CN104108131B - 3D printing forming method for ceramic materials - Google Patents
3D printing forming method for ceramic materials Download PDFInfo
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- CN104108131B CN104108131B CN201410315556.XA CN201410315556A CN104108131B CN 104108131 B CN104108131 B CN 104108131B CN 201410315556 A CN201410315556 A CN 201410315556A CN 104108131 B CN104108131 B CN 104108131B
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- printing
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B28—WORKING CEMENT, CLAY, OR STONE
- B28B—SHAPING CLAY OR OTHER CERAMIC COMPOSITIONS; SHAPING SLAG; SHAPING MIXTURES CONTAINING CEMENTITIOUS MATERIAL, e.g. PLASTER
- B28B1/00—Producing shaped prefabricated articles from the material
- B28B1/001—Rapid manufacturing of 3D objects by additive depositing, agglomerating or laminating of material
Abstract
The invention provides a 3D printing forming method for ceramic materials. Sol with the low-temperature freezing feature is adopted to be mixed with powder such as ceramic or metal to be prepared into sizing with the freezing and coagulating property, the sizing is sprayed on a low-temperature printing platform through a printing nozzle to be frozen and coagulated, and various materials and products are printed layer by layer. According to the 3D printing forming method for the ceramic materials, the feature that some sol can be coagulated and solidified in a low-temperature freezing state is utilized, the preparing technology of raw materials is simple, convenient to conduct and fast, cost is low, coagulation and solidification can be achieved simply in the freezing state, and the application field of the 3D printing technology is expanded.
Description
Technical field
The present invention relates to a kind of 3D printing forming method of ceramic material, belong to function, structural ceramic material 3D printing skill
Art field.
Background technology
3D printing is a kind of 3D solid rapid prototyping ＆ manufacturing technology, combines computer graphical processing, digital information
With the advantage of the multinomial technology such as control, laser technology, mechanical ＆ electrical technology and material technology, this technology originate from 1988 be born
" rapid prototype manufacturing " technology.Rapid prototyping technique employs a kind of brand-new no mold freedom forming principle to manufacture three
Dimension entity component, obtains certain 3D shape by the method being gradually increased material.This forming method does not need mould, saves
Go the processes such as Design of Dies, manufacture and matched moulds, the demoulding, significantly shorten research and development and manufacturing cycle, reduce the one-tenth of product
This.
The basic functional principle of 3D printing is discrete-accumulation.First the physical form of product is passed through modeling software or three
Dimension scanner be converted into 3-dimensional digital stereomodel, will be discrete in Z axis for this model with delamination software, formed a series of have specific
The thin layer of thickness.Then using various methods, this series of thin layers is successively piled up.Eventually pass suitable post processing side
Method, obtains required product.
3D printing forming technique can be divided into two big class：The first kind is the forming method based on laser technology, such as stereolithography
(Sterolithography Apparatus, SLA), quires layer (Laminated Object Manufacturing, LOM),
Selective laser sintering (Select ive Laser Sintered, SLS), selective laser melting (Select ive Laser
Melted, SLM) etc.；Equations of The Second Kind is the forming method of non-laser technology, and such as fuse deposits (Fused Depos ition
Modeling, FDM), mask photocuring (Mask Stereolithography, MS), impact microgranule manufacture (Ballistic
Particle Manufacturing, BPM), entity grinding solidification (Solid Ground, SGC) etc..Come from current development
See, non-laser technology does not need the laser system of costliness, equipment reliability of operation preferably, has been over the 3D based on laser
Printing technique, becomes the main flow of rapid shaping technique.But these 3D printing techniques require higher, such as powder to the raw material being adopted
The shape and size of body raw material will be easy to transport, photocuring raw material then will add dispersant, polymerization inhibitor, many according to technological requirement
Plant the compositions such as light trigger, these raw materials are generally required to be synthesized by special producer according to certain principles and equipment or manufacture,
Limit the further genralrlization application of 3D printing technique.
Content of the invention
It is an object of the invention to overcoming prior art not enough, there is provided a kind of versatility is good, low cost, be easy to promote
The 3D printing forming method of ceramic material.
The technical solution of the present invention：A kind of 3D printing forming method of ceramic material, comprises the following steps：
Set up the threedimensional model of product, layered shaping is carried out to model, set up 3D printing program.
In threedimensional model, the thickness of each layering cross section structure can not be too thick, otherwise can affect the combination between two-layer, and three
In dimension module, the thickness of each layering cross section structure can meet requirement less than 0.5mm.
Preparation has the slurry of freezing gel property,
The slurry with freezing gel property is formed by colloidal sol and powder material mix homogeneously, the colloidal sol selected by the present invention
Meeting gel solidification under freezing state, still keeps shape when freezing and chi when the base substrate of solidification is more than thaw point
Very little, also notable deformation and contraction after being fully dried.Conventional such colloidal sol with freezing gel property include Ludox,
Alumina gel, mullite sol and zirconium colloidal sol, but be not limited, preferably solid volume fraction is 10～25% Ludox.Powder
Body raw material includes ceramic powder or the powder body etc. containing metallic element, can by the oxide of metal and/or one or more element,
Mixed oxide, nitride or carbide composition, metal can be with magnesium, aluminum, potassium, calcium, titanium, ferrum, copper, zinc, stannum, lead etc., element bag
Include boron, sodium, magnesium, aluminum, silicon, potassium, calcium, ferrum, copper, zinc, yttrium, zirconium, stannum, lead, barium etc., concrete powder body species is according to product to be prepared
Product determine.Also can need to add other additives such as dispersant, binding agent according to technique in slurry.
The slurry with freezing gel property will have mobility, can be transported under pressure by pipeline, its solid phase
Volume fraction is 35～85%, can guarantee that being smoothed out of follow-up 3D printing, if solid volume fraction is too little, slurry is too dilute,
3D printing process is also easy to produce trickling, is unfavorable for gel；If solid volume fraction is too big, slurry is too thick, in the injection of 3D printing process
Have some setbacks, be unfavorable for printing.
The work platformses of 3D printing equipment are placed in reefer space；
The temperature of reefer space will be less than the freezing point of the slurry with freezing gel property, and slurry at such a temperature can be with
Certain rate freezers gel solidification.Typically have the colloidal sol of freezing gel property≤- 40 DEG C in the case of all can freeze
Gel, is most commonly filled with liquid nitrogen in Engineering operation.
3D printing, 3D printing equipment sprays on work platformses according to 3D printing preset program and has freezing gel property
Slurry, obtains the model base substrate of 3D printing.
Start 3D printing equipment, printhead moves to y direction guiding rail along x, spray slurry according to predetermined print routine, complete
Become first layer section print after, work platformses along z to decline a thickness, carry out the printing in the second layering section, repeat on
State process, successively complete the printing that threedimensional model is respectively layered section, obtain model base substrate.
The jet velocity of slurry should not be too fast, with selected collosol and gel speed as standard it is ensured that slurry can complete cold
Congeal glue, be typically advisable in 2～200mL/h, selected as the case may be；Two in printhead or work platformses motor process
The relative velocity of person is unsuitable too fast, corresponding with the jet velocity of slurry and every layer of print thickness, is typically advisable in 1～100mm/s,
Selected as the case may be；The distance that printhead and the threedimensional model printing are layered section is≤10mm, and distance is too
Far, the seriality of the slurry ejecting is bad, forms drop, is unfavorable for that slurry forms uniform material in each layering section.
Being dried according to technological requirement and/or sintering of the model base substrate of 3D printing, obtains final products.
Body drying mode is lyophilization and/or is commonly dried, temperature is≤100 DEG C, and pressure condition is negative pressure or normal
Pressure.The sintering processing of base substrate is air calcination, pressureless sintering, gas pressure sintering or hot pressed sintering.
Present invention beneficial effect compared with prior art：
(1) present invention utilizes the characteristic of some colloidal sols meeting gel solidification under freezing state, raw material preparation technology
Simple and efficient, low cost, as long as can gel solidification in a cold or frozen state, expanded the application of 3D printing technique；
(2) 3D printing of the present invention need not special printing device, equipment is simple, only work platformses need to be placed in freezing environment
In, without the need for Design of Dies and manufacture, shorten development and production cycle, reduce cost；
(3) blank strength of molding of the present invention is high, and uniformity is good, can be used for preparing the product of various sizes and complicated shape
Product；
(4) the 3D forming method based on freezing gel for the present invention, low cost, versatility are good, are easy to be extended and applied.
Figure of description
Fig. 1 is process principle figure of the present invention；
Fig. 2 is present configuration schematic diagram.
Specific embodiment
The present invention utilizes some colloidal sols meeting gel solidification under freezing state, and the base substrate of solidification is more than thaw point
When still keep when freezing shape and size, also notable after being fully dried deform and shrink.Based on this property of colloidal sol,
The slurry with freezing gel property is prepared by mixing into powder body such as pottery or metals using the colloidal sol with freezing characteristic,
Slurry is injected in freezing, gel solidification on the print platform of low temperature by printhead, successively prints and obtains various types of materials and product.
The present invention is as shown in figure 1, realized by following steps：
1st, set up the threedimensional model of product as shown in Figure 2, model is carried out with layered shaping, the thickness of each layering cross section structure
Spend for≤0.5mm, set up print routine.
2nd, adopt ball milling or high-speed stirred technique that colloidal sol is mixed homogeneously with ceramic powder or metal powder etc., obtain having cold
Freeze the slurry of gelling properties, its solid volume fraction is 35～85%, and this slurry is added to syringe pump 3, and (as shown in Figure 2 beats
Printing apparatus) storage tank in.
The 3rd, the temperature in target product place space on print job platform 2, temperature≤- 40 DEG C of reefer space are set.
4th, start printing device, printhead 1 moves along x direction guiding rail 4 and y direction guiding rail 5, according to pre- under syringe pump 3 drives
Determine program injection slurry, the jet velocity of slurry is 2～200mL/h, complete after first layer section prints, work platformses are along z
Direction guiding rail 6 declines a thickness, carries out the printing in the second layering section, repeats said process, successively completes each point of threedimensional model
The printing of layer cross section, obtains model base substrate.During printing, in printhead 1 or work platformses 2 motor process, both relative velocities are
1～100mm/s, the distance that printhead 1 and the threedimensional model printing are layered section is≤10mm.
5th, base substrate temperature be 1～100 DEG C common or vacuum drying oven in dry moisture, complete the molding of product.
To explain in detail the present invention below by way of accompanying drawing and instantiation.
Embodiment 1
Set up three-dimensional entity model using computer, along z to generating the stratified model that every thickness degree is 2.0mm, complete every
The scanning pattern program of layer cross section.
Measure 100mL Ludox, solid volume fraction is 23%；Weigh 176g silicon-dioxide powdery, particle diameter is 15 microns,
Purity is 98%.By above-mentioned raw materials mix homogeneously under high velocity agitation, obtain the slurry that solid volume fraction is 72%, add note
Penetrate in the storage tank of pump.
Setting print job platform temperature is -75 DEG C, and the jet velocity of setting printhead is 30mL/h, printhead and printing
The distance of platform is 1.5mm.
Start printing device, run print routine, printhead completes first layer section according to default scanning pattern
Print.Work platformses decline 2.0mm, start the second layering section and print, said process circulation is carried out, and successively obtains model base
Body.
Base substrate is transferred in drying baker, dries 48h at 40 DEG C, complete the molding of silica article.
Embodiment 2
Set up three-dimensional entity model using computer, along z to generating the stratified model that every thickness degree is 1.0mm, complete every
The scanning pattern program of layer cross section.
Weigh 88.96 grams of beta-silicon nitride powders, α phase content is 93%, and particle diameter is 0.40～0.60 micron；Weigh 81.98 grams
Aluminium nitride powder, particle diameter is 0.50～6.00 micron, and purity is 98.5%；Weigh 20 grams of silicon-dioxide powderies, particle diameter is micro- for 15
Rice, purity is 98%；Weigh 11 grams of yttrium oxide powders, particle diameter is 0.6～0.8 micron, purity is 99.5%；Measure 80 milliliter two
Silica sol, its solid concentration is 23%；By above-mentioned powder body and colloidal sol mixing, after 30 minutes, obtain solid content is ball milling
57% slurry, adds in the storage tank of syringe pump.
Setting print job platform temperature is -196 DEG C (reefer space topping up nitrogen), and the jet velocity of setting printhead is
10mL/h, printhead is 1.5mm with the distance of print platform.
Start printing device, run print routine, printhead completes first layer section according to default scanning pattern
Print.Work platformses decline 1.0mm, start the second layering section and print, said process circulation is carried out, and successively obtains model base
Body.
Base substrate is transferred in drying baker, dries 48h at 40 DEG C, complete the molding of Sialon ceramic.
Embodiment 3
Set up three-dimensional entity model using computer, along z to generating the stratified model that every thickness degree is 0.5mm, complete every
The scanning pattern program of layer cross section.
Measure 20mL Alumina gel, solid volume fraction is 12%；Weigh 28g alumina powder jointed, particle diameter is 8 microns, purity
For 99%.By above-mentioned raw materials mix homogeneously under high velocity agitation, obtain the slurry that solid volume fraction is 35%, add syringe pump
Storage tank in.
Setting print job platform temperature is -196 DEG C, and the jet velocity of setting printhead is 2mL/h, printhead and printing
The distance of platform is 1.0mm.
Start printing device, run print routine, printhead completes first layer section according to default scanning pattern
Print.Work platformses decline 0.5mm, start the second layering section and print, said process circulation is carried out, and successively obtains model base
Body.
Base substrate is transferred in vacuum drying oven, is vacuum dried 36h at 30 DEG C, completes the molding of alumina article.
Unspecified part of the present invention is known to the skilled person technology.
Claims (4)
1. a kind of 3D printing forming method of ceramic material is it is characterised in that comprise the following steps：
Preparation has the slurry of freezing gel property,
The slurry with freezing gel property is formed by colloidal sol and powder material mix homogeneously, the consolidating of the slurry of freezing gel property
Phase volume fraction is 35～85%；
The work platformses of 3D printing equipment are placed in reefer space；With
3D printing equipment sprays the slurry with freezing gel property according to 3D printing preset program on work platformses, obtains 3D
The model base substrate printing,
In described 3D printing preset program, the thickness of each layering cross section structure of threedimensional model is≤0.5mm, 3D printing
The distance that in journey, the printhead of 3D equipment is layered section with the current threedimensional model printing is≤10mm, and the jet velocity of slurry is
2～200mL/h；In printhead or work platformses motor process, both relative velocities are 1～100mm/s.
2. a kind of ceramic material according to claim 1 3D printing forming method it is characterised in that：Described colloidal sol is bag
Include Ludox, Alumina gel, mullite sol or zirconium colloidal sol.
3. a kind of ceramic material according to claim 1 3D printing forming method it is characterised in that：Described reefer space
Temperature be≤- 40 DEG C.
4. a kind of ceramic material according to claim 1 3D printing forming method it is characterised in that：Described powder material
Powder body including ceramic powder or containing metallic element.
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| CN201410315556.XA CN104108131B (en) | 2014-07-04 | 2014-07-04 | 3D printing forming method for ceramic materials |
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| CN201410315556.XA CN104108131B (en) | 2014-07-04 | 2014-07-04 | 3D printing forming method for ceramic materials |
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| CN104108131A CN104108131A (en) | 2014-10-22 |
| CN104108131B true CN104108131B (en) | 2017-02-22 |
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| CN105777180A (en) * | 2016-03-01 | 2016-07-20 | 贵州师范大学 | Method for preparing porous silicon nitride through three-dimensional printing |
| CN106003363B (en) * | 2016-05-20 | 2018-09-11 | 西安工业大学 | A kind of 3D printing method of bioceramic green body |
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| CN107698261B (en) * | 2017-07-26 | 2019-11-22 | 航天特种材料及工艺技术研究所 | A kind of 3D printing ceramic material |
| CN107696233B (en) * | 2017-07-26 | 2019-07-09 | 航天特种材料及工艺技术研究所 | A kind of ceramics 3D printing equipment |
| CN107698260B (en) * | 2017-07-26 | 2019-09-13 | 航天特种材料及工艺技术研究所 | A kind of molding method of ceramics 3D printing |
| CN110355991A (en) * | 2018-04-09 | 2019-10-22 | 北京大学 | 3D printing method and 3D printing equipment |
| CN108582416B (en) * | 2018-04-25 | 2020-09-08 | 湖南筑巢智能科技有限公司 | Manufacturing method of large and medium ceramic ware |
| CN109485430B (en) * | 2018-11-30 | 2021-09-07 | 中南大学 | Method for preparing bionic porous ceramic with complex three-dimensional structure |
| CN110815491B (en) * | 2019-11-19 | 2021-05-11 | 航天特种材料及工艺技术研究所 | 3D (three-dimensional) freezing printing method of ceramic component |
| CN111943688B (en) * | 2020-08-21 | 2022-04-26 | 航天特种材料及工艺技术研究所 | 3D (three-dimensional) freezing printing method |
| CN112299855B (en) * | 2020-11-16 | 2022-05-13 | 中国工程物理研究院材料研究所 | MgAlON ceramic powder preparation method based on 3D printing forming |
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| CN1270883A (en) * | 1999-08-18 | 2000-10-25 | 仲伟虹 | Equipment and process for layer manufacture |
| DE102006055281B4 (en) * | 2006-11-23 | 2009-02-12 | Universität Bremen | Process for producing a ceramic shaped body |
| CN1962547A (en) * | 2006-12-06 | 2007-05-16 | 中国科学院上海硅酸盐研究所 | Method for preparing alumina porous ceramic using gelatin wrapping-freeze drying process |
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| CN104108131A (en) | 2014-10-22 |
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