CN108285333B - Two-component ceramic 3D printing material and 3D printing method thereof - Google Patents

Two-component ceramic 3D printing material and 3D printing method thereof Download PDF

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Publication number
CN108285333B
CN108285333B CN201810054433.3A CN201810054433A CN108285333B CN 108285333 B CN108285333 B CN 108285333B CN 201810054433 A CN201810054433 A CN 201810054433A CN 108285333 B CN108285333 B CN 108285333B
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parts
ceramic
additive
slurry
printing
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CN108285333A (en
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陈洁
吴艳芳
张鹤
邱振江
徐晓辉
王武
梅景丰
李启岳
柯振宇
金莹
胡旭华
兰俊杰
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Longquan Jinhong Porcelain Co ltd
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Longquan Jinhong Porcelain Co ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
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Abstract

The invention relates to the technical field of 3D printing. The invention provides a two-component ceramic 3D printing material which comprises ceramic slurry and an additive, wherein the ceramic slurry comprises the following components in parts by weight: 75-80 parts of ceramic microspheres, 0.1-0.3 part of anionic surfactant, 1-2 parts of auxiliary adhesive and 6-8 parts of citric acid; the additive comprises the following components in parts by weight: 3-4 parts of silicon carbide powder, 5-7 parts of sulfanilic acid and 5-6 parts of triethylamine. The invention also provides a 3D printing method of the two-component ceramic, which comprises the steps of constructing a three-dimensional model, conveying the ceramic slurry to a slurry sprayer through a feeding system, simultaneously conveying an additive to an additive sprayer through another system, and simultaneously feeding the slurry sprayer and the additive sprayer to perform layered printing; standing the blank, and drying in an oven; and sintering the dried green body. The invention has the advantages of rapid solidification and forming, and high hardness and strength of the ceramic.

Description

Two-component ceramic 3D printing material and 3D printing method thereof
Technical Field
The invention relates to the technical field of 3D printing, in particular to a two-component ceramic 3D printing material and a 3D printing method thereof.
Background
The invention discloses a three-dimensional printing technology in 90 s of the 20 th century by the American academy of labor technology, which is a technology for constructing an object by using bondable materials such as powdered metal or plastic and the like in a layer-by-layer printing mode on the basis of a digital model file. It has been used to manufacture models in the fields of mold manufacturing, industrial design, etc., and is now increasingly used for direct manufacture of some products. In particular, high value applications (such as hip joints or teeth, or aircraft parts) already have parts printed using this technique. With the application of the three-dimensional printing technology in ceramic materials, the adoption of three-dimensional printing ceramic devices becomes practical. In the traditional ceramic manufacture, pottery clay is used for molding, forming, airing, die sinking, blank pouring, firing and the like, the investment time is long, the capital cost is high, and the modification is not easy. Therefore, the 3D printed ceramic device can be suitable for manufacturing small-batch models, constructing complex devices and greatly reducing the time for modifying the models and the manufacturing cost.
The prior art, chinese patent CN104339437A, discloses a method for producing ceramic casting molds by 3D printing technology, which comprises loading ceramic powder and adhesive into a 3D printing head, inputting a three-dimensional drawing of a casting mold to be printed into a 3D printer, printing the casting mold layer by layer according to the drawing, finally forming the required casting mold, and sintering the ceramic powder and the adhesive in a heating furnace to form the ceramic casting mold.
However, in this prior art, a layer of powder binder is laid between two layers of ceramic powder, and the newly added ceramic layer is bonded to the formed ceramic layer by laser sintering. However, the scheme has the defect of low curing speed, and ceramic particles are easy to be dislocated under the action of external force before curing during printing, so that on one hand, a blank is easy to deform, on the other hand, the casting structure is loose, and the hardness and the strength of the casting prepared by the technology are difficult to improve. Meanwhile, the residual adhesive after printing sometimes blocks the printing head, thereby affecting the normal use of the printer.
Therefore, a ceramic material which is fast in curing and forming and contributes to improving the hardness and strength of the ceramic and a 3D printing method thereof are needed at present.
Disclosure of Invention
In order to solve the problems, the invention provides a ceramic material which is fast in curing and forming and is beneficial to improving the hardness and strength of the ceramic, and a 3D printing method thereof, and the invention adopts the following technical scheme:
the two-component ceramic 3D printing material comprises ceramic slurry and an additive, wherein the ceramic slurry comprises the following components in parts by weight:
75-80 parts of ceramic microspheres, 0.1-0.3 part of anionic surfactant, 1-2 parts of auxiliary adhesive and 6-8 parts of citric acid;
the additive comprises the following components in parts by weight: 3-4 parts of silicon carbide powder, 5-7 parts of sulfanilic acid and 5-6 parts of triethylamine.
The invention adopts the proposal of the combined action of the sulfanilic acid and the anionic surfactant, the sulfanilic acid and the anionic surfactant act together, and the amino group, the carboxyl group and the triethylamine in the sulfanilic acid are mutually connected or form a macromolecular polymer under the action of the anionic surfactant, thereby playing the effect of quick curing.
Preferably, the ceramic microspheres comprise the following components in parts by weight:
30-40 parts of wood porcelain clay, 10-15 parts of kaolin, 16-23 parts of alumina, 10-18 parts of zirconia, 3-6 parts of carrageenan and 7-15 parts of polyvinyl alcohol.
The ceramic microspheres prepared by the formula have the characteristic of high strength, and the corrosion resistance of the ceramic is enhanced through the action of the zirconium oxide, so that the form integrity of the ceramic microspheres in the printing process is further enhanced.
Preferably, the auxiliary adhesive is water-based silicone resin.
The water-based organic silicon resin is used as the auxiliary adhesive, the water-based organic silicon resin has the advantages of being fast in curing and strong in solution resistance, in the 3D printing process, the macromolecular polymer is formed in a combined action mode of the sulfanilic acid and the anionic surfactant to play a role in curing, but along with the printing process, due to the fact that the pressure applied to the bottom is increased, the green body is likely to deform under the pressure effect, the structure is loose, the water-based organic silicon resin is gradually cured in the printing process, and the stability of the whole structure is enhanced in the printing process.
Preferably, the metal powder is aluminum powder.
The invention adopts aluminum powder as raw material, and the aluminum powder is added to ensure that the aluminum powder is attached to the surface of the ceramic microsphere, thereby enhancing the wear resistance of the material.
Preferably, the particle size of the metal powder is 4000-5000 meshes.
Preferably, the ceramic microspheres are one or more of titanium nitride ceramics, aluminum oxide ceramics, silicon carbide ceramics, boron carbide ceramics and silicon oxide ceramics, and the particle size of the ceramic microspheres is 80-100 meshes.
Preferably, the ceramic microspheres are titanium nitride ceramics.
According to the technical scheme, the titanium nitride ceramic is adopted as the raw material, so that the mechanical strength of a printed product can be improved, the smooth printing process is facilitated, and the quality of the product is guaranteed.
Preferably, the anionic surfactant is sodium dodecyl benzene sulfonate.
The invention adopts the sodium dodecyl benzene sulfonate which has more branched chains and is beneficial to the generation of macromolecular polymers, thereby improving the curing efficiency of ceramic slurry during curing, shortening the curing time, being beneficial to the rapid molding of ceramics and preventing the printed ceramics from generating the conditions of blank body deformation and loose structure due to the slow curing speed of the slurry in the printing process.
A two-component ceramic 3D printing method comprises the following steps:
(1) constructing a three-dimensional model of the target part;
(2) ceramic slurry is conveyed to a slurry spray head through a feeding system, an additive is conveyed to an additive spray head through another system, and the slurry spray head and the additive spray head feed simultaneously to perform layered printing;
(3) standing the blank for 10-60 min, and drying in an oven at 40-80 ℃ for 10-60 min;
(4) and sintering the dried green body, wherein the sintering temperature is 1200-1400 ℃, and the sintering time is 30-36 h.
According to the scheme of feeding materials simultaneously by the slurry nozzle and the additive nozzle, the problem that the pipeline is blocked due to the fact that the slurry is solidified in the conveying pipe due to the fact that the slurry and the adhesive are mixed and printed in the traditional printing method is solved, in addition, the bonding efficiency can be improved due to the fact that the slurry and the additive are conveyed simultaneously and layered printing is conducted, and the situations that blanks are deformed and casting structures are loose due to the fact that the additives are not uniformly dispersed are prevented.
The invention has the beneficial effects that: the invention has the advantages of rapid solidification and forming, and high hardness and strength of the ceramic.
Detailed Description
The invention is further explained below with reference to specific embodiments:
example 1
The two-component ceramic 3D printing material comprises ceramic slurry and an additive, wherein the ceramic slurry comprises the following components in parts by weight:
75 parts of ceramic microspheres, 0.1 part of anionic surfactant, 1 part of auxiliary adhesive and 6-8 parts of citric acid;
the additive comprises the following components in parts by weight: 3 parts of silicon carbide powder, 5 parts of sulfanilic acid and 5 parts of triethylamine.
The ceramic microspheres comprise the following components in parts by weight:
30 parts of wood porcelain clay, 10 parts of kaolin, 16 parts of alumina, 10 parts of zirconia, 3 parts of carrageenan and 7 parts of polyvinyl alcohol.
The auxiliary adhesive is water-based organic silicon resin.
Wherein the metal powder adopts aluminum powder.
Wherein the particle size of the metal powder is 4000 meshes.
The ceramic microspheres are one or more of titanium nitride ceramics, alumina ceramics, silicon carbide ceramics, boron carbide ceramics and silicon oxide ceramics, and the particle size of the ceramic microspheres is sieved by a sieve of 80 meshes.
Wherein, the anionic surfactant adopts sodium dodecyl benzene sulfonate.
A two-component ceramic 3D printing method comprises the following steps:
(1) constructing a three-dimensional model of the target part;
(2) ceramic slurry is conveyed to a slurry spray head through a feeding system, an additive is conveyed to an additive spray head through another system, and the slurry spray head and the additive spray head feed simultaneously to perform layered printing;
(3) standing the blank for 10-60 min, and drying in an oven at 40 ℃ for 10 min;
(4) and sintering the dried green body, wherein the sintering temperature is 1200 ℃, and the sintering time is 30 h.
Example 2
The two-component ceramic 3D printing material comprises ceramic slurry and an additive, wherein the ceramic slurry comprises the following components in parts by weight:
75 parts of ceramic microspheres, 0.13 part of anionic surfactant, 1 part of auxiliary adhesive and 6 parts of citric acid;
the additive comprises the following components in parts by weight: 3 parts of silicon carbide powder, 5 parts of sulfanilic acid and 5 parts of triethylamine.
The ceramic microspheres comprise the following components in parts by weight:
40 parts of wood porcelain clay, 15 parts of kaolin, 23 parts of alumina, 10 parts of zirconia, 3-6 parts of carrageenan and 15 parts of polyvinyl alcohol.
The auxiliary adhesive is water-based organic silicon resin.
Wherein the metal powder adopts aluminum powder.
Wherein the particle size of the metal powder is 5000 meshes.
The ceramic microspheres are one or more of titanium nitride ceramics, alumina ceramics, silicon carbide ceramics, boron carbide ceramics and silicon oxide ceramics, and the particle size of the ceramic microspheres is 100 meshes.
Wherein, the anionic surfactant adopts sodium dodecyl benzene sulfonate.
A two-component ceramic 3D printing method comprises the following steps:
(1) constructing a three-dimensional model of the target part;
(2) ceramic slurry is conveyed to a slurry spray head through a feeding system, an additive is conveyed to an additive spray head through another system, and the slurry spray head and the additive spray head feed simultaneously to perform layered printing;
(3) standing the blank for 10-60 min, and drying in an oven at 40-80 ℃ for 60 min;
(4) and sintering the dried green body, wherein the sintering temperature is 1400 ℃, and the sintering time is 36 h.
Example 3
The two-component ceramic 3D printing material comprises ceramic slurry and an additive, wherein the ceramic slurry comprises the following components in parts by weight:
80 parts of ceramic microspheres, 0.3 part of anionic surfactant, 2 parts of auxiliary adhesive and 8 parts of citric acid;
the additive comprises the following components in parts by weight: 4 parts of silicon carbide powder, 7 parts of sulfanilic acid and 6 parts of triethylamine.
The ceramic microspheres comprise the following components in parts by weight:
40 parts of wood porcelain clay, 15 parts of kaolin, 23 parts of alumina, 18 parts of zirconia, 6 parts of carrageenan and 15 parts of polyvinyl alcohol.
The auxiliary adhesive is water-based organic silicon resin.
Wherein the metal powder adopts aluminum powder.
Wherein the particle size of the metal powder is 5000 meshes.
The ceramic microspheres are one or more of titanium nitride ceramics, alumina ceramics, silicon carbide ceramics, boron carbide ceramics and silicon oxide ceramics, and the particle size of the ceramic microspheres is 100 meshes.
Wherein, the anionic surfactant adopts sodium dodecyl benzene sulfonate.
A two-component ceramic 3D printing method comprises the following steps:
(1) constructing a three-dimensional model of the target part;
(2) ceramic slurry is conveyed to a slurry spray head through a feeding system, an additive is conveyed to an additive spray head through another system, and the slurry spray head and the additive spray head feed simultaneously to perform layered printing;
(3) standing the blank for 60min, and drying in an oven at 80 deg.C for 60 min;
(4) and sintering the dried green body, wherein the sintering temperature is 1400 ℃, and the sintering time is 36 h.
Example 4
The two-component ceramic 3D printing material comprises ceramic slurry and an additive, wherein the ceramic slurry comprises the following components in parts by weight:
77 parts of ceramic microspheres, 0.2 part of anionic surfactant, 1.5 parts of auxiliary adhesive and 7 parts of citric acid;
the additive comprises the following components in parts by weight: 4 parts of silicon carbide powder, 6 parts of sulfanilic acid and 5 parts of triethylamine.
The ceramic microspheres comprise the following components in parts by weight:
35 parts of wood porcelain clay, 12 parts of kaolin, 20 parts of alumina, 15 parts of zirconia, 5 parts of carrageenan and 10 parts of polyvinyl alcohol.
The auxiliary adhesive is water-based organic silicon resin.
Wherein the metal powder adopts aluminum powder.
Wherein, the particle size of the metal powder is 4500 mesh.
The ceramic microspheres are one or more of titanium nitride ceramics, alumina ceramics, silicon carbide ceramics, boron carbide ceramics and silicon oxide ceramics, and the particle size of the ceramic microspheres is 90-mesh sieved.
Wherein, the anionic surfactant adopts sodium dodecyl benzene sulfonate.
A two-component ceramic 3D printing method comprises the following steps:
(1) constructing a three-dimensional model of the target part;
(2) ceramic slurry is conveyed to a slurry spray head through a feeding system, an additive is conveyed to an additive spray head through another system, and the slurry spray head and the additive spray head feed simultaneously to perform layered printing;
(3) standing the blank for 30min, and drying in an oven at 50 deg.C for 30 min;
(4) and sintering the dried green body, wherein the sintering temperature is 1300 ℃, and the sintering time is 32 h.
Example 5
The two-component ceramic 3D printing material comprises ceramic slurry and an additive, wherein the ceramic slurry comprises the following components in parts by weight:
78 parts of ceramic microspheres, 0.2 part of anionic surfactant, 1.6 parts of auxiliary adhesive and 7.5 parts of citric acid;
the additive comprises the following components in parts by weight: 3.5 parts of silicon carbide powder, 6 parts of sulfanilic acid and 5.5 parts of triethylamine.
The ceramic microspheres comprise the following components in parts by weight:
35 parts of wood porcelain clay, 12 parts of kaolin, 18 parts of alumina, 14 parts of zirconia, 5 parts of carrageenan and 10 parts of polyvinyl alcohol.
The auxiliary adhesive is water-based organic silicon resin.
Wherein the metal powder adopts aluminum powder.
Wherein, the particle size of the metal powder is 4500 mesh.
The ceramic microspheres are one or more of titanium nitride ceramics, alumina ceramics, silicon carbide ceramics, boron carbide ceramics and silicon oxide ceramics, and the particle size of the ceramic microspheres is 90-mesh sieved.
Wherein, the anionic surfactant adopts sodium dodecyl benzene sulfonate.
A two-component ceramic 3D printing method comprises the following steps:
(1) constructing a three-dimensional model of the target part;
(2) ceramic slurry is conveyed to a slurry spray head through a feeding system, an additive is conveyed to an additive spray head through another system, and the slurry spray head and the additive spray head feed simultaneously to perform layered printing;
(3) standing the blank for 30min, and drying in an oven at 45 deg.C for 40 min;
(4) and sintering the dried green body, wherein the sintering temperature is 1300 ℃, and the sintering time is 32 h.

Claims (6)

1. The two-component ceramic 3D printing material is characterized by comprising ceramic slurry and an additive, wherein the ceramic slurry comprises the following components in parts by weight:
75-80 parts of ceramic microspheres, 0.1-0.3 part of anionic surfactant, 1-2 parts of auxiliary adhesive and 6-8 parts of citric acid; the auxiliary adhesive adopts water-based organic silicon resin;
the additive comprises the following components in parts by weight: 3-4 parts of silicon carbide powder, 5-7 parts of sulfanilic acid and 5-6 parts of triethylamine;
the ceramic slurry or the additive also comprises metal powder, wherein the metal powder is aluminum powder, and the particle size of the aluminum powder is 4000-5000 meshes.
2. The two-component ceramic 3D printing material according to claim 1, wherein the ceramic microspheres comprise the following components in parts by weight:
30-40 parts of wood porcelain clay, 10-15 parts of kaolin, 16-23 parts of alumina, 10-18 parts of zirconia, 3-6 parts of carrageenan and 7-15 parts of polyvinyl alcohol.
3. The two-component ceramic 3D printing material according to claim 1, characterized in that: the ceramic microspheres are one or more of titanium nitride ceramics, alumina ceramics, silicon carbide ceramics, boron carbide ceramics and silicon oxide ceramics, and the particle size of the ceramic microspheres is sieved by a sieve of 80-100 meshes.
4. The two-component ceramic 3D printing material according to claim 1, characterized in that: the ceramic microspheres are titanium nitride ceramics.
5. The two-component ceramic 3D printing material according to claim 1, characterized in that: the anionic surfactant is sodium dodecyl benzene sulfonate.
6. A method of 3D printing of two-component ceramics according to one of claims 1 to 5, characterized by comprising the steps of:
(1) constructing a three-dimensional model of the target part;
(2) conveying ceramic slurry to a slurry spray head through a feeding system, simultaneously conveying an initiator to an additive spray head by adopting another system, and simultaneously feeding the slurry spray head and the additive spray head for layered printing;
(3) standing the blank for 10-60 min, and drying in an oven at 40-80 ℃ for 10-60 min;
(4) and sintering the dried green body, wherein the sintering temperature is 1200-1400 ℃, and the sintering time is 30-36 h.
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1562889A (en) * 2004-04-07 2005-01-12 中国科学院上海硅酸盐研究所 Solidified agent in use for water based pulp of ceramics
CN105645840A (en) * 2015-12-30 2016-06-08 成都新柯力化工科技有限公司 Ceramic material for 3D printing and manufacturing method thereof
CN106810200A (en) * 2017-02-20 2017-06-09 醴陵市陶瓷3D打印研究所 Double-component ceramics 3D printing extrusion molding material and its application method

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1562889A (en) * 2004-04-07 2005-01-12 中国科学院上海硅酸盐研究所 Solidified agent in use for water based pulp of ceramics
CN105645840A (en) * 2015-12-30 2016-06-08 成都新柯力化工科技有限公司 Ceramic material for 3D printing and manufacturing method thereof
CN106810200A (en) * 2017-02-20 2017-06-09 醴陵市陶瓷3D打印研究所 Double-component ceramics 3D printing extrusion molding material and its application method

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