CN117164330A - 3D printing ceramic slurry and preparation method thereof, and preparation method of ceramic material - Google Patents
3D printing ceramic slurry and preparation method thereof, and preparation method of ceramic material Download PDFInfo
- Publication number
- CN117164330A CN117164330A CN202311098366.2A CN202311098366A CN117164330A CN 117164330 A CN117164330 A CN 117164330A CN 202311098366 A CN202311098366 A CN 202311098366A CN 117164330 A CN117164330 A CN 117164330A
- Authority
- CN
- China
- Prior art keywords
- printing
- ceramic
- gelatin
- ceramic slurry
- powder
- 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
- 239000000919 ceramic Substances 0.000 title claims abstract description 188
- 239000002002 slurry Substances 0.000 title claims abstract description 111
- 238000010146 3D printing Methods 0.000 title claims abstract description 83
- 229910010293 ceramic material Inorganic materials 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 35
- 238000007613 slurry method Methods 0.000 title description 2
- 108010010803 Gelatin Proteins 0.000 claims abstract description 120
- 239000008273 gelatin Substances 0.000 claims abstract description 120
- 229920000159 gelatin Polymers 0.000 claims abstract description 120
- 235000019322 gelatine Nutrition 0.000 claims abstract description 120
- 235000011852 gelatine desserts Nutrition 0.000 claims abstract description 120
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims abstract description 109
- 239000000843 powder Substances 0.000 claims abstract description 65
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 51
- 238000007639 printing Methods 0.000 claims description 76
- 235000011187 glycerol Nutrition 0.000 claims description 39
- 238000000034 method Methods 0.000 claims description 33
- 239000000463 material Substances 0.000 claims description 25
- 239000002245 particle Substances 0.000 claims description 23
- 230000008569 process Effects 0.000 claims description 22
- 239000004927 clay Substances 0.000 claims description 21
- BPJYAXCTOHRFDQ-UHFFFAOYSA-L tetracopper;2,4,6-trioxido-1,3,5,2,4,6-trioxatriarsinane;diacetate Chemical compound [Cu+2].[Cu+2].[Cu+2].[Cu+2].CC([O-])=O.CC([O-])=O.[O-][As]1O[As]([O-])O[As]([O-])O1.[O-][As]1O[As]([O-])O[As]([O-])O1 BPJYAXCTOHRFDQ-UHFFFAOYSA-L 0.000 claims description 20
- 230000008021 deposition Effects 0.000 claims description 19
- 238000000498 ball milling Methods 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 18
- 238000001354 calcination Methods 0.000 claims description 17
- 238000003756 stirring Methods 0.000 claims description 17
- 238000002156 mixing Methods 0.000 claims description 14
- 238000007873 sieving Methods 0.000 claims description 7
- 238000007493 shaping process Methods 0.000 claims description 5
- 240000000760 Viola betonicifolia Species 0.000 claims 1
- 239000000499 gel Substances 0.000 abstract description 17
- 239000011230 binding agent Substances 0.000 abstract description 10
- 239000012752 auxiliary agent Substances 0.000 abstract description 6
- 239000004014 plasticizer Substances 0.000 abstract description 3
- 239000011343 solid material Substances 0.000 abstract description 3
- 230000007704 transition Effects 0.000 abstract description 3
- 238000009827 uniform distribution Methods 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 39
- 230000000052 comparative effect Effects 0.000 description 14
- 238000000465 moulding Methods 0.000 description 10
- 238000005245 sintering Methods 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 238000005360 mashing Methods 0.000 description 5
- 238000012216 screening Methods 0.000 description 5
- 238000012512 characterization method Methods 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 241001408630 Chloroclystis Species 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000000227 bioadhesive Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 235000012438 extruded product Nutrition 0.000 description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 238000005498 polishing Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000013530 defoamer Substances 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000000703 high-speed centrifugation Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052622 kaolinite Inorganic materials 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/60—Production of ceramic materials or ceramic elements, e.g. substitution of clay or shale by alternative raw materials, e.g. ashes
Abstract
The application provides 3D printing ceramic slurry, a preparation method thereof and a preparation method of a ceramic material. The ceramic slurry comprises ceramic powder, glycerol, gelatin and water; gelatin is soluble in hot water, and when the warm gelatin water solution is cooled, the viscosity of the gelatin water solution gradually rises, and if the concentration is large enough, the temperature is low enough, and the gelatin water solution is converted into gel; gelatin gels resemble solid materials, are capable of retaining their shape, and are elastic; the glycerol is used as a plasticizer, so that the viscosity and the sol-gel transition temperature of the gelatin can be increased, and the uniform distribution of ceramic powder is induced. The viscosity of the ceramic slurry is obviously increased after the binder gelatin is added, and the viscosity of the gelatin can be correspondingly increased after the auxiliary agent glycerol is added, so that the viscosity of the ceramic slurry is further increased, and the cohesiveness and plasticity of the ceramic slurry are effectively increased.
Description
Technical Field
The application relates to the technical field of ceramic material preparation, in particular to 3D printing ceramic slurry and a preparation method thereof, and a preparation method of a ceramic material.
Background
Extrusion stacking forming is a rapid forming technology capable of forming complex shapes in a short time and having certain functional components, and has been developed rapidly due to the advantages of simple operation, high forming efficiency, low cost and the like. The method is mainly divided into direct writing (Direct Ink Writing, DIW) and fused deposition (Fused Deposition Modeling, FDM), wherein during DIW, the adopted ink has certain rheological properties (such as viscoelasticity, shear thinning, yield stress and the like) generally, and the viscoelasticity ink is extruded from a nozzle of a 3D printer to form fibers, and can be deposited into a specific pattern along with the movement of the nozzle. While FDM is a method of melting by heating, the material is continuously supplied to a cylinder at a temperature slightly higher than the melting point thereof, and heated therein and extruded through a nozzle, thereby realizing fused deposition modeling.
Because most traditional ceramic materials have lower plasticity, certain plastic materials are often required to be added in the 3D printing process to facilitate molding, and firstly, organic synthetic resin is added to enhance the plasticity, the defects of high cost and large addition proportion of the additive, the requirement of subsequent degreasing treatment, large shrinkage rate of the finished product and environmental protection are overcome. Secondly, extrusion molding conditions, such as kaolin, clay, bentonite and the like, are realized by adding high-quality pug with good plasticity. The defects are that the cost is increased, the color of the finished product is affected, more important plastic pugs cannot be removed after ceramic sintering, the ceramic sintered body is impure, and the pugs are not preferable for some ceramic sintered bodies with requirements on functions and textures. Thirdly, the addition of a polymeric binder has the disadvantage that it generally requires mixing with ceramic particles to produce a linear material, which is cumbersome and requires high energy consumption equipment with a relatively high printing temperature.
In summary, the existing ceramic materials for 3D printing have large environmental pollution, high production cost and poor product performance, and are difficult to meet the actual demands of industrial and large-scale production, so that the existing ceramic materials for 3D printing are required to be improved.
Disclosure of Invention
In view of the above, the present application provides a 3D printing ceramic slurry, a preparation method thereof, and a preparation method of ceramic material, so as to solve or at least partially solve the defects existing in the prior art.
In a first aspect, the present application provides a 3D printing ceramic slurry comprising ceramic powder and a gelatin solution comprising glycerol, gelatin and water.
Preferably, the mass ratio of glycerin, gelatin and water in the gelatin solution is (0.1-1): 1:10.
Preferably, the mass ratio of the ceramic powder to the gelatin solution of the 3D printing ceramic slurry is 1 (0.3-0.5).
Preferably, the 3D printing ceramic slurry is at least one of the ceramic powder of Benshan green mud, miao blue and Benshan purple mud.
In a second aspect, the application also provides a preparation method of the 3D printing ceramic slurry, which comprises the following steps:
mixing glycerol with water, adding gelatin, and stirring to obtain gelatin solution;
and adding the ceramic powder into the gelatin solution, and stirring to obtain the 3D printing ceramic slurry.
Preferably, the preparation method of the 3D printing ceramic slurry further comprises ball milling treatment of the ceramic powder before adding the ceramic powder into the gelatin solution, wherein the ball milling treatment specifically comprises the following steps: placing the ceramic powder into a ball mill for ball milling and sieving; wherein the rotating speed of the ball mill is 300-600 r/min, and the ball milling time is 1-3 h; and sieving to obtain ceramic powder with particle size less than or equal to 62 μm.
Preferably, in the preparation method of the 3D printing ceramic slurry, after glycerin and water are mixed, gelatin is added, and in the step of stirring to obtain gelatin solution, the stirring speed is 300-500 rpm, and the stirring time is 20-30 min.
In a third aspect, the present application also provides a method for preparing a ceramic material, comprising the steps of:
providing the 3D printing ceramic slurry or the 3D printing ceramic slurry prepared by the preparation method;
according to a three-dimensional model of the ceramic material to be manufactured, utilizing the 3D printing ceramic slurry, and obtaining a printing piece by adopting a fused deposition modeling process;
drying the printing piece, and calcining to obtain a ceramic material;
or placing the 3D printing ceramic slurry in a mould for shaping, drying to obtain a clay blank, drying the clay blank, and calcining to obtain the ceramic material.
Preferably, in the preparation method of the ceramic material, in the step of obtaining the printed part by adopting a fused deposition modeling process, the controlled technological parameters are as follows: the inner diameter of the nozzle of the printing needle head is 0.5-1.2 mm, the height of the printing layer is 0.2-0.5 mm, the printing speed is 50-100 mm/min, and the printing temperature is 30-40 ℃.
Preferably, the preparation method of the ceramic material further comprises the step of carrying out centrifugal defoaming treatment on the 3D printing ceramic slurry before obtaining a printing piece by using the 3D printing ceramic slurry and adopting a fused deposition modeling process, wherein the centrifugal speed is 2500-4300 rpm, and the centrifugal treatment time is 10-20 min;
the calcination temperature is 1100-1200 ℃ and the calcination time is 24-36 h.
Compared with the prior art, the application has the following technical effects:
1. the 3D printing ceramic slurry comprises ceramic powder, glycerol, gelatin and water; gelatin is soluble in hot water, and when the warm gelatin water solution is cooled, the viscosity of the gelatin water solution gradually rises, and if the concentration is large enough, the temperature is low enough, and the gelatin water solution is converted into gel; gelatin gels resemble solid materials, are capable of retaining their shape, and are elastic; the glycerol is used as a plasticizer, so that the viscosity of gelatin and the sol-gel transition temperature can be increased, and the uniform distribution of ceramic powder is induced. The viscosity of the ceramic slurry is obviously increased after the binder gelatin is added, and the viscosity of the gelatin can be correspondingly increased after the auxiliary agent glycerol is added, so that the viscosity of the ceramic slurry is further increased, and the cohesiveness and plasticity of the ceramic slurry are effectively increased;
2. according to the preparation method of the ceramic material, the sol-gel method is adopted for molding, the ceramic slurry is in a sol form in the printing cylinder, and is immediately converted into a gel form when extruded out of the substrate, so that the molding speed is high, the ceramic material can be moved after printing, and standing is not needed to wait for water evaporation; the ceramic slurry is extruded in a sol state, so that the ceramic slurry has certain fluidity, the surface of an extruded product is smooth, no obvious layering exists, and subsequent polishing treatment is not needed; the application adopts a natural adhesive which is soluble in water, nontoxic and pollution-free, can be rapidly formed through sol-gel conversion, can be suitable for various ceramic raw materials, and does not change the properties of original finished products of the ceramic materials, such as components, color, stability and the like; the application can improve the mechanical property of the 3D printing ceramic product by utilizing sol-gel molding, reduce the occurrence of problems such as collapse, cracking, shrinkage, deformation and the like, and improve the dimensional accuracy of the product.
Drawings
In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below. It is evident that the drawings in the following description are only some embodiments of the present application and that other drawings may be obtained from these drawings without inventive effort for a person of ordinary skill in the art.
FIG. 1 is viscosity data for an unadditized ceramic slurry (comprising 49.2g and 50.8g water), a gelatin-added ceramic slurry (comprising 49.2g Benshan green mud, 4.2g gelatin and 46.6g water), and a gelatin-and-glycerin-added ceramic slurry (comprising 49.2g Benshan green mud, 4.2g glycerin, 4.2g gelatin and 42.2g water);
FIG. 2 is surface Rockwell hardness data of the ceramic products prepared in comparative example 2 and example 2;
FIG. 3 is an XRD (X-ray diffraction) characterization of the ceramic products prepared in comparative example 2 and example 2;
FIG. 4 is a photograph of a master blank of the printing of comparative example 1;
FIG. 5 is a photograph of a master blank of the printing member of example 1;
FIG. 6 is a diagram showing an example of a ceramic product obtained by sintering a ceramic frit provided in example 1 after 3D printing and molding of a mixed frit of binder gelatin and glycerin;
fig. 7 is an SEM (scanning electron microscope) characterization diagram of a ceramic finished product obtained by sintering a ceramic frit provided in example 1 after 3D printing and molding of a mixed frit of binder gelatin and glycerin.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present application more clear, the technical solutions of the embodiments of the present application will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present application. It will be apparent that the described embodiments are some, but not all, embodiments of the application.
The following description of the embodiments of the present application will be made in detail and with reference to the embodiments of the present application, but it should be apparent that the described embodiments are only some embodiments of the present application, and not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the present application without making any inventive effort, are intended to fall within the scope of the present application.
The following description of the embodiments is not intended to limit the preferred embodiments. In addition, in the description of the present application, the term "comprising" means "including but not limited to". Various embodiments of the application may exist in a range of forms; it should be understood that the description in a range format is merely for convenience and brevity and should not be construed as a rigid limitation on the scope of the application; it is therefore to be understood that the range description has specifically disclosed all possible sub-ranges and individual values within that range. For example, it should be considered that a description of a range from 1 to 6 has specifically disclosed sub-ranges, such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 to 6, etc., as well as single numbers within the ranges, such as 1, 2, 3, 4, 5, and 6, wherever applicable. In addition, whenever a numerical range is referred to herein, it is meant to include any reference number (fractional or integer) within the indicated range.
The 3D printing ceramic slurry comprises ceramic powder and gelatin solution, wherein the gelatin solution comprises glycerol, gelatin and water.
In some embodiments, the mass ratio of glycerin, gelatin, and water in the gelatin solution is (0.1-1): 1:10.
In some embodiments, the mass ratio of ceramic powder to gelatin solution is 1 (0.3-0.5).
In some embodiments, the ceramic powder comprises the present mountain green mud 、 At least one of mud materials such as the bottom groove green and the purple mud of the present mountain.
Specifically, the present mountain green mud used in the present application 、 Ceramic powder such as the bottom groove green, the purple mud of the mountain and the like are all from the Yixing city Tao Gongsu five-color mill purple sand institute.
Specifically, the mountain green mud comprises hydromica, kaolinite, quartz and a small amount of iron oxide.
The 3D printing ceramic slurry comprises ceramic powder, glycerol, gelatin and water; gelatin is soluble in hot water, and when the warm gelatin water solution is cooled, the viscosity of the gelatin water solution gradually rises, and if the concentration is large enough, the temperature is low enough, and the gelatin water solution is converted into gel; gelatin gels resemble solid materials, are capable of retaining their shape, and are elastic; the glycerol is used as a plasticizer, so that the viscosity of gelatin and the sol-gel transition temperature can be increased, and the uniform distribution of ceramic powder is induced. The viscosity of the ceramic slurry is obviously increased after the binder gelatin is added, and the viscosity of the gelatin can be correspondingly increased after the auxiliary agent glycerol is added, so that the viscosity of the ceramic slurry is further increased, and the cohesiveness and plasticity of the ceramic slurry are effectively increased.
Based on the same inventive concept, the application also provides a preparation method of the 3D printing ceramic slurry, which comprises the following steps:
s1, mixing glycerol with water, adding gelatin, and stirring to obtain a gelatin solution;
and S2, adding the ceramic powder into the gelatin solution, and stirring to obtain the 3D printing ceramic slurry.
In some embodiments, the adding of the ceramic powder to the gelatin solution further comprises ball milling the ceramic powder, the ball milling specifically comprising: placing the ceramic powder into a ball mill for ball milling and sieving; wherein the rotating speed of the ball mill is 300-600 r/min, and the ball milling time is 1-3 h; and sieving to obtain ceramic powder with particle size less than or equal to 62 μm.
Specifically, the ceramic powder is crushed into block particles after being dried, the block particles are put into a ball mill for ball milling into high-definition powder, and then the powder is sieved to obtain the ceramic powder with uniform size, wherein the rotation speed of the ball mill is 300-600 r/min, and the ball milling time is 1-3 h; and sieving to obtain ceramic powder with particle size less than or equal to 62 μm.
In some embodiments, after mixing glycerol with water, gelatin is added and the step of stirring to obtain a gelatin solution is performed at a stirring rate of 300 to 500rpm for 20 to 30 minutes.
Based on the same inventive concept, the application also provides a preparation method of the ceramic material, which comprises the following steps:
s1, providing the 3D printing ceramic slurry or the 3D printing ceramic slurry prepared by the preparation method;
s2, according to a three-dimensional model of the ceramic material to be manufactured, utilizing 3D printing ceramic slurry, and adopting a fused deposition modeling process to obtain a printing piece;
s3, drying the printing piece, and calcining to obtain a ceramic material;
or placing the 3D printing ceramic slurry in a mould for shaping, drying to obtain a clay blank, drying the clay blank, and calcining to obtain the ceramic material.
Specifically, 3D printing ceramic slurry is injected into a printing material pipe of 3D printing equipment, the printing material pipe is preheated according to a three-dimensional model of ceramic materials to be manufactured, technological parameters are adjusted, 3D printing is carried out, a printing part clay blank is obtained, the printing part clay blank is placed into an oven to be dried, then the printing part clay blank is placed into a muffle furnace to be calcined, and finally a ceramic finished product is obtained, namely the ceramic materials.
In some embodiments, in the step of obtaining a printed article using a fused deposition modeling process, the process parameters are controlled as follows: the inner diameter of the nozzle of the printing needle head is 0.5-1.2 mm, the height of the printing layer is 0.2-0.5 mm, the printing speed is 50-100 mm/min, and the printing temperature is 30-40 ℃.
In some embodiments, a fused deposition modeling process is adopted to obtain a printing part clay blank, and then the printing part clay blank is dried and calcined to obtain a ceramic product, namely a ceramic material; wherein the drying temperature is 45-60 ℃ and the drying time is 12-24 h.
In some embodiments, the method further comprises the step of carrying out centrifugal defoaming treatment on the 3D printing ceramic slurry before obtaining the printing piece by adopting a fused deposition modeling process, wherein the centrifugal rotation speed is 2500-4300 rpm, and the centrifugal treatment time is 10-20 min; the air in the slurry is removed by high-speed centrifugation of the ceramic slurry in a centrifuge.
In some embodiments, the calcination temperature is 1100-1200 ℃ and the calcination time is 24-36 hours.
In some embodiments, the 3D printed ceramic slurry is placed in a mold to set while vacuum defoaming treatment is performed in a defoamer or centrifuge for 0.1 to 1 hour.
According to the preparation method of the ceramic material, the sol-gel method is adopted for molding, the ceramic slurry is in a sol form in the printing cylinder, and is immediately converted into a gel form when extruded out of the substrate, so that the molding speed is high, the ceramic material can be moved after printing, and standing is not needed to wait for water evaporation; the ceramic slurry is extruded in a sol state, so that the ceramic slurry has certain fluidity, the surface of an extruded product is smooth, no obvious layering exists, and subsequent polishing treatment is not needed; the application adopts a natural adhesive which is soluble in water, nontoxic and pollution-free, can be rapidly formed through sol-gel conversion, can be suitable for various ceramic raw materials, and does not change the properties of original finished products of the ceramic materials, such as components, color, stability and the like; the application can improve the mechanical property of the 3D printing ceramic product by utilizing sol-gel molding, reduce the occurrence of problems such as collapse, cracking, shrinkage, deformation and the like, and improve the dimensional accuracy of the product.
The 3D printing ceramic slurry and the preparation method thereof, and the preparation method of the ceramic material according to the present application are further described in specific examples. This section further illustrates the summary of the application in connection with specific embodiments, but should not be construed as limiting the application. The technical means employed in the examples are conventional means well known to those skilled in the art, unless specifically stated. Unless specifically stated otherwise, the reagents, methods and apparatus employed in the present application are those conventional in the art.
Example 1
The embodiment of the application provides 3D printing ceramic slurry, which comprises ceramic powder and gelatin solution, wherein the gelatin solution comprises glycerol, gelatin and water;
wherein the ceramic powder is 49.2g of Benshan green mud, and the gelatin solution comprises 4.2g of glycerin, 4.2g of gelatin and 42.2g of water.
The preparation method of the 3D printing ceramic slurry comprises the following steps:
s1, drying the mountain green mud material, mashing the mountain green mud material into block-shaped particles, putting the block-shaped particles into a ball mill, ball milling for 1h at 300r/min to obtain high-definition powder, and screening to obtain the mountain green mud powder with the particle size of less than 62 mu m;
s2, mixing 4.2g of glycerol with 42.2g of deionized water to form a gelatin solvent, dissolving 4.2g of gelatin in the gelatin solvent, and placing the gelatin solvent on a magnetic stirrer to stir at 300rpm for 20min to obtain a gelatin solution;
and S3, adding 49.2g of the mountain green mud powder in the S1 into the gelatin solution in the S2, and uniformly mixing under a stirrer to obtain the 3D printing ceramic slurry.
The embodiment of the application also provides a preparation method of the ceramic material, which comprises the following steps:
s1, providing the 3D printing ceramic slurry prepared in the embodiment 1;
s2, printing ceramic slurry by using 3D according to a three-dimensional model (particularly a teacup model) of a ceramic material to be manufactured, and obtaining a printing part clay blank by adopting a fused deposition modeling process; before printing, carrying out centrifugal defoaming treatment on the 3D printing ceramic slurry, wherein the centrifugal rotating speed is 3500rpm, and the centrifugal treatment time is 10min; in the step of obtaining a printed piece by adopting a fused deposition modeling process, 3D printing ceramic slurry is injected into a printing material pipe, the printing material pipe is preheated for 30min at 40 ℃, then the printing material pipe is adjusted to 38 ℃ for printing, and the controlled printing process parameters are as follows: the inner diameter of the nozzle of the printing needle head is 1.2mm, the height of the printing layer is 0.5mm, and the printing speed is 100mm/min;
s3, placing the printing piece clay blank in an oven to be dried for 12 hours at 60 ℃;
and S4, placing the dried printing piece clay blank into a muffle furnace, calcining for 24 hours at the temperature of 1150 ℃, and finally obtaining a ceramic finished product.
Example 2
The embodiment of the application provides 3D printing ceramic slurry, which comprises ceramic powder and gelatin solution, wherein the gelatin solution comprises glycerol, gelatin and water;
wherein the ceramic powder is 49.2g of Benshan green mud, and the gelatin solution comprises 4.2g of glycerin, 4.2g of gelatin and 42.2g of water.
The preparation method of the 3D printing ceramic slurry comprises the following steps:
s1, drying the mountain green mud material, mashing the mountain green mud material into block-shaped particles, putting the block-shaped particles into a ball mill, ball milling for 1h at 300r/min to obtain high-definition powder, and screening to obtain the mountain green mud powder with the particle size of less than 62 mu m;
s2, mixing 4.2g of glycerol with 42.2g of deionized water to form a gelatin solvent, dissolving 4.2g of gelatin in the gelatin solvent, and placing the gelatin solvent on a magnetic stirrer to stir at 300rpm for 20min to obtain a gelatin solution;
and S3, adding 49.2g of the mountain green mud powder in the S1 into the gelatin solution in the S2, and uniformly mixing under a stirrer to obtain the 3D printing ceramic slurry.
The embodiment of the application also provides a preparation method of the ceramic material, which comprises the following steps:
s1, providing the 3D printing ceramic slurry prepared in the embodiment 2;
s2, placing the 3D printing ceramic slurry in a mould for shaping, adopting a vacuum machine for defoaming treatment for 0.5h, and then placing the ceramic slurry in an oven for drying at 60 ℃ for 12h to obtain a green body;
and S4, placing the green blanks into a muffle furnace, calcining for 24 hours at the temperature of 1150 ℃, and finally obtaining ceramic finished products (specifically ceramic plates).
Example 3
The embodiment of the application provides 3D printing ceramic slurry, which comprises ceramic powder and gelatin solution, wherein the gelatin solution comprises glycerol, gelatin and water;
wherein the ceramic powder is 50g of bottom groove green powder, and the gelatin solution comprises 3.4g of glycerin, 4.2g of gelatin and 42.2g of water.
The preparation method of the 3D printing ceramic slurry comprises the following steps:
s1, drying the bottom groove green powder, mashing the dried bottom groove green powder into block-shaped particles, putting the block-shaped particles into a ball mill, ball milling the block-shaped particles in the ball mill for 1h at 300r/min to obtain high-definition powder, and screening the high-definition powder to obtain the bottom groove green powder with the particle size of less than 62 mu m;
s2, mixing 3.4g of glycerol with 42.2g of deionized water to form a gelatin solvent, dissolving 4.2g of gelatin in the gelatin solvent, and placing the gelatin solvent on a magnetic stirrer to stir at 300rpm for 20min to obtain a gelatin solution;
and S3, adding 50g of the bottom groove green powder in the S1 into the gelatin solution in the S2, and uniformly mixing under a stirrer to obtain the 3D printing ceramic slurry.
The embodiment of the application also provides a preparation method of the ceramic material, which comprises the following steps:
s1, providing the 3D printing ceramic slurry prepared in the embodiment 3;
s2, printing ceramic slurry by using 3D according to a three-dimensional model (particularly a teacup model) of a ceramic material to be manufactured, and obtaining a printing part clay blank by adopting a fused deposition modeling process; before printing, carrying out centrifugal defoaming treatment on the 3D printing ceramic slurry, wherein the centrifugal rotating speed is 3500rpm, and the centrifugal treatment time is 10min; in the step of obtaining a printed piece by adopting a fused deposition modeling process, 3D printing ceramic slurry is injected into a printing material pipe, the printing material pipe is preheated for 30min at 40 ℃, then the printing material pipe is adjusted to 38 ℃ for printing, and the controlled printing process parameters are as follows: the inner diameter of the nozzle of the printing needle head is 1.2mm, the height of the printing layer is 0.5mm, and the printing speed is 100mm/min;
s3, placing the printing piece clay blank in an oven to be dried for 12 hours at 60 ℃;
and S4, placing the dried printing piece clay blank into a muffle furnace, calcining for 24 hours at the temperature of 1150 ℃, and finally obtaining a ceramic finished product.
Comparative example 1
The comparative example provides a 3D printing ceramic slurry comprising ceramic powder and water;
wherein, the ceramic powder is 49.2g of Benshan green mud, and the mass of water is 50.8g.
The preparation method of the 3D printing ceramic slurry comprises the following steps:
s1, drying the mountain green mud material, mashing the mountain green mud material into block-shaped particles, putting the block-shaped particles into a ball mill, ball milling for 1h at 300r/min to obtain high-definition powder, and screening to obtain the mountain green mud powder with the particle size of less than 62 mu m;
s2, adding 49.2g of the mountain green mud powder in S1 into 50.8g of water, and placing the mixture under a stirrer for uniform mixing to obtain the 3D printing ceramic slurry.
The embodiment of the application also provides a preparation method of the ceramic material, which comprises the following steps:
s1, providing the 3D printing ceramic slurry prepared in the comparison 1;
s2, printing ceramic slurry by using 3D according to a three-dimensional model (particularly a teacup model) of a ceramic material to be manufactured, and obtaining a printing part clay blank by adopting a fused deposition modeling process; before printing, carrying out centrifugal defoaming treatment on the 3D printing ceramic slurry, wherein the centrifugal rotating speed is 3500rpm, and the centrifugal treatment time is 10min; in the step of obtaining a printed piece by adopting a fused deposition modeling process, 3D printing ceramic slurry is injected into a printing material pipe, the printing material pipe is preheated for 30min at 40 ℃, then the printing material pipe is adjusted to 38 ℃ for printing, and the controlled printing process parameters are as follows: the inner diameter of the nozzle of the printing needle head is 1.2mm, the height of the printing layer is 0.5mm, and the printing speed is 100mm/min;
s3, placing the printing piece clay blank in an oven to be dried for 12 hours at 60 ℃;
and S4, placing the dried printing piece clay blank into a muffle furnace, calcining for 24 hours at the temperature of 1150 ℃, and finally obtaining a ceramic finished product.
Comparative example 2
The comparative example provides a 3D printing ceramic slurry comprising ceramic powder and water, wherein the ceramic powder is 49.2g of Benshan green mud, and the water has a mass of 50.8g.
The preparation method of the 3D printing ceramic slurry comprises the following steps:
s1, drying the mountain green mud material, mashing the mountain green mud material into block-shaped particles, putting the block-shaped particles into a ball mill, ball milling for 1h at 300r/min to obtain high-definition powder, and screening to obtain the mountain green mud powder with the particle size of less than 62 mu m;
s2, adding 49.2g of the mountain green mud powder in S1 into 50.8g of aqueous solution, and placing under a stirrer for uniform mixing to obtain the 3D printing ceramic slurry.
The embodiment of the application also provides a preparation method of the ceramic material, which comprises the following steps:
s1, providing the 3D printing ceramic slurry prepared in the embodiment 2;
s2, placing the 3D printing ceramic slurry in a mould for shaping, adopting a vacuum machine for defoaming treatment for 0.5h, and then placing the ceramic slurry in an oven for drying at 60 ℃ for 12h to obtain a green body;
and S4, placing the green blanks into a muffle furnace, calcining for 24 hours at the temperature of 1150 ℃, and finally obtaining ceramic finished products (specifically ceramic plates).
Performance testing
The ceramic slurry not added in fig. 1 (including 49.2g and 50.8g of water, corresponding to the ceramic slurry in comparative example 1), the ceramic slurry added with gelatin (including 49.2g of benshan green mud, 4.2g of gelatin and 46.6g of water), and the ceramic slurry added with gelatin and glycerin (including 49.2g of benshan green mud, 4.2g of glycerin, 4.2g of gelatin and 42.2g of water, corresponding to the ceramic slurry in example 1); in fig. 1, the ceramic slurry of comparative example 1 was not added, and the addition of gelatin and glycerin represents the ceramic slurry of example 1, and the addition of gelatin represents the ceramic slurry to which gelatin was added.
As can be seen from fig. 1, the viscosity of the ceramic slurry is obviously increased after gelatin is added, and the viscosity of the gelatin can be correspondingly increased after the auxiliary agent glycerin is added, so that the viscosity of the ceramic slurry is further increased, and the cohesiveness and plasticity of the ceramic slurry are effectively improved.
Fig. 2 is surface rockwell hardness data of the ceramic products prepared in comparative example 2 and example 2. Comparative example 2 was not added in fig. 2, and the addition of gelatin and glycerin corresponds to example 2. The abscissa in fig. 2 represents the surface rockwell hardness data at 5 different locations on the surface of the finished ceramic product.
As can be seen from FIG. 2, the hardness is only slightly reduced after gelatin is added, and the hardness distribution of each point of the ceramic sheet is relatively even, and the average value is 69.26HRC.
FIG. 3 is an XRD (X-ray diffraction) characterization of the ceramic products prepared in comparative example 2 and example 2; in fig. 3, a is comparative example 2 and b corresponds to example 2.
As can be seen from fig. 3, the XRD pattern after sintering with gelatin is substantially identical to the pure benshan green mud pattern, and no new diffraction peak appears, which indicates that the binder gelatin and the auxiliary agent glycerin can be completely removed after sintering, and no influence is exerted on the mud purity.
Fig. 4 is a picture of the printing member green in comparative example 1, and fig. 5 is a picture of the printing member green in example 1.
As can be seen from fig. 4 to 5, the 3D printed example graph of the mixed pug of the ceramic pug and the binder gelatin shows that the finished product printed from the pure green mud is extremely easy to collapse and deform, and the printed finished product after the gelatin and the glycerol are added has smooth surface and good supportability, because the sol-gel conversion property of the gelatin is heated into a sol state in a printing material pipe, the fluidity is strong, and the gelatin is immediately converted into a gel solid state after extrusion, the mixed pug has a certain supporting force, and the mixed pug has a certain viscoelastic and shear thinning property, so that the problems of collapse, cracking, deformation and the like are reduced, and the dimensional accuracy of the product is improved.
FIG. 6 is a diagram showing an example of a ceramic product obtained by sintering a ceramic frit provided in example 1 after 3D printing and molding of a mixed frit of a binder gelatin and an auxiliary agent glycerol; from fig. 6, it can be seen that the sintered product is substantially identical to the green body, and has a smooth surface and no obvious layering, which indicates that the addition of gelatin increases the product accuracy and improves the yield.
FIG. 7 is an SEM (scanning electron microscope) characterization diagram of a ceramic finished product obtained by sintering a ceramic frit provided in example 1 after 3D printing of the ceramic frit with binder gelatin and additive glycerin;
as can be seen from fig. 7, the ceramic product has compact surface after sintering, no obvious air holes, which indicates that the plasticity of the ceramic slurry is improved after gelatin is added, the product precision is increased, and meanwhile, the sintering quality is not affected.
The foregoing description of the preferred embodiments of the application is not intended to be limiting, but rather is intended to cover all modifications, equivalents, alternatives, and improvements that fall within the spirit and scope of the application.
Claims (10)
1. A 3D printing ceramic slurry, comprising ceramic powder and a gelatin solution, wherein the gelatin solution comprises glycerol, gelatin and water.
2. The 3D printing ceramic slurry according to claim 1, wherein the mass ratio of glycerin, gelatin and water in the gelatin solution is (0.1-1): 1:10.
3. The 3D printing ceramic slurry according to claim 1, wherein the mass ratio of the ceramic powder to the gelatin solution is 1 (0.3-0.5).
4. The 3D printing ceramic slurry of any one of claims 1-3, wherein the ceramic powder comprises at least one of present mountain green mud, foundation pit green, present mountain violet mud.
5. A method of preparing the 3D printing ceramic slurry according to any one of claims 1 to 4, comprising the steps of:
mixing glycerol with water, adding gelatin, and stirring to obtain gelatin solution;
and adding the ceramic powder into the gelatin solution, and stirring to obtain the 3D printing ceramic slurry.
6. The method for preparing 3D printing ceramic slurry according to claim 5, wherein the step of ball milling the ceramic powder before adding the ceramic powder to the gelatin solution comprises: placing the ceramic powder into a ball mill for ball milling and sieving; wherein the rotating speed of the ball mill is 300-600 r/min, and the ball milling time is 1-3 h; and sieving to obtain ceramic powder with particle size less than or equal to 62 μm.
7. The method for preparing a 3D printing ceramic slurry according to claim 5, wherein in the step of mixing glycerol with water, adding gelatin, and stirring to obtain a gelatin solution, the stirring speed is 300-500 rpm, and the stirring time is 20-30 min.
8. A method for preparing a ceramic material, comprising the steps of:
providing the 3D printing ceramic slurry according to any one of claims 1 to 4 or the 3D printing ceramic slurry prepared by the preparation method according to any one of claims 5 to 7;
according to a three-dimensional model of the ceramic material to be manufactured, utilizing the 3D printing ceramic slurry, and obtaining a printing piece by adopting a fused deposition modeling process;
drying the printing piece, and calcining to obtain a ceramic material;
or placing the 3D printing ceramic slurry in a mould for shaping, drying to obtain a clay blank, drying the clay blank, and calcining to obtain the ceramic material.
9. The method of producing a ceramic material according to claim 8, wherein in the step of obtaining a printed article by a fused deposition modeling process, the process parameters are controlled as follows: the inner diameter of the nozzle of the printing needle head is 0.5-1.2 mm, the height of the printing layer is 0.2-0.5 mm, the printing speed is 50-100 mm/min, and the printing temperature is 30-40 ℃.
10. The method for preparing ceramic material according to claim 8, wherein the step of using the 3D printing ceramic slurry, before obtaining a printed material by a fused deposition modeling process, further comprises performing centrifugal defoaming treatment on the 3D printing ceramic slurry, wherein the centrifugal speed is 2500-4300 rpm, and the centrifugal treatment time is 10-20 min;
the calcination temperature is 1100-1200 ℃ and the calcination time is 24-36 h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311098366.2A CN117164330A (en) | 2023-08-29 | 2023-08-29 | 3D printing ceramic slurry and preparation method thereof, and preparation method of ceramic material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311098366.2A CN117164330A (en) | 2023-08-29 | 2023-08-29 | 3D printing ceramic slurry and preparation method thereof, and preparation method of ceramic material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117164330A true CN117164330A (en) | 2023-12-05 |
Family
ID=88938793
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311098366.2A Pending CN117164330A (en) | 2023-08-29 | 2023-08-29 | 3D printing ceramic slurry and preparation method thereof, and preparation method of ceramic material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117164330A (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5279994A (en) * | 1993-02-11 | 1994-01-18 | W. R. Grace & Co.-Conn. | Aqueous processing of green ceramic tapes |
| KR20020085055A (en) * | 2001-05-04 | 2002-11-16 | 한국과학기술연구원 | Aqueous ceramic slurry using pvp and gelatin as a binding agent and method for producing a ceramic tape using them |
| CN107459328A (en) * | 2016-06-06 | 2017-12-12 | 研能科技股份有限公司 | 3 D-printing preparation method of ceramic article shaped and combinations thereof |
| US20180000987A1 (en) * | 2016-06-30 | 2018-01-04 | Electronics And Telecommunications Research Institute | Porous bone substitutes and method of preparing the same |
| CN111825454A (en) * | 2019-08-29 | 2020-10-27 | 宁波伏尔肯科技股份有限公司 | Preparation method of layered structure ceramic ring for mechanical seal |
| US20210163361A1 (en) * | 2018-05-31 | 2021-06-03 | Bioalpha Corporation | Composition for fdm 3d printers |
-
2023
- 2023-08-29 CN CN202311098366.2A patent/CN117164330A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5279994A (en) * | 1993-02-11 | 1994-01-18 | W. R. Grace & Co.-Conn. | Aqueous processing of green ceramic tapes |
| KR20020085055A (en) * | 2001-05-04 | 2002-11-16 | 한국과학기술연구원 | Aqueous ceramic slurry using pvp and gelatin as a binding agent and method for producing a ceramic tape using them |
| CN107459328A (en) * | 2016-06-06 | 2017-12-12 | 研能科技股份有限公司 | 3 D-printing preparation method of ceramic article shaped and combinations thereof |
| US20180000987A1 (en) * | 2016-06-30 | 2018-01-04 | Electronics And Telecommunications Research Institute | Porous bone substitutes and method of preparing the same |
| US20210163361A1 (en) * | 2018-05-31 | 2021-06-03 | Bioalpha Corporation | Composition for fdm 3d printers |
| CN111825454A (en) * | 2019-08-29 | 2020-10-27 | 宁波伏尔肯科技股份有限公司 | Preparation method of layered structure ceramic ring for mechanical seal |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106242507B (en) | Clay mud for directly-formed 3D ceramic printing and preparation method and application thereof | |
| CN105130402B (en) | A kind of nano ceramic material and its 3D printing forming method for 3D printing | |
| CN112047727B (en) | Preparation method of 3D printing alumina ceramic material | |
| JP2604592B2 (en) | Molding method of metal, ceramic powder, etc. and composition therefor | |
| CN111848141A (en) | Preparation method of ceramic paste for 3D printing by direct-writing forming of slurry | |
| CN107216155B (en) | PF/PVA double-coated ceramic powder for laser 3D printing/cold isostatic pressing composite molding and preparation method thereof | |
| CN104163929A (en) | Preparation method of high-molecular nylon powder material used for 3D printing | |
| CN111763090B (en) | Adhesive, preparation method and application thereof | |
| CN104788102A (en) | Preparation method for nano-silicon nitride powder for laser sintering 3D printing technology | |
| CN112919904A (en) | Zirconia ceramic substrate and preparation method thereof | |
| CN110963788A (en) | Preparation method of ceramic slurry and ceramic device | |
| CN113458387A (en) | 3D printing gradient ceramic metal material and preparation method thereof | |
| CN105619572A (en) | 3D printing forming method of ceramic material | |
| CN103553632A (en) | Preparation method for dense silicon nitride ceramic material | |
| CN108530028B (en) | Ceramic powder for 3D printing sanitary appliance and production process of ceramic sanitary appliance | |
| CN117164330A (en) | 3D printing ceramic slurry and preparation method thereof, and preparation method of ceramic material | |
| CN111302785A (en) | High-performance microwave dielectric ceramic and photocuring manufacturing method thereof | |
| CN113880563B (en) | High-temperature creep-resistant ceramic material and preparation method thereof | |
| CN112250473B (en) | Gradient porous ceramic core and preparation method thereof | |
| CN111646803B (en) | Molten 3D direct-writing printing slurry and preparation method and application thereof | |
| TWI806320B (en) | Method for preparing ceramic slurry that can be used for three-dimensional printing | |
| CN111777412A (en) | 3D ceramic printing process for large-size model | |
| CN114101593B (en) | High-collapsibility recyclable silica-based ceramic core and preparation method and application thereof | |
| CN109650901A (en) | A kind of BN-Mg2Al4Si5O18Diphase ceramic material, preparation method and ceramic component | |
| CN112047730B (en) | Preparation method of photo-curing diatomite ceramic paste |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20231204 Address after: No. 333 Taodu Road, Dingshu Town, Yixing City, Wuxi City, Jiangsu Province, 214200 Applicant after: Shen Yi Address before: China University of Geosciences (Wuhan) Baogu Innovation and Entrepreneurship Center, No. 388 Lumo Road, Hongshan District, Wuhan City, Hubei Province, 430074 Applicant before: Dida (Wuhan) Asset Management Co.,Ltd. |
|
| TA01 | Transfer of patent application right | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20240319 Address after: No. 333 Taodu Road, Dingshu Town, Yixing City, Wuxi City, Jiangsu Province, 214200 Applicant after: Zhongdi University (Yixing) Functional Materials and Environmental Research Institute Co.,Ltd. Country or region after: Zhong Guo Address before: No. 333 Taodu Road, Dingshu Town, Yixing City, Wuxi City, Jiangsu Province, 214200 Applicant before: Shen Yi Country or region before: Zhong Guo |
|
| TA01 | Transfer of patent application right |