation method based on 3D printing molding
CN113429831B (en) * 2021-07-31 2023-03-14 石河子大学 Method for preparing water-based zirconia ceramic ink for ink-jet printing by using microreactor
CN114836076A (en) * 2022-06-13 2022-08-02 广西碧清源环保投资有限公司 Ink-jet printing ink and preparation method and application thereof

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CN102350236A (en) * 2011-07-11 2012-02-15 北京纳辰科技发展有限责任公司 Nano zirconia alcohol slurry and preparation method thereof
CN103509409A (en) * 2012-06-18 2014-01-15 苏州忠辉蜂窝陶瓷有限公司 Preparation method of ceramic ink used in ink jet printer
CN103224727B (en) * 2013-04-08 2014-12-24 佛山市道氏科技有限公司 Eco-friendly glaze ink for ceramic jet printing and preparation method thereof

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