CN113698179A - Toughened ceramic-based material for 3D printing and preparation method thereof - Google Patents
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- 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
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Abstract
The invention discloses a toughened ceramic-based material for 3D printing and a preparation method thereof, wherein the toughened ceramic-based material comprises the following raw materials in parts by weight: 40-50 parts of kaolin, 10-15 parts of quartz, 12-20 parts of alumina, 5-10 parts of zirconia, 6-12 parts of titanium dioxide and 9-15 parts of silicon oxide; 8-15 parts of acrylic resin, 2-5 parts of dispersing agent, 0.5-1 part of interface modifier, 0.1-0.5 part of binder, 4-8 parts of metal fiber and 1-3 parts of sodium hydroxymethyl sulfonate. The invention also discloses a preparation method of the toughened ceramic base for 3D printing. According to the invention, the metal fiber and the sodium hydroxymethyl sulfonate are added into the formula of the ceramic at the same time, and the problem of poor toughness of the ceramic manufactured by 3D printing is solved by utilizing the synergistic effect of the metal fiber and the sodium hydroxymethyl sulfonate.
Description
Technical Field
The invention relates to the technical field of 3D printing ceramics, in particular to a toughened ceramic-based material for 3D printing and a preparation method thereof.
Background
3D printing (3DP), a technique for constructing objects by layer-by-layer printing using bondable materials such as powdered metals or plastics based on digital model files, is one of the rapid prototyping techniques, also known as additive manufacturing. 3D printing is typically achieved using digital technology material printers. The method is often used for manufacturing models in the fields of mold manufacturing, industrial design and the like, and is gradually used for directly manufacturing some products, and parts printed by the technology are already available. The technology has applications in jewelry, footwear, industrial design, construction, engineering and construction (AEC), automotive, aerospace, dental and medical industries, education, geographic information systems, civil engineering, firearms, and other fields.
Ceramics are the historical evidence of the development of Chinese civilization, and play an important role in tableware and artistic decorations from ancient times to present. The ceramic parts are all manufactured by kiln sintering, and because of the unnecessary development of other functions of the ceramic, the selection of the ceramic raw material varieties in China is single and traditional. The advent of 3D printing and the excavation of ceramic functionality has made ceramic materials newer both from a formulation standpoint and from a process standpoint.
The raw materials used for 3D printing are special, must be capable of being liquefied, powdered or filamentized, recombined after printing is complete, and have acceptable physical and chemical properties. At present, the consumable materials for 3D printing are very limited, and mainly comprise gypsum, inorganic powder, photosensitive resin, plastic, metal powder, ceramic powder and the like. When gypsum, inorganic powder, photosensitive resin, plastic, metal and the like are used for 3D printing, products with stable performance can be formed by self solidification, cooling and the like. When the ceramic powder is used for 3D printing, due to the influences of various factors such as powder components, impurities, oxidation, melting temperature, sintering temperature and the like, the content of the impurities in the product is high, the compactness is poor, the structure is uneven, the crystal structure is even and poor, pores exist in the product and the like, and the strength of the product is influenced. And also becomes a main factor which hinders the application of the 3D printing technology in the field of ceramic product manufacturing at present.
The ceramic matrix composite is a composite material compounded with various fibers by taking ceramic as a matrix. The ceramic matrix can be high temperature structural ceramic such as silicon nitride, silicon carbide, etc. These advanced ceramics have excellent properties of high temperature resistance, high strength and rigidity, relatively light weight, corrosion resistance and the like, and have the fatal weakness of brittleness, and when in a stress state, the advanced ceramics can generate cracks and even break to cause material failure. The adoption of high-strength and high-elasticity fiber and matrix composite is an effective method for improving the toughness and reliability of the ceramic. The fiber can prevent the crack from expanding, thereby obtaining the fiber reinforced ceramic matrix composite material with excellent toughness. The ceramic matrix composite material has been used as a liquid rocket engine nozzle, a missile radome, a nose cone of a space shuttle, a brake disc of an airplane, a brake disc of a high-grade automobile and the like, and becomes an important branch of a high-technology new material.
Chinese invention patent CN105130482A discloses a metal toughening ceramic matrix composite material for 3D printing, which adds metal fibers into ceramic microspheres to realize toughening of ceramics, but the patent does not disclose whether adding some substances can enhance the toughening effect of the original metal fibers on the ceramics.
In the prior art, when ceramic powder is used for manufacturing ceramic products through 3D printing, the plasticity and toughness of the ceramic products are often reduced due to uneven structure, uniform and poor crystal structure and the like, so that the toughness of the ceramic is poor, and the requirements of people on the ceramic at the present stage can not be met.
Disclosure of Invention
The invention aims to provide a toughened ceramic-based material for 3D printing and a preparation method thereof, which are used for solving the problems that the toughness of ceramics is poor when ceramic products are manufactured by 3D printing in the prior art, and the requirements of people on the ceramics at the present stage cannot be met.
To achieve the above object, in one embodiment of the present invention, there is provided a toughened ceramic-based material for 3D printing, wherein: the material comprises the following raw materials in parts by weight:
40-50 parts of kaolin, 10-15 parts of quartz, 12-20 parts of alumina,
5-10 parts of zirconium oxide, 6-12 parts of titanium dioxide and 9-15 parts of silicon oxide;
8-15 parts of acrylic resin, 2-5 parts of dispersant, 0.5-1 part of interface modifier,
0.1-0.5 part of binder, 4-8 parts of metal fiber and 1-3 parts of sodium hydroxymethyl sulfonate.
In a preferred embodiment of the present invention, the dispersant is at least one of a copolymer dispersant having an acidic group and a polyether polyol-modified polyurethane polymer dispersant.
In one preferred embodiment of the present invention, the interfacial modifier is a carboxylated polyether interfacial modifier.
In a preferred embodiment of the present invention, the binder is at least one selected from paraffin wax, microcrystalline wax, polyethylene wax, polypropylene wax, polyvinyl alcohol, and dimethiconol.
In a preferred embodiment of the present invention, the metal fibers are at least one of aluminum fibers, titanium fibers, nickel fibers, and tin fibers.
Based on the toughened ceramic-based material for 3D printing disclosed by the invention, the invention also discloses a preparation method of the toughened ceramic-based material for 3D printing, which comprises the following steps:
ball milling: weighing kaolin, quartz, alumina, zirconia, titanium dioxide and silicon oxide according to parts by weight, putting the raw materials and a dispersing agent into a ball mill together for ball milling, and sieving the ball-milled materials;
dispersing in step (2): putting the material obtained in the step (1) and an interface modifier into a high-speed dispersion machine together for dispersion;
grinding in step (3): putting the material obtained in the step (2), the metal fiber and the acrylic resin into a grinding machine for grinding, and sieving after grinding;
mixing in step (4): and (4) putting the material obtained in the step (3) and the binder into a high-speed mixer together for mixing, and adding water in the mixing process to obtain the slurry finally.
In the step (1), the ball milling speed is 1500-; the sieved mesh is 200 mesh.
In the step (2), the rotation speed of the high-speed dispersion machine is 6000-.
In one preferable scheme of the invention, in the step (3), the rotation speed of the grinding machine is 500-800r/min, the grinding time is 30-40min, and the sieved mesh is 200 meshes.
In one preferable scheme of the invention, in the step (4), the rotating speed of the high-speed mixer is 800-1200r/min, the time of the high-speed mixing is 1-2h, and the working temperature of the high-speed mixer is 95-115 ℃.
In summary, the invention has the following advantages:
1. according to the invention, the metal fiber and the sodium hydroxymethyl sulfonate are added into the formula of the ceramic at the same time, and the problem of poor toughness of the ceramic manufactured by 3D printing is solved by utilizing the synergistic effect of the metal fiber and the sodium hydroxymethyl sulfonate.
2. The printing product obtained by the invention has the characteristics of small internal stress, good mechanical property, good plastic toughness and smooth and fine surface, and meanwhile, the preparation method has the advantages of simple process, short flow, low cost, suitability for mass preparation and easy realization of industrialization.
Detailed Description
Example 1
A toughened ceramic-based material for 3D printing, characterized in that: the material comprises the following raw materials in parts by weight:
45 parts of kaolin, 12.5 parts of quartz, 16 parts of alumina, 7.5 parts of zirconia, 9 parts of titanium dioxide and 12 parts of silicon oxide; 11.5 parts of acrylic resin, 3.5 parts of a dispersing agent, 0.75 part of an interface modifier carboxylated polyether interface modifier, 0.3 part of binder paraffin, 6 parts of aluminum fiber and 2 parts of sodium hydroxymethyl sulfonate.
Wherein the dispersant is at least one of a copolymer dispersant with an acid group and a polyether polyol modified polyurethane polymer dispersant.
A preparation method of a toughened ceramic-based material for 3D printing comprises the following steps:
ball milling: weighing kaolin, quartz, alumina, zirconia, titanium dioxide and silicon oxide according to parts by weight, then putting the raw materials and a dispersing agent into a ball mill together for ball milling, wherein the ball milling speed is 1500-;
dispersing in step (2): putting the material obtained in the step (1) and an interface modifier into a high-speed dispersion machine for dispersion, wherein the rotating speed of the high-speed dispersion machine is 6000-;
grinding in step (3): putting the material obtained in the step (2), the metal fiber and the acrylic resin into a grinding machine for grinding at the rotating speed of 500-800r/min for 30-40min, and sieving with a 200-mesh sieve after grinding;
mixing in step (4): and (4) putting the material obtained in the step (3) and the binder into a high-speed mixer together for mixing, wherein the rotating speed of the high-speed mixer is 800-1200r/min, the high-speed mixing time is 1-2h, the working temperature of the high-speed mixer is 95-115 ℃, and water is added in the high-speed mixing process to finally obtain the slurry.
Example 2
A toughened ceramic-based material for 3D printing, characterized in that: the material comprises the following raw materials in parts by weight:
40 parts of kaolin, 15 parts of quartz, 12 parts of alumina, 5 parts of zirconia, 12 parts of titanium dioxide and 15 parts of silicon oxide; 8 parts of acrylic resin, 2 parts of a dispersing agent, 1 part of an interface modifier carboxylated polyether interface modifier, 0.5 part of a binder microcrystalline wax, 4 parts of nickel fiber and 1 part of sodium hydroxymethyl sulfonate.
Wherein the dispersant is at least one of a copolymer dispersant with an acid group and a polyether polyol modified polyurethane polymer dispersant.
Example 2 the preparation method of the toughened ceramic-based material for 3D printing was the same as in example 1.
Example 3
A toughened ceramic-based material for 3D printing, characterized in that: the material comprises the following raw materials in parts by weight:
50 parts of kaolin, 10 parts of quartz, 20 parts of alumina, 10 parts of zirconia, 6 parts of titanium dioxide and 9 parts of silicon oxide; 15 parts of acrylic resin, 5 parts of a dispersing agent, 0.5 part of an interface modifier carboxylated polyether interface modifier, 0.1 part of a binder polypropylene wax, 8 parts of titanium fiber and 3 parts of sodium hydroxymethyl sulfonate.
Wherein the dispersant is at least one of a copolymer dispersant with an acid group and a polyether polyol modified polyurethane polymer dispersant.
Example 3 the preparation method of the toughened ceramic-based material for 3D printing was the same as in example 1.
Example 4
A toughened ceramic-based material for 3D printing, characterized in that: the material comprises the following raw materials in parts by weight:
42.5 parts of kaolin, 10.75 parts of quartz, 14 parts of alumina, 8.75 parts of zirconia, 10.5 parts of titanium dioxide and 13.5 parts of silicon oxide; 9.25 parts of acrylic resin, 2.75 parts of a dispersing agent, 0.875 part of an interfacial modifier carboxylated polyether interfacial modifier, 0.2 part of a binder polyvinyl alcohol, 7 parts of tin fiber and 1.5 parts of sodium hydroxymethyl sulfonate.
Wherein the dispersant is at least one of a copolymer dispersant with an acid group and a polyether polyol modified polyurethane polymer dispersant.
Example 4 the preparation method of the toughened ceramic-based material for 3D printing was the same as in example 1.
Example 5
A toughened ceramic-based material for 3D printing, characterized in that: the material comprises the following raw materials in parts by weight:
47.5 parts of kaolin, 13.725 parts of quartz, 18 parts of alumina, 6.25 parts of zirconia, 7.5 parts of titanium dioxide and 10.5 parts of silicon oxide; 13.75 parts of acrylic resin, 2.75 parts of a dispersing agent, 0.625 part of an interface modifier carboxylated polyether interface modifier, 0.4 part of a binder dimethiconol, 5 parts of nickel fiber and 2.5 parts of sodium hydroxymethyl sulfonate.
Wherein the dispersant is at least one of a copolymer dispersant with an acid group and a polyether polyol modified polyurethane polymer dispersant.
Example 5 a method of preparing a toughened ceramic-based material for 3D printing was the same as in example 1.
In conclusion, the toughened ceramic-based material is prepared from kaolin, quartz, alumina, zirconia, titanium dioxide, silicon oxide, acrylic resin, a dispersing agent, an interface modifier, a binder, metal fibers and sodium hydroxymethyl sulfonate.
Claims (10)
1. A toughened ceramic-based material for 3D printing, characterized in that: the material comprises the following raw materials in parts by weight:
40-50 parts of kaolin, 10-15 parts of quartz, 12-20 parts of alumina,
5-10 parts of zirconium oxide, 6-12 parts of titanium dioxide and 9-15 parts of silicon oxide;
8-15 parts of acrylic resin, 2-5 parts of dispersant, 0.5-1 part of interface modifier,
0.1-0.5 part of binder, 4-8 parts of metal fiber and 1-3 parts of sodium hydroxymethyl sulfonate.
2. The toughened ceramic-based material for 3D printing as claimed in claim 1, wherein: the dispersant is at least one of a copolymer dispersant with an acid group and a polyether polyol modified polyurethane polymer dispersant.
3. The toughened ceramic-based material for 3D printing as claimed in claim 1, wherein: the interfacial modifier is a carboxylated polyether interfacial modifier.
4. The toughened ceramic-based material for 3D printing as claimed in claim 1, wherein: the binder is at least one of paraffin, microcrystalline wax, polyethylene wax, polypropylene wax, polyvinyl alcohol and dimethiconol.
5. The toughened ceramic-based material for 3D printing as claimed in claim 1, wherein: the metal fiber is at least one of aluminum fiber, titanium fiber, nickel fiber and tin fiber.
6. A preparation method of a toughened ceramic-based material for 3D printing comprises the following steps:
ball milling: weighing kaolin, quartz, alumina, zirconia, titanium dioxide and silicon oxide according to parts by weight, putting the raw materials and a dispersing agent into a ball mill together for ball milling, and sieving the ball-milled materials;
dispersing in step (2): putting the material obtained in the step (1) and an interface modifier into a high-speed dispersion machine together for dispersion;
grinding in step (3): putting the material obtained in the step (2), the metal fiber and the acrylic resin into a grinding machine for grinding, and sieving after grinding;
mixing in step (4): and (4) putting the material obtained in the step (3) and the binder into a high-speed mixer together for mixing, and adding water in the mixing process to obtain the slurry finally.
7. The method of preparing a toughened ceramic-based material for 3D printing according to claim 6 wherein: in the step (1), the ball milling speed is 1500-; the sieved mesh is 200 mesh.
8. The method of preparing a toughened ceramic-based material for 3D printing according to claim 6 wherein: in the step (2), the rotating speed of the high-speed dispersion machine is 6000-.
9. The method of preparing a toughened ceramic-based material for 3D printing according to claim 6 wherein: in the step (3), the rotation speed of the grinding machine is 500-800r/min, the grinding time is 30-40min, and the sieved mesh is 200 meshes.
10. The method of preparing a toughened ceramic-based material for 3D printing according to claim 6 wherein: in the step (4), the rotating speed of the high-speed mixer is 800-1200r/min, the high-speed mixing time is 1-2h, and the working temperature of the high-speed mixer is 95-115 ℃.
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| CN110606760A (en) * | 2019-10-15 | 2019-12-24 | 常州增材制造研究院有限公司 | Polymer ceramic composite 3D printing material and preparation method thereof |
| CN111548120A (en) * | 2020-05-14 | 2020-08-18 | 福建省德化同鑫陶瓷有限公司 | 3D printing crater-shaped texture ceramic and processing method thereof |
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- 2021-09-22 CN CN202111104829.2A patent/CN113698179A/en active Pending
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| CN105130482A (en) * | 2015-08-04 | 2015-12-09 | 成都新柯力化工科技有限公司 | Metal toughened ceramic-based composite material for 3D printing |
| CN105563610A (en) * | 2015-12-24 | 2016-05-11 | 成都新柯力化工科技有限公司 | Method for preparing ceramic metal through 3D printing technology |
| CN109467385A (en) * | 2018-01-15 | 2019-03-15 | 杭州创屹机电科技有限公司 | A kind of antibacterial environment protection 3D printing ceramic material and preparation method thereof |
| CN110606760A (en) * | 2019-10-15 | 2019-12-24 | 常州增材制造研究院有限公司 | Polymer ceramic composite 3D printing material and preparation method thereof |
| CN111548120A (en) * | 2020-05-14 | 2020-08-18 | 福建省德化同鑫陶瓷有限公司 | 3D printing crater-shaped texture ceramic and processing method thereof |
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