CN106699137A - Method for preparing ZTA multi-phase ceramic through 3D printing based on stereo lithography appearance - Google Patents
Method for preparing ZTA multi-phase ceramic through 3D printing based on stereo lithography appearance Download PDFInfo
- Publication number
- CN106699137A CN106699137A CN201710047897.7A CN201710047897A CN106699137A CN 106699137 A CN106699137 A CN 106699137A CN 201710047897 A CN201710047897 A CN 201710047897A CN 106699137 A CN106699137 A CN 106699137A
- Authority
- CN
- China
- Prior art keywords
- degreasing
- stereolithography
- product
- base substrate
- obtains
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y70/00—Materials specially adapted for additive manufacturing
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—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
-
- 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
- C04B35/634—Polymers
- C04B35/63404—Polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C04B35/63424—Polyacrylates; Polymethacrylates
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/64—Burning or sintering processes
- C04B35/65—Reaction sintering of free metal- or free silicon-containing compositions
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—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
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
- C04B2235/3244—Zirconium oxides, zirconates, hafnium oxides, hafnates, or oxide-forming salts thereof
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
- C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
- C04B2235/6562—Heating rate
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Compositions Of Oxide Ceramics (AREA)
Abstract
The invention belongs to the technical field of 3D printing, and particularly relates to a method for preparing ZTA multi-phase ceramic through 3D printing based on stereo lithography appearance. The invention provides a composition. The raw materials of the composition comprise a ceramic powder, a premixed liquid, a photoinitiator, a dispersing agent, a surfactant, zirconium salt and titanium salt. The invention also provides a method for preparing ZTA ceramic by using the composition. The method comprises the steps of preparing slurry, forming, drying and degreasing, performing impregnation and performing aftertreatment. In the technical scheme provided by the invention, a ceramic green body is prepared by a stereo lithography appearance method, so the forming efficiency is high and the dimensional precision of the product is high; the parameters in the degreasing step are optimized, so deformation and cracking of the green body in the degreasing process are avoided; through the impregnation step, the sintering temperature of the toughed ZTA ceramic material is reduced under the condition that the additive has minute quantity. Moreover, the microstructure of the product is uniform after the product structure is observed by an electronic speculum, and the defect that the sintering temperature of the ZTA ceramic is high in the prior art is overcome.
Description
Technical field
Prepare ZTA and answer the invention belongs to 3D printing technique field, more particularly to a kind of 3D printing based on Stereolithography
The method of phase ceramics.
Background technology
3D printing technique is Stereolithography technology (Stereo lithography Appearance, abridge SLA), its
Principle is：It is scanned in x-y faces with the laser beam of intensity by computer controls specific wavelength, is allowed to by point to line, by line
To face consecutive solidification, ceramic size is selectively solidified, complete a drawing performance for aspect, then lifting platform is in vertical direction
A mobile height for synusia, resolidification another aspect, one ceramic body of the composition that is so layering.But utilize light to consolidate
Although changing moulding process can be easy to prepare the ZTA ceramic components of labyrinth, there is low temperature aging and show in ZTA ceramics
As, its intensity, hardness and related mechanical property are reduced, its application industrially is further limited, therefore have very much
It is necessary that ZTA is adulterated, to regulate and control its mechanical property.
In the prior art, the doping method of ZTA, is not only difficult to prepare the ZTA ceramic materials of homogeneous texture, can add on the contrary
The inhomogeneities of acute microstructure.
Therefore, a kind of method that 3D printing based on Stereolithography prepares ZTA complex phase ceramics is developed, it is existing for solving
Have in technology, ZTA ceramic materials structure is uneven obtained in the doping method of ZTA, particularly the uneven technology of microstructure
Defect, becomes those skilled in the art's problem demanding prompt solution.
The content of the invention
In view of this, the invention provides a kind of method that 3D printing based on Stereolithography prepares ZTA complex phase ceramics,
For solving in the prior art, ZTA ceramic materials structure is uneven obtained in the doping method of ZTA, and particularly microstructure is not
Uniform technological deficiency.
The invention provides a kind of composition, the raw material of the composition includes：Ceramic powder, premixed liquid, light trigger,
Dispersant, surface modifier, zirconates and titanium salt；
The solute of the premixed liquid is selected from：Acrylamide, dimethylacrylate, Methacrylamide, methacrylic acid
One or more in 2- hydroxy methacrylates and N-N ' methylene-bisacrylamides.
Preferably, in terms of mass parts, the raw material of the composition includes：40~90 parts of ceramic powder, premixed liquid 30~50
Part, 1~3 part of light trigger, 1~3 part of dispersant, 1~3 part of surface modifier, 5~20 parts of zirconates and 5~20 parts of titanium salt.
Preferably, the solvent of the premixed liquid is selected from：One or more in deionized water, glycerine and absolute ethyl alcohol；
In the premixed liquid, the mass concentration of solute is 20~85%.
Preferably, the light trigger is selected from：One kind or many in BASF 819, BASF 907 and BASF 1173
Kind；
The dispersant is selected from：One or more in Sodium Polyacrylate, ammonium polyacrylate and BYK-9077；
The surface modifier is selected from：One or more in Aluminate, titanate esters and stearic acid.
Preferably, the ceramic powder is alumina ceramic powder, and the zirconates is selected from：ZrOCl2·8H2O、Zr
(NO3)4·5H2O and Zr (SO4)2·4H2One or more in O.
Preferably, the alumina ceramic powder has bimodal distribution structure, i.e.,：The particle diameter of the alumina ceramic powder
Wider distribution.
Preferably, the alumina ceramic powder is obtained by the alumina ceramic powder compounding of two kinds of different-grain diameters.
Present invention also offers the preparation method that the composition described in a kind of utilization any of the above one prepares ZTA ceramics,
The preparation method is：
Step one, prepare slurry：Ball milling after the mixing of ceramic powder, premixed liquid, dispersant, zirconates and surface modifier, then
Mix with light trigger, obtain slurry；
Step 2, shaping：The slurry Stereolithography, obtains base substrate；
Step 3, drying and degreasing：The base substrate is dried and degreasing through first time successively, obtains porous body；
Step 4, infiltration：The porous body infiltrates in impregnating solution, obtains infiltration base substrate；
Step 5, post processing：The infiltration base substrate is dried and sintered through second successively, obtains ceramic product.
Preferably, the preparation method of the slurry is：
Solute stirs to obtain premixed liquid in being dissolved in solvent；
After alumina ceramic powder and zirconium salt solution mixing, pH to 9~10 is adjusted, sieved after drying, obtain composite granule, institute
The solvent for stating zirconium salt solution is selected from：One or more in deionized water, ethanol and acetone；
After the composite granule, ethanol and dispersant, first time ball milling obtains the first product；
After the mixing of first product, premixed liquid, dispersant and surface modifier, second ball milling obtains the second product；
Mix with light trigger after the second product bubble removing, obtain slurry.
Preferably, the ball-milling medium of the first time ball milling is aluminum oxide, the ball-milling medium shape of the first time ball milling
It is spherical, a diameter of 5~10mm of ball-milling medium of the first time ball milling, the material ball ratio of the first time ball milling is 3:1~8:
1, the time of the first time ball milling is 3~8h.
Preferably, the ball-milling medium of second ball milling is aluminum oxide, the ball-milling medium shape of second ball milling
It is spherical, a diameter of 1~3mm of ball-milling medium of second ball milling, the material ball ratio of second ball milling is 1:1~5:1,
The time of second ball milling is 6~12h.
Preferably, the method for the bubble removing is：Second product stirs 10~60min under condition of negative pressure.
Preferably, the impregnating solution is titanium salt solution；
Titanium salt in the impregnating solution is selected from；Ti(SO4)2、Ti(S2O7)2、TiO(SO4)、Ti4O5(SO4)3、Ti7O13
(SO4)、Ti2O3(SO4), the solvent of the impregnating solution is water and/or ethanol；
In the impregnating solution, Ti4+Concentration be 0.1~5mol/L；
The time of the infiltration is 1~12h.
Preferably, the vacuum of the infiltration is more than 0.08MPa.
Preferably, the compound method of the impregnating solution is：After the titanium salt is dissolved in the solvent of the impregnating solution, 30~
10~30min of ultrasound under 90 DEG C of condition of water bath heating.
Preferably, the first time dry method is that liquid is dried and/or microwave drying, when first time is dry
Between be 5~36h；
The method of the degreasing is：After dried base substrate first carries out vacuum degreasing or atmosphere protection degreasing, then carry out sky
Qi exhaustion fat, the porosity of the porous body is 40~60%；
Second dry temperature is 30~100 DEG C, and the second dry time is 6~24h；
The method of the sintering is：Second dried base substrate is warming up to 1350 with the speed of 10~15 DEG C/min~
After 1550 DEG C, 1~4h is incubated.
Preferably, the first time dry temperature is 25~60 DEG C.
Preferably, the vacuum degreasing or the method for atmosphere protection degreasing are：It is warming up to the speed of 0.1~5 DEG C/min
After 600~1000 DEG C and 1~4h of insulation, room temperature is cooled to；In temperature-rise period, 30-60min is incubated every 100~200 DEG C.
Preferably, the vacuum of the vacuum degreasing is less than 0.09MPa, and the protection gas of the atmosphere protection degreasing is：N2
Or inert gas.
Preferably, the method for the air degreasing is：600~800 DEG C and insulation 2 are warming up to the speed of 3~8 DEG C/min
~4h, is cooled to room temperature.
Preferably, the sweep speed of the Stereolithography is 2000~4000mm/s, the scanning of the Stereolithography
Mode is XYSTA, and the sweep span of the Stereolithography is 0.1~0.5mm, the light wave a length of 355 of the Stereolithography
~460nm.
In sum, the invention provides a kind of composition, the raw material of the composition includes：Ceramic powder, premixed liquid,
Light trigger, dispersant, surface modifier and zirconates；The solute of the premixed liquid is selected from：Acrylamide, dimethacrylate
One or more in ester, Methacrylamide, 2-hydroxyethyl methacrylate and N-N ' methylene-bisacrylamides.This
Invention additionally provides the preparation method that a kind of utilization above-mentioned composition prepares ZTA ceramics, and the preparation method is：Step one, system
Standby slurry：Ball milling after the mixing of ceramic powder, premixed liquid, dispersant, zirconates and surface modifier, then mix with light trigger, obtain
Slurry；Step 2, shaping：The slurry Stereolithography, obtains base substrate；Step 3, drying and degreasing：The base substrate is successively through
Primary drying and degreasing, obtain porous body；Step 4, infiltration：The porous body infiltrates in impregnating solution, obtains infiltration base
Body；Step 5, post processing：The infiltration base substrate is dried and sintered through second successively, obtains ceramic product.The skill that the present invention is provided
In art scheme, ceramic body is prepared by Stereolithography method, shaping efficiency is high, product size high precision；By defatting step
The optimization of parameter, skimming processes base substrate is indeformable, do not ftracture；By impregnation step, feelings of the very small amount as additive are realized
Under condition, toughness reinforcing ZTA ceramic materials are obtained.Meanwhile, through electron microscopic observation product structure, product microstructure is uniform, solves existing
In technology, ZTA ceramic materials structure is uneven obtained in the doping method of ZTA, and particularly the uneven technology of microstructure lacks
Fall into.
Specific embodiment
The invention provides a kind of method that 3D printing based on Stereolithography prepares ZTA complex phase ceramics, for solving
In the prior art, ZTA ceramic materials structure is uneven obtained in the doping method of ZTA, particularly the uneven skill of microstructure
Art defect.
The technical scheme in the embodiment of the present invention will be clearly and completely described below, it is clear that described implementation
Example is only a part of embodiment of the invention, rather than whole embodiments.Based on the embodiment in the present invention, this area is common
The every other embodiment that technical staff is obtained under the premise of creative work is not made, belongs to the model of present invention protection
Enclose.
In order to the present invention is described in more detail, with reference to embodiment the present invention is provided it is a kind of based on Stereolithography
The method that 3D printing prepares ZTA complex phase ceramics, is specifically described.
Embodiment 1
The present embodiment prepares the specific reality of ceramic product 1 for a kind of preparation method of ZTA ceramics provided using the present invention
Apply example.
Step one, prepare slurry
50g solutes are dissolved in 50g solvents, and premixed liquid 1 is stirred to obtain after mixing.In the present embodiment, solute is acrylamide, molten
Agent is deionized water.
12g zirconates is dissolved in 100ml deionized waters, and zirconium salt solution 1 is obtained.Zirconium salt solution 1 and 78g alumina ceramic powders
1 mixing, it is ensured that the pH of mixed system is dried after the completion of mixing, crossed 100 mesh sieves between 9~10 in mixed process, obtains composite powder
Body 1.In the present embodiment, the purity that alumina ceramic powder has two peak structure, alumina ceramic powder is more than 99%, aluminum oxide
Ceramic powder is α-Al2O3, the particle diameter of aluminium oxide ceramics is：0.1~0.5 μm；Zirconates is ZrOCl2·8H2O。
After 80g composite granules 1,240g ethanol and 0.8g dispersants, first time ball milling obtains the first product 1.For the first time
In ball milling, ball-milling medium is aluminum oxide, and a diameter of 5mm of ball-milling medium, being shaped as ball-milling medium is spherical, and material ball ratio is 3:1；
Dispersant is Sodium Polyacrylate.
After the mixing of the first products of 40g 1,60g premixed liquids 1,0.4g dispersants and 0.4g surfactants, second ball milling,
Obtain the second product 1.In second ball milling, ball-milling medium is aluminum oxide, a diameter of 1mm of ball-milling medium, the shape of ball-milling medium
For spherical, material ball ratio is 1:1.In the present embodiment, dispersant is Sodium Polyacrylate, and surfactant is stearic acid.
After the second products of 50g 1 stir 10min bubble removings under condition of negative pressure, mix with 0.5g light triggers, obtain slurry 1.
In the present embodiment, light trigger is BASF 819.
Step 2, shaping
The Stereolithography in Stereolithography equipment of slurry 1, base substrate 1 is drawn to obtain according to designed ceramic shape.Its
In, the sweep speed of Stereolithography is 2000mm/s, the scan mode of Stereolithography is XYSTA, and Stereolithography is swept
Spacing is retouched for 0.1mm, a length of 365nm of light wave of Stereolithography.
Step 3, drying and degreasing：
Base substrate 1 is placed in after drying 6h in liquid drier, degreasing, obtains porous body 1；Wherein, the porosity of porous body 1
It is 40%.In the present embodiment, liquid drier is polyethylene glycol.
Degreasing method is：After dried base substrate 1 first carries out vacuum degreasing, then carry out air degreasing.
In the present embodiment, the method for vacuum degreasing is：600 DEG C are warming up to the speed of 0.5 DEG C/min and are incubated 1h, and rise
After being incubated 30min every 100 DEG C during temperature, room temperature is cooled to the furnace；Wherein, the vacuum of vacuum degreasing is less than 0.09MPa.
The method of air degreasing is：600 DEG C are warming up to the speed of 3 DEG C/min and are incubated 2h, be cooled to room temperature.
Step 4, infiltration
Under the conditions of vacuum is more than 0.08MPa, porous body 1 is in Ti4+2h is infiltrated in solution, the infiltration for wiping surface is molten
After liquid, in NH3·H215min is stood in O, base substrate 1 must be infiltrated.
In the present embodiment, Ti is infiltrated4+The solvent of solution is water, and the solute of impregnating solution is Ti (SO4)2, in impregnating solution
Ti4+Concentration be 0.5mol/min；Wherein, Ti is infiltrated4+After solution is mixed by solvent and solute, heating water bath under the conditions of 45 DEG C
Ultrasonic 10min is obtained.
Step 5, post processing
Infiltration base substrate 1 is sintered after drying 12h under the conditions of 50 DEG C, obtains ceramic product 1.
In the present embodiment, the method for sintering is：1350 DEG C are warming up to the speed of 10 DEG C/min and be incubated 1h, furnace cooling
To room temperature.
Embodiment 2
The present embodiment prepares the specific reality of ceramic product 2 for a kind of preparation method of ZTA ceramics provided using the present invention
Apply example.
Step one, prepare slurry
50g solutes are dissolved in 50g solvents, and premixed liquid 2 is stirred to obtain after mixing.In the present embodiment, solute is methacryl
Amine, solvent is deionized water and glycerine.
18g zirconates is dissolved in 100ml deionized waters, and zirconium salt solution 2 is obtained.Zirconium salt solution 2 and 72g alumina ceramic powders
2 mixing, it is ensured that the pH of mixed system is dried after the completion of mixing, crossed 100 mesh sieves between 9~10 in mixed process, obtains composite powder
Body 2.In the present embodiment, the purity that alumina ceramic powder has two peak structure, alumina ceramic powder is more than 99%, aluminum oxide
Ceramic powder is α-Al2O3, the particle diameter of aluminium oxide ceramics is：0.1~0.5 μm；Zirconates is Zr (NO3)4·5H2O。
After 80g composite granules 2,240g ethanol and 1.6g dispersants, first time ball milling obtains the first product 2.For the first time
In ball milling, ball-milling medium is aluminum oxide, and a diameter of 7mm of ball-milling medium, being shaped as ball-milling medium is spherical, and material ball ratio is 5:1；
Dispersant is Sodium Polyacrylate.
After the mixing of the first products of 45g 2,55g premixed liquids 2,0.9g dispersants and 0.9g surfactants, second ball milling,
Obtain the second product 2.In second ball milling, ball-milling medium is aluminum oxide, a diameter of 1mm of ball-milling medium, the shape of ball-milling medium
For spherical, material ball ratio is 2:1.In the present embodiment, dispersant is Sodium Polyacrylate, and surfactant is stearic acid.
After the second products of 50g 2 stir 20min bubble removings under condition of negative pressure, mix with 1g light triggers, obtain slurry 2.This
In embodiment, light trigger is BASF 1173.
Step 2, shaping
The Stereolithography in Stereolithography equipment of slurry 2, base substrate 2 is drawn to obtain according to designed ceramic shape.Its
In, the sweep speed of Stereolithography is 2500mm/s, the scan mode of Stereolithography is XYSTA, and Stereolithography is swept
Spacing is retouched for 0.3mm, a length of 365nm of light wave of Stereolithography.
Step 3, drying and degreasing：
Base substrate 2 is placed in after drying 8h in liquid drier, degreasing, obtains porous body 2；Wherein, the porosity of porous body 2
It is 45%.In the present embodiment, liquid drier is polyethylene glycol.
Degreasing method is：After dried base substrate 2 first carries out vacuum degreasing, then carry out air degreasing.
In the present embodiment, the method for vacuum degreasing is：700 DEG C are warming up to the speed of 1 DEG C/min and are incubated 2h, and heat up
During every 150 DEG C be incubated 40min after, cool to room temperature with the furnace；Wherein, the vacuum of vacuum degreasing is less than 0.09MPa.It is empty
The method of qi exhaustion fat is：700 DEG C are warming up to the speed of 5 DEG C/min and are incubated 3h, be cooled to room temperature.
Step 4, infiltration
Under the conditions of vacuum is more than 0.08MPa, porous body 2 is in infiltration Ti4+4h is infiltrated in solution, the leaching on surface is wiped
After osmometer solution, in NH3·H215min is stood in O, base substrate 2 must be infiltrated.
In the present embodiment, Ti is infiltrated4+The solvent of solution is water, and the solute of impregnating solution is TiO (SO4), in impregnating solution
Ti4+Concentration be 1mol/min；Wherein, Ti is infiltrated4+After solution is mixed by solvent and solute, heating water bath surpasses under the conditions of 55 DEG C
Sound 20min is obtained.
Step 5, post processing
Infiltration base substrate 2 is sintered after drying 24h under the conditions of 50 DEG C, obtains ceramic product 2.
In the present embodiment, the method for sintering is：1450 DEG C are warming up to the speed of 10 DEG C/min and be incubated 1h, furnace cooling
To room temperature.
Embodiment 3
The present embodiment prepares the specific reality of ceramic product 3 for a kind of preparation method of ZTA ceramics provided using the present invention
Apply example.
Step one, prepare slurry
50g solutes are dissolved in 50g solvents, and premixed liquid 3 is stirred to obtain after mixing.In the present embodiment, solute be acrylamide and
Dimethylacrylate, solvent is deionized water.
20g zirconates is dissolved in 100ml deionized waters, and zirconium salt solution 3 is obtained.Zirconium salt solution 3 and 80g alumina ceramic powders
3 mixing, it is ensured that the pH of mixed system is dried after the completion of mixing, crossed 100 mesh sieves between 9~10 in mixed process, obtains composite powder
Body 3.In the present embodiment, the purity that alumina ceramic powder has two peak structure, alumina ceramic powder is more than 99%, aluminum oxide
Ceramic powder is α-Al2O3, the particle diameter of aluminium oxide ceramics is：0.1~0.5 μm；Zirconates is Zr (NO3)4·5H2O。
After 80g composite granules 3,240g ethanol and 2.4g dispersants, first time ball milling obtains the first product 3.For the first time
In ball milling, ball-milling medium is aluminum oxide, and a diameter of 10mm of ball-milling medium, being shaped as ball-milling medium is spherical, and material ball ratio is 8:
1；Dispersant is ammonium polyacrylate.
After the mixing of the first products of 50g 3,50g premixed liquids 3,1.5g dispersants and 1.5g surfactants, second ball milling,
Obtain the second product 3.In second ball milling, ball-milling medium is aluminum oxide, a diameter of 1mm of ball-milling medium, the shape of ball-milling medium
For spherical, material ball ratio is 3:1.In the present embodiment, dispersant is ammonium polyacrylate, and surfactant is stearic acid.
After the second products of 50g 3 stir 30min bubble removings under condition of negative pressure, mix with 1.5g light triggers, obtain slurry 3.
In the present embodiment, light trigger is BASF 907.
Step 2, shaping
The Stereolithography in Stereolithography equipment of slurry 3, base substrate 3 is drawn to obtain according to designed ceramic shape.Its
In, the sweep speed of Stereolithography is 3000mm/s, the scan mode of Stereolithography is XYSTA, and Stereolithography is swept
Spacing is retouched for 0.3mm, a length of 365nm of light wave of Stereolithography.
Step 3, drying and degreasing：
Base substrate 3 is placed in after drying 10h in liquid drier, degreasing, obtains porous body 3；Wherein, the hole of porous body 3
Rate is 50%.In the present embodiment, liquid drier is polyethylene glycol.
Degreasing method is：After dried base substrate 3 first carries out vacuum degreasing, then carry out air degreasing.
In the present embodiment, the method for vacuum degreasing is：800 DEG C are warming up to the speed of 2 DEG C/min and are incubated 4h, and heat up
During every 200 DEG C be incubated 45min after, cool to room temperature with the furnace；Wherein, the vacuum of vacuum degreasing is less than 0.09MPa.It is empty
The method of qi exhaustion fat is：800 DEG C are warming up to the speed of 8 DEG C/min and are incubated 3h, be cooled to room temperature.
Step 4, infiltration
Under the conditions of vacuum is more than 0.08MPa, porous body 3 is in infiltration Ti4+6h is infiltrated in solution, the leaching on surface is wiped
Ooze Ti4+After solution, in NH3·H215min is stood in O, base substrate 3 must be infiltrated.
In the present embodiment, Ti is infiltrated4+The solvent of solution is ethanol, and the solute of impregnating solution is Ti2O3(SO4), impregnating solution
Middle Ti4+Concentration be 1.5mol/min；Wherein, Ti is infiltrated4+After solution is mixed by solvent and solute, water-bath adds under the conditions of 60 DEG C
Hot ultrasound 20min is obtained.
Step 5, post processing
Infiltration base substrate 3 is sintered after drying 24h under the conditions of 80 DEG C, obtains ceramic product 3.
In the present embodiment, the method for sintering is：1550 DEG C are warming up to the speed of 10 DEG C/min and be incubated 1h, furnace cooling
To room temperature.
Embodiment 4
The present embodiment prepares the specific reality of ceramic product 4 for a kind of preparation method of ZTA ceramics provided using the present invention
Apply example.
Step one, prepare slurry
50g solutes are dissolved in 50g solvents, and premixed liquid 4 is stirred to obtain after mixing.In the present embodiment, solute be acrylamide and
N-N ' methylene-bisacrylamides, solvent is deionized water.
25g zirconates is dissolved in 100ml deionized waters, and zirconium salt solution 4 is obtained.Zirconium salt solution 4 and 75g alumina ceramic powders
4 mixing, it is ensured that the pH of mixed system is dried after the completion of mixing, crossed 100 mesh sieves between 9~10 in mixed process, obtains composite powder
Body 4.In the present embodiment, the purity that alumina ceramic powder has two peak structure, alumina ceramic powder is more than 99%, aluminum oxide
Ceramic powder is α-Al2O3, the particle diameter of aluminium oxide ceramics is：0.1~0.5 μm；Zirconates is ZrOCl2·8H2O、Zr(NO3)4·
5H2O。
After 80g composite granules 4,240g ethanol and 3.2g dispersants, first time ball milling obtains the first product 4.For the first time
In ball milling, ball-milling medium is aluminum oxide, and a diameter of 5mm of ball-milling medium, being shaped as ball-milling medium is spherical, and material ball ratio is 3:1；
Dispersant is BYK-9077.
After the mixing of the first products of 55g 4,45g premixed liquids 4,1.65g dispersants and 1.65g surfactants, second ball
Mill, obtains the second product 4.In second ball milling, ball-milling medium is aluminum oxide, a diameter of 3mm of ball-milling medium, the shape of ball-milling medium
Shape is spherical, and material ball ratio is 1:1.In the present embodiment, dispersant is BYK-9077, and surfactant is Aluminate.
After the second products of 50g 4 stir 40min bubble removings under condition of negative pressure, mix with 1.5g light triggers, obtain slurry 4.
In the present embodiment, light trigger is BASF 819 and BASF 1173.
Step 2, shaping
The Stereolithography in Stereolithography equipment of slurry 4, base substrate 4 is drawn to obtain according to designed ceramic shape.Its
In, the sweep speed of Stereolithography is 3500mm/s, the scan mode of Stereolithography is XYSTA, and Stereolithography is swept
Spacing is retouched for 0.3mm, a length of 365nm of light wave of Stereolithography.
Step 3, drying and degreasing：
Base substrate 4 is placed in after drying 12h in liquid drier, degreasing, obtains porous body 4；Wherein, the hole of porous body 4
Rate is 50%.In the present embodiment, liquid drier is polyethylene glycol.
Degreasing method is：After dried base substrate 4 first carries out vacuum degreasing, then carry out air degreasing.
In the present embodiment, the method for vacuum degreasing is：900 DEG C are warming up to the speed of 3 DEG C/min and are incubated 2h, and heat up
During every 100 DEG C be incubated 60min after, cool to room temperature with the furnace；Wherein, the vacuum of vacuum degreasing is less than 0.09MPa.It is empty
The method of qi exhaustion fat is：800 DEG C are warming up to the speed of 5 DEG C/min and are incubated 4h, be cooled to room temperature.
Step 4, infiltration
Under the conditions of vacuum is more than 0.08MPa, porous body 4 is in infiltration Ti4+8h is infiltrated in solution, the leaching on surface is wiped
Ooze Ti4+After solution, in NH3·H215min is stood in O, base substrate 4 must be infiltrated.
In the present embodiment, Ti is infiltrated4+The solvent of solution is water, and the solute of impregnating solution is Ti4O5(SO4)3, impregnating solution
Middle Ti4+Concentration be 2.0mol/min；Wherein, Ti is infiltrated4+After solution is mixed by solvent and solute, water-bath adds under the conditions of 65 DEG C
Hot ultrasound 20min is obtained.
Step 5, post processing
Infiltration base substrate 4 is sintered after drying 12h under the conditions of 100 DEG C, obtains ceramic product 4.
In the present embodiment, the method for sintering is：1550 DEG C are warming up to the speed of 10 DEG C/min and be incubated 2h, furnace cooling
To room temperature.
Embodiment 5
The present embodiment prepares the specific reality of ceramic product 5 for a kind of preparation method of ZTA ceramics provided using the present invention
Apply example.
Step one, prepare slurry
50g solutes are dissolved in 50g solvents, and premixed liquid 5 is stirred to obtain after mixing.In the present embodiment, solute be acrylamide and
N-N ' methylene-bisacrylamides, solvent is deionized water and glycerine.
30g zirconates is dissolved in 100ml acetone, and zirconium salt solution 5 is obtained.Zirconium salt solution 5 and 70g alumina ceramic powders 5 are mixed
Close, it is ensured that the pH of mixed system is dried after the completion of mixing, crossed 100 mesh sieves between 9~10 in mixed process, obtains composite granule
5.In the present embodiment, the purity that alumina ceramic powder has two peak structure, alumina ceramic powder is more than 99%, aluminum oxide pottery
Porcelain powder is α-Al2O3, the particle diameter of aluminium oxide ceramics is：0.1~0.5 μm；Zirconates is ZrOCl2·8H2O、Zr(NO3)4·5H2O
With Zr (SO4)2·4H2O。
After 80g composite granules 5,240g ethanol and 4.0g dispersants, first time ball milling obtains the first product 5.For the first time
In ball milling, ball-milling medium is aluminum oxide, and a diameter of 7mm of ball-milling medium, being shaped as ball-milling medium is spherical, and material ball ratio is 5:1；
Dispersant is Sodium Polyacrylate and ammonium polyacrylate.
After the mixing of the first products of 60g 5,10g premixed liquids 5,1.8g dispersants and 1.8g surfactants, second ball milling,
Obtain the second product 5.In second ball milling, ball-milling medium is aluminum oxide, a diameter of 3mm of ball-milling medium, the shape of ball-milling medium
For spherical, material ball ratio is 5:1.In the present embodiment, dispersant is Sodium Polyacrylate and ammonium polyacrylate, and surfactant is aluminic acid
Ester.
After the second products of 50g 5 stir 50min bubble removings under condition of negative pressure, mix with 1g light triggers, obtain slurry 5.This
In embodiment, light trigger is BASF 819 and BASF 907.
Step 2, shaping
The Stereolithography in Stereolithography equipment of slurry 5, base substrate 5 is drawn to obtain according to designed ceramic shape.Its
In, the sweep speed of Stereolithography is 4000mm/s, the scan mode of Stereolithography is XYSTA, and Stereolithography is swept
Spacing is retouched for 0.1mm, a length of 405nm of light wave of Stereolithography.
Step 3, drying and degreasing：
Base substrate 5 is placed in after drying 16h in liquid drier, degreasing, obtains porous body 5；Wherein, the hole of porous body 5
Rate is 50%.In the present embodiment, liquid drier is polyethylene glycol and ethanol.
Degreasing method is：After dried base substrate 5 first carries out vacuum degreasing, then carry out air degreasing.
In the present embodiment, the method for vacuum degreasing is：1000 DEG C are warming up to the speed of 5 DEG C/min and are incubated 2h, and rise
After being incubated 60min every 150 DEG C during temperature, room temperature is cooled to the furnace；Wherein, the vacuum of vacuum degreasing is less than 0.09MPa.
The method of air degreasing is：800 DEG C are warming up to the speed of 8 DEG C/min and are incubated 4h, be cooled to room temperature.
Step 4, infiltration
Under the conditions of vacuum is more than 0.08MPa, porous body 5 is in infiltration Ti4+10h is infiltrated in solution, surface is wiped
Infiltration Ti4+After solution, in NH3·H215min is stood in O, base substrate 5 must be infiltrated.
In the present embodiment, Ti is infiltrated4+The solvent of solution is water and ethanol, and the solute of impregnating solution is TiO (SO4), infiltration
Ti in solution4+Concentration be 3.0mol/min；Wherein, Ti is infiltrated4+After solution is mixed by solvent and solute, water under the conditions of 70 DEG C
Bath heating ultrasound 30min is obtained.
Step 5, post processing
Infiltration base substrate 5 is sintered after drying 24h under the conditions of 100 DEG C, obtains ceramic product 5.
In the present embodiment, the method for sintering is：1550 DEG C are warming up to the speed of 10 DEG C/min and be incubated 3h, furnace cooling
To room temperature.
Embodiment 6
The present embodiment prepares the specific reality of ceramic product 6 for a kind of preparation method of ZTA ceramics provided using the present invention
Apply example.
Step one, prepare slurry
50g solutes are dissolved in 50g solvents, and premixed liquid 6 is stirred to obtain after mixing.In the present embodiment, solute be acrylamide and
N-N ' methylene-bisacrylamides, solvent deionized water and ethanol.
35g zirconates is dissolved in 100ml ethanol, and zirconium salt solution 6 is obtained.Zirconium salt solution 6 and 65g alumina ceramic powders 6 are mixed
Close, it is ensured that the pH of mixed system is dried after the completion of mixing, crossed 100 mesh sieves between 9~10 in mixed process, obtains composite granule
6.In the present embodiment, the purity that alumina ceramic powder has two peak structure, alumina ceramic powder is more than 99%, aluminum oxide pottery
Porcelain powder is α-Al2O3, the particle diameter of aluminium oxide ceramics is：0.1~0.5 μm；Zirconates is ZrOCl2·8H2O and Zr (SO4)2·
4H2O。
After 80g composite granules 6,240g ethanol and 4.8g dispersants, first time ball milling obtains the first product 6.For the first time
In ball milling, ball-milling medium is aluminum oxide, and a diameter of 10mm of ball-milling medium, being shaped as ball-milling medium is spherical, and material ball ratio is 8:
1；Dispersant is BYK-9077, ammonium polyacrylate and Sodium Polyacrylate.
After the mixing of the first products of 65g 6,35g premixed liquids 6,1.95g dispersants and 1.95g surfactants, second ball
Mill, obtains the second product 6.In second ball milling, ball-milling medium is aluminum oxide, a diameter of 3mm of ball-milling medium, the shape of ball-milling medium
Shape is spherical, and material ball ratio is 3:1.In the present embodiment, dispersant is BYK-9077, ammonium polyacrylate and Sodium Polyacrylate, surface
Activating agent is Aluminate.
After the second products of 50g 6 stir 60min bubble removings under condition of negative pressure, mix with 1.5g light triggers, obtain slurry 6.
In the present embodiment, light trigger is BASF 818, BASF 907 and BASF 1173.
Step 2, shaping
The Stereolithography in Stereolithography equipment of slurry 6, base substrate 6 is drawn to obtain according to designed ceramic shape.Its
In, the sweep speed of Stereolithography is 4000mm/s, the scan mode of Stereolithography is XYSTA, and Stereolithography is swept
Spacing is retouched for 0.5mm, a length of 405nm of light wave of Stereolithography.
Step 3, drying and degreasing：
Base substrate 6 is placed in after drying 36h in liquid drier, degreasing, obtains porous body 6；Wherein, the hole of porous body 6
Rate is 60%.In the present embodiment, liquid drier is polyethylene glycol and ethanol.
Degreasing method is：After dried base substrate 6 first carries out vacuum degreasing, then carry out air degreasing.
In the present embodiment, the method for vacuum degreasing is：1000 DEG C are warming up to the speed of 5 DEG C/min and are incubated 1h, and rise
After being incubated 30min every 200 DEG C during temperature, room temperature is cooled to the furnace；Wherein, the vacuum of vacuum degreasing is less than 0.09MPa.
The method of air degreasing is：800 DEG C are warming up to the speed of 8 DEG C/min and are incubated 4h, be cooled to room temperature.
Step 4, infiltration
Under the conditions of vacuum is more than 0.08MPa, porous body 6 is in infiltration Ti4+12h is infiltrated in solution, surface is wiped
Infiltration Ti4+After solution, in NH3·H215min is stood in O, base substrate 6 must be infiltrated.
In the present embodiment, Ti is infiltrated4+The solvent of solution is water and ethanol, and the solute of impregnating solution is Ti (SO4)2, infiltration
Ti in solution4+Concentration be 4.5mol/min；Wherein, Ti is infiltrated4+After solution is mixed by solvent and solute, water under the conditions of 75 DEG C
Bath heating ultrasound 30min is obtained.
Step 5, post processing
Infiltration base substrate 6 is sintered after drying 12h under the conditions of 100 DEG C, obtains ceramic product 6.
In the present embodiment, the method for sintering is：1550 DEG C are warming up to the speed of 10 DEG C/min and be incubated 4h, furnace cooling
To room temperature.
Embodiment 7
The present embodiment is the embodiment for verifying product 1 obtained in embodiment 1 to embodiment 6 to the beneficial effect of product 6.
Electron microscopic observation：By Ti4+After infiltration, we can clearly have found that crystallite dimension is substantially grown up, and consistency is carried
Height, in the case where hardness reduces less, toughness is significantly improved.
The Vickers hardness of product 1 is 17.0GPa, and toughness is 4.6MPam1/2, crystallite dimension is 1.2 μm.
The Vickers hardness of product 2 is 17.3GPa, and toughness is 4.8MPam1/2, crystallite dimension is 1.6 μm.
The Vickers hardness of product 3 is 16.8GPa, and toughness is 5.4MPam1/2, crystallite dimension is 1.8 μm.
The Vickers hardness of product 4 is 16GPa, and toughness is 5.5MPam1/2, crystallite dimension is 1.8 μm.
The Vickers hardness of product 5 is 15.8GPa, and toughness is 5.3MPam1/2, crystallite dimension is 2.0 μm.
The Vickers hardness of product 6 is 15.5GPa, and toughness is 5.7MPam1/2, crystallite dimension is 2.2 μm.
In sum, the invention provides a kind of composition, the raw material of the composition includes：Ceramic powder, premixed liquid,
Light trigger, dispersant, surface modifier and zirconates；The solute of the premixed liquid is selected from：Acrylamide, dimethacrylate
One or more in ester, Methacrylamide, 2-hydroxyethyl methacrylate and N-N ' methylene-bisacrylamides.This
The composition that invention is additionally provided described in a kind of utilization any of the above one prepares the preparation method of ZTA ceramics, the preparation side
Method is：Step one, prepare slurry：Ceramic powder, premixed liquid, dispersant, zirconates and surface modifier mixing after ball milling, then with light
Initiator mixes, and obtains slurry；Step 2, shaping：The slurry Stereolithography, obtains base substrate；Step 3, drying and degreasing：Institute
State base substrate to be dried and degreasing through first time successively, obtain porous body；Step 4, infiltration：The porous body is in impregnating solution
Infiltration, obtains infiltration base substrate；Step 5, post processing：The infiltration base substrate is dried and sintered through second successively, obtains aluminium oxide ceramics
Product.In the technical scheme that the present invention is provided, ceramic body is prepared by Stereolithography method, shaping efficiency is high, product size
High precision；By the optimization of defatting step parameter, skimming processes base substrate is indeformable, do not ftracture；By impregnation step, pole is realized
It is a small amount of as additive in the case of, toughness reinforcing ZTA ceramic materials are obtained.Meanwhile, through electron microscopic observation product structure, the microcosmic knot of product
Structure is uniform, solves in the prior art, and ZTA ceramic materials structure is uneven obtained in the doping method of ZTA, particularly microcosmic knot
The uneven technological deficiency of structure.
The above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, under the premise without departing from the principles of the invention, some improvements and modifications can also be made, these improvements and modifications also should
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of composition, it is characterised in that the raw material of the composition includes：Ceramic powder, premixed liquid, light trigger, point
Powder, surface modifier, zirconates and titanium salt；
The solute of the premixed liquid is selected from：Acrylamide, dimethylacrylate, Methacrylamide, methacrylic acid 2- hydroxyls
One or more in base ethyl ester and N-N ' methylene-bisacrylamides.
2. composition according to claim 1, it is characterised in that in terms of mass parts, the raw material of the composition includes：Pottery
40~90 parts of porcelain powder, 30~50 parts of premixed liquid, 1~3 part of light trigger, 1~3 part of dispersant, 1~3 part of surface modifier, zirconium
5~20 parts of 5~20 parts of salt and titanium salt.
3. composition according to claim 1, it is characterised in that the solvent of the premixed liquid is selected from：Deionized water, glycerine
And one or more in absolute ethyl alcohol；
In the premixed liquid, the mass concentration of solute is 20~85%.
4. composition according to claim 1, it is characterised in that the light trigger is selected from：BASF 819, BASF
907 and BASF 1173 in one or more；
The dispersant is selected from：One or more in Sodium Polyacrylate, ammonium polyacrylate and BYK-9077；
The surface modifier is selected from：One or more in Aluminate, titanate esters and stearic acid.
5. composition according to claim 1, it is characterised in that the ceramic powder is alumina ceramic powder, described
Zirconates is selected from：ZrOCl2·8H2O、Zr(NO3)4·5H2O and Zr (SO4)2·4H2One or more in O.
6. the composition described in a kind of utilization claim 1 to 5 any one prepares the preparation method of ZTA ceramics, and its feature exists
In the preparation method is：
Step one, prepare slurry：Ceramic powder, premixed liquid, dispersant, zirconates and surface modifier mixing after ball milling, then with light
Initiator mixes, and obtains slurry；
Step 2, shaping：The slurry Stereolithography, obtains base substrate；
Step 3, drying and degreasing：The base substrate is dried and degreasing through first time successively, obtains porous body；
Step 4, infiltration：The porous body infiltrates in impregnating solution, obtains infiltration base substrate；
Step 5, post processing：The infiltration base substrate is dried and sintered through second successively, obtains ceramic product.
7. preparation method according to claim 6, it is characterised in that the preparation method of the slurry is：
Solute stirs to obtain premixed liquid in being dissolved in solvent；
After alumina ceramic powder and zirconium salt solution mixing, pH to 9~10 is adjusted, sieved after drying, obtain composite granule, the zirconium
The solvent of salting liquid is selected from：One or more in deionized water, ethanol and acetone；
After the composite granule, ethanol and dispersant, first time ball milling obtains the first product；
After the mixing of first product, premixed liquid, dispersant and surface modifier, second ball milling obtains the second product；
Mix with light trigger after the second product bubble removing, obtain slurry.
8. preparation method according to claim 6, it is characterised in that the impregnating solution is titanium salt solution；
Titanium salt in the impregnating solution is selected from；Ti(SO4)2、Ti(S2O7)2、TiO(SO4)、Ti4O5(SO4)3、Ti7O13(SO4)、
Ti2O3(SO4), the solvent of the impregnating solution is water and/or ethanol；
In the impregnating solution, Ti4+Concentration be 0.1~5mol/L；
The time of the infiltration is 1~12h.
9. preparation method according to claim 6, it is characterised in that the first time dry method is that liquid is dried
And/or microwave drying, the first time dry time is 5~36h；
The method of the degreasing is：After dried base substrate first carries out vacuum degreasing or atmosphere protection degreasing, then carry out air take off
Fat, the porosity of the porous body is 40~60%；
Second dry temperature is 30~100 DEG C, and the second dry time is 6~24h；
The method of the sintering is：Second dried base substrate is warming up to 1350~1550 DEG C with the speed of 10~15 DEG C/min
Afterwards, it is incubated 1~4h.
10. preparation method according to claim 6, it is characterised in that the sweep speed of the Stereolithography is 2000
~4000mm/s, the scan mode of the Stereolithography is XYSTA, the sweep span of the Stereolithography for 0.1~
0.5mm, a length of 355~460nm of light wave of the Stereolithography.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710047897.7A CN106699137A (en) | 2017-01-20 | 2017-01-20 | Method for preparing ZTA multi-phase ceramic through 3D printing based on stereo lithography appearance |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710047897.7A CN106699137A (en) | 2017-01-20 | 2017-01-20 | Method for preparing ZTA multi-phase ceramic through 3D printing based on stereo lithography appearance |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106699137A true CN106699137A (en) | 2017-05-24 |
Family
ID=58910130
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710047897.7A Pending CN106699137A (en) | 2017-01-20 | 2017-01-20 | Method for preparing ZTA multi-phase ceramic through 3D printing based on stereo lithography appearance |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106699137A (en) |
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107382312A (en) * | 2017-07-11 | 2017-11-24 | 宁波匠心快速成型技术有限公司 | The preparation method and its 3D printing forming method of a kind of 3D printing ceramic slurry |
| CN107417262A (en) * | 2017-09-20 | 2017-12-01 | 吴江中瑞机电科技有限公司 | 3D printing technique prepares material of graded ceramicses and preparation method thereof |
| CN108033777A (en) * | 2017-10-31 | 2018-05-15 | 西安铂力特增材技术股份有限公司 | A kind of alumina slurry for photocuring technology and preparation method thereof |
| CN108456002A (en) * | 2018-02-08 | 2018-08-28 | 广东工业大学 | A method of being suitable for the 3D printing ceramic component based on Stereolithography of selfreparing/self-reinforcing |
| CN108675798A (en) * | 2018-08-03 | 2018-10-19 | 广东工业大学 | A kind of silicon nitride ceramics and preparation method thereof |
| CN108814991A (en) * | 2018-06-21 | 2018-11-16 | 温州医科大学附属口腔医院 | A kind of bionical enamel material and its production method for being fabricated to bionical tooth |
| CN109020605A (en) * | 2018-09-30 | 2018-12-18 | 广东工业大学 | A kind of ceramic material and its preparation method and application |
| CN109761615A (en) * | 2019-03-15 | 2019-05-17 | 广东工业大学 | A kind of preparation method of photocuring Behavior of Slurry for Aluminum Nitride Ceramics and aluminium nitride ceramics |
| CN109794301A (en) * | 2019-01-16 | 2019-05-24 | 武汉理工大学 | A kind of ceramic photocatalysis carrier structure based on increasing material manufacturing |
| CN110028324A (en) * | 2019-05-29 | 2019-07-19 | 广东工业大学 | A kind of preparation method of nitride ceramics |
| CN110317001A (en) * | 2019-07-15 | 2019-10-11 | 威海市济合材料工程研究院 | A kind of light-cured resin of the 3D printing ZTA ceramics for DLP rapid shaping |
| CN110511017A (en) * | 2019-07-31 | 2019-11-29 | 映维(苏州)数字科技有限公司 | A kind of preparation method of rapid photocuring high solids content ceramic slurry |
| CN110511002A (en) * | 2019-09-26 | 2019-11-29 | 上海应用技术大学 | The method that DLP 3D printing technique prepares ZTA ceramic component |
| CN111925193A (en) * | 2020-07-17 | 2020-11-13 | 长沙理工大学 | 3D printing preparation method of fine-grain alumina ceramic |
| CN113878113A (en) * | 2021-08-30 | 2022-01-04 | 广东省科学院新材料研究所 | Ceramic-stainless steel composite material and preparation method thereof |
| CN114380583A (en) * | 2022-01-26 | 2022-04-22 | 重庆恩辰新材料科技有限责任公司 | Preparation method of ceramic material |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105198449A (en) * | 2015-09-16 | 2015-12-30 | 广东工业大学 | Method for preparing photocuring-formed high-density ceramic |
| CN105330266A (en) * | 2015-12-03 | 2016-02-17 | 广东工业大学 | Preparation method of tooth-like special-shaped ceramics |
-
2017
- 2017-01-20 CN CN201710047897.7A patent/CN106699137A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105198449A (en) * | 2015-09-16 | 2015-12-30 | 广东工业大学 | Method for preparing photocuring-formed high-density ceramic |
| CN105330266A (en) * | 2015-12-03 | 2016-02-17 | 广东工业大学 | Preparation method of tooth-like special-shaped ceramics |
Non-Patent Citations (3)
| Title |
|---|
| HAIDONG WU ET AL.: "Fabrication of dense zirconia-toughened alumina ceramics through a stereolithography-based additive manufacturing", 《CERAMICS INTERNATIONAL》 * |
| HANISAH MANSHOR ET AL.: "Effects of TiO2 addition on the phase, mechanical properties, and microstructure of zirconia-toughened alumina ceramic composite", 《CERAMICS INTERNATIONAL》 * |
| WEI LIU ET AL.: "Fabrication of fine-grained alumina ceramics by a novel process integrating stereolithography and liquid precursor infiltration processing", 《CERAMICS INTERNATIONAL》 * |
Cited By (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107382312B (en) * | 2017-07-11 | 2021-01-01 | 宁波匠心快速成型技术有限公司 | Preparation method of ceramic slurry for 3D printing and 3D printing forming method thereof |
| CN107382312A (en) * | 2017-07-11 | 2017-11-24 | 宁波匠心快速成型技术有限公司 | The preparation method and its 3D printing forming method of a kind of 3D printing ceramic slurry |
| CN107417262A (en) * | 2017-09-20 | 2017-12-01 | 吴江中瑞机电科技有限公司 | 3D printing technique prepares material of graded ceramicses and preparation method thereof |
| CN108033777A (en) * | 2017-10-31 | 2018-05-15 | 西安铂力特增材技术股份有限公司 | A kind of alumina slurry for photocuring technology and preparation method thereof |
| CN108456002A (en) * | 2018-02-08 | 2018-08-28 | 广东工业大学 | A method of being suitable for the 3D printing ceramic component based on Stereolithography of selfreparing/self-reinforcing |
| CN108814991B (en) * | 2018-06-21 | 2021-06-29 | 温州医科大学附属口腔医院 | Bionic enamel material and manufacturing method for manufacturing bionic tooth by using same |
| CN108814991A (en) * | 2018-06-21 | 2018-11-16 | 温州医科大学附属口腔医院 | A kind of bionical enamel material and its production method for being fabricated to bionical tooth |
| CN108675798B (en) * | 2018-08-03 | 2021-08-13 | 广东工业大学 | Silicon nitride ceramic and preparation method thereof |
| CN108675798A (en) * | 2018-08-03 | 2018-10-19 | 广东工业大学 | A kind of silicon nitride ceramics and preparation method thereof |
| CN109020605A (en) * | 2018-09-30 | 2018-12-18 | 广东工业大学 | A kind of ceramic material and its preparation method and application |
| CN109794301A (en) * | 2019-01-16 | 2019-05-24 | 武汉理工大学 | A kind of ceramic photocatalysis carrier structure based on increasing material manufacturing |
| CN109761615A (en) * | 2019-03-15 | 2019-05-17 | 广东工业大学 | A kind of preparation method of photocuring Behavior of Slurry for Aluminum Nitride Ceramics and aluminium nitride ceramics |
| CN109761615B (en) * | 2019-03-15 | 2021-10-29 | 广东工业大学 | Photocuring aluminum nitride ceramic slurry and preparation method of aluminum nitride ceramic |
| CN110028324A (en) * | 2019-05-29 | 2019-07-19 | 广东工业大学 | A kind of preparation method of nitride ceramics |
| CN110317001A (en) * | 2019-07-15 | 2019-10-11 | 威海市济合材料工程研究院 | A kind of light-cured resin of the 3D printing ZTA ceramics for DLP rapid shaping |
| CN110511017A (en) * | 2019-07-31 | 2019-11-29 | 映维(苏州)数字科技有限公司 | A kind of preparation method of rapid photocuring high solids content ceramic slurry |
| CN110511002A (en) * | 2019-09-26 | 2019-11-29 | 上海应用技术大学 | The method that DLP 3D printing technique prepares ZTA ceramic component |
| CN111925193A (en) * | 2020-07-17 | 2020-11-13 | 长沙理工大学 | 3D printing preparation method of fine-grain alumina ceramic |
| CN113878113A (en) * | 2021-08-30 | 2022-01-04 | 广东省科学院新材料研究所 | Ceramic-stainless steel composite material and preparation method thereof |
| CN114380583A (en) * | 2022-01-26 | 2022-04-22 | 重庆恩辰新材料科技有限责任公司 | Preparation method of ceramic material |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106699137A (en) | Method for preparing ZTA multi-phase ceramic through 3D printing based on stereo lithography appearance | |
| CN106673627A (en) | Method for preparing toughened aluminum oxide ceramic based on stereo lithography appearance namely 3D printing | |
| CN105198449B (en) | A kind of preparation method of the high ceramic of compact of Stereolithography | |
| CN105563616B (en) | The forming method of zirconia ceramic product | |
| CN105541324B (en) | The preparation method of phone housing | |
| CN108456002A (en) | A method of being suitable for the 3D printing ceramic component based on Stereolithography of selfreparing/self-reinforcing | |
| CN106966709A (en) | A kind of preparation method of transparent alumina ceramics | |
| CN104326766A (en) | Preparation method of porous silicon nitride ceramic material with spherical pore structure | |
| CN105218095B (en) | The method that yttrium aluminum garnet transparent ceramic is prepared using gel casting forming reaction-sintered | |
| CN106810215A (en) | A kind of preparation of ceramic size and 3D printing Stereolithography method | |
| WO2010048529A2 (en) | Compound transparent ceramics and methods of preparation thereof | |
| CN105330266A (en) | Preparation method of tooth-like special-shaped ceramics | |
| CN102825649B (en) | Method for preparing MgAlON transparent ceramic bisque by gel casting and molding | |
| CN103111585A (en) | Method for preparing ceramic gypsum composite mould by using magnesium alloy | |
| CN111331527B (en) | Ultra-high porosity ceramic bond diamond ultra-precision grinding tool and preparation method thereof | |
| CN106007709A (en) | Method for preparing high-strength ceramic through gel casting | |
| CN113716951B (en) | Preparation method of YAG-based transparent ceramic with large-size sheet composite structure | |
| CN107721424A (en) | A kind of method that gel casting forming prepares YAG crystalline ceramics | |
| CN105272223B (en) | A kind of preparation method of large scale oxidation zirconium base heat-barrier material | |
| CN110483008A (en) | A kind of slurry and its ceramic product preparation method for photocuring 3D printing ceramics | |
| CN105435303A (en) | Enhanced type bioactive glass scaffold and preparation method thereof | |
| US20210309575A1 (en) | Ceramic article production method and ceramic article | |
| CN110357642A (en) | Photocuring 3D printing slurry, preparation method and silicon nitride ceramics | |
| CN108395240A (en) | The preparation method of lanthanum orthophosphate, lanthanum orthophosphate porous ceramics and its preparation method and application | |
| CN111233493A (en) | Photo-curing silicon-based ceramic core biscuit sintering method for investment casting |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20170524 |