CN108285333A - A kind of two-component ceramics 3D printing material and its 3D printing method - Google Patents

A kind of two-component ceramics 3D printing material and its 3D printing method Download PDF

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Publication number
CN108285333A
CN108285333A CN201810054433.3A CN201810054433A CN108285333A CN 108285333 A CN108285333 A CN 108285333A CN 201810054433 A CN201810054433 A CN 201810054433A CN 108285333 A CN108285333 A CN 108285333A
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parts
ceramics
component
ceramic
additive
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CN108285333B (en
Inventor
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 CERAMICS INDUSTRY Co Ltd
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LONGQUAN JINHONG CERAMICS INDUSTRY 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
    • B33Y70/00—Materials specially adapted for additive manufacturing
    • 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

Invention is related to 3D printing technique field.The present invention provides a kind of two-component ceramics 3D printing material, including ceramic slurry and additive, ceramic slurry includes the component of following parts by weight：75 ~ 80 parts of ceramic microsphere, 0.1 ~ 0.3 part of anion surfactant assist 1 ~ 2 part of adhesive, 6 ~ 8 parts of citric acid；Additive includes the component of following parts by weight：3 ~ 4 parts of silicon carbide powder, 5 ~ 7 parts of p-aminobenzene sulfonic acid, 5 ~ 6 parts of triethylamine.The present invention also provides a kind of two-component ceramics 3D printing methods:Threedimensional model is built, ceramic slurry slurry nozzle is delivered to by feed system, while additive is delivered to by additive nozzle, slurry nozzle and the feeding simultaneously of additive nozzle using another set of system, carries out layering printing；After green body is stood, it is placed in baking oven in drying；Green body after drying is sintered.The present invention has solidified forming quick, ceramic hardness and the high advantage of intensity.

Description

A kind of two-component ceramics 3D printing material and its 3D printing method
Technical field
The present invention relates to 3D printing technique fields, are beaten in particular to a kind of two-component ceramics 3D printing material and its 3D Impression method.
Background technology
In the 1990s, a kind of three-dimensional printing technology has been invented by Massachusetts Institute Technology, it is a kind of mathematical model Based on file, with powdery metal or plastic etc. can bonding material, construct the skill of object by layer-by-layer printing Art.Past, it was often used for modeling in fields such as mold manufacturing, industrial designs, was now increasingly used for the direct of some products Manufacture.Especially some high value applications（Such as hip joint or tooth or some airplane components）Have and has used this skill Parts made of art printing.The research applied in ceramic material with three-dimensional printing technology is goed deep into, using 3 D-printing ceramics Device becomes a reality.Traditional ceramic making mould molding using clay, dries, molds, falls base, firing etc., input Time is long, fund cost is big, and be not easy to change.Therefore, the ceramic component that 3D printing goes out is applicable to manufacture small lot Model constructs complicated device, greatly reduces time and the manufacturing cost of modification model.
Prior art China patent CN104339437A discloses a kind of method general producing ceramic-mould with 3D printing technique Ceramic powder and adhesive, which are respectively charged into 3D printing head, will need the graphics for printing casting mold to input 3D printer, then according to figure Paper successively prints casting mold, ultimately forms required casting mold, then by entire casting mold be put into heating furnace to ceramic powder and adhesive into Row sintering, forms ceramic-mould.
However, the prior art is laid with the adhesive of one layer of powdery between two-layer ceramic powder, by laser sintered so that Newly add ceramic layer to cohere with molded ceramic layer.But the program haves the shortcomings that curing rate is slow, the ceramic particle in printing Between before curing be easy misplaced by outer force effect, be on the one hand easy to cause green body and deform upon, on the other hand can lead It causes casting structure loose, its hardness and strength is difficult to improve using casting made from the technology.It is remained after printing simultaneously Adhesive block print head sometimes, to influence the normal use of printer.
Therefore it needs a kind of solidified forming quick at present, helps to improve ceramic hardness and the ceramic material and its 3D of intensity Method of printing.
Invention content
To solve the above-mentioned problems provide solidified forming it is quick, help to improve ceramic hardness and intensity ceramic material and Its 3D printing method, the present invention use following technical scheme：
A kind of two-component ceramics 3D printing material, including ceramic slurry and additive, the ceramic slurry include following weight The component of part：
75 ~ 80 parts of ceramic microsphere, 0.1 ~ 0.3 part of anion surfactant assist 1 ~ 2 part of adhesive, 6 ~ 8 parts of citric acid；
The additive includes the component of following parts by weight：3 ~ 4 parts of silicon carbide powder, 5 ~ 7 parts of p-aminobenzene sulfonic acid, triethylamine 5 ~ 6 parts.
Present invention employs p-aminobenzene sulfonic acid and the coefficient scheme of anion surfactant, the two is made jointly With amino and carboxyl and triethylamine in p-aminobenzene sulfonic acid are interconnected under anion surfactant effect or, being formed Macromolecule polyalcohol, to play quick-setting effect.
Preferably, the ceramic microsphere includes the component of following parts by weight：
30 ~ 40 parts of the wooden Mount Tai china clay, 10 ~ 15 parts of kaolin, 16 ~ 23 parts of aluminium oxide, 10 ~ 18 parts of zirconium oxide, 3 ~ 6 parts of carragheen gather 7 ~ 15 parts of vinyl alcohol.
The present invention prepares ceramic microsphere using this kind of formula, and prepared ceramic microsphere has the characteristics that intensity is high, passes through The effect of zirconium oxide, strengthens the corrosion resistance of ceramics, and the form that further enhances ceramic microsphere in print procedure is complete It is whole.
Preferably, the auxiliary adhesive uses waterborne organic silicon resin.
Present invention employs waterborne organic silicon resins as auxiliary adhesive, present invention employs waterborne organic silicon resin, Waterborne organic silicon resin has solidification quickly, the strong advantage of solvent resistant, during 3D printing, by p-aminobenzene sulfonic acid Form macromolecule polyalcohol with the coefficient mode of anion surfactant, play the role of it is cured, but with printing It carries out, since the pressure that bottom is subject to increases, it is possible to green body occurs under pressure and deforms upon, loosely organized feelings Condition, and waterborne organic silicon resin is gradually cured in print procedure, enhances the integrally-built stability in printing.
Preferably, the metal-powder uses aluminium powder.
Present invention employs aluminium powders as raw material, and adding aluminium powder can allow aluminium powder to be attached on the surface of ceramic microsphere, Strengthen the abrasive resistance of material.
Preferably, the metal-powder grain size crosses 4000 ~ 5000 mesh sieve.
Preferably, the ceramic microsphere be titanium nitride ceramic, aluminium oxide ceramics, silicon carbide ceramics, boron carbide ceramics, The grain size of one or more of silicon oxide ceramics, the ceramic microsphere crosses 80 ~ 100 mesh sieve.
Preferably, the ceramic microsphere is titanium nitride ceramic.
Titanium nitride ceramic is used in the inventive solutions as raw material, and the machinery that can improve printed product is strong Degree, contributes to being smoothed out for print procedure, while also having ensured the quality of product.
Preferably, the anion surfactant uses neopelex.
Present invention employs neopelex, neopelex has more branch, is conducive to big The generation of Molecularly Imprinted Polymer shortens hardening time, contributes to ceramics to improve curing efficiency of the ceramic slurry in solidification Rapid shaping, it is therefore prevented that in print procedure, since slurry curing speed is slow, the ceramics printed is caused green body hair occur Raw deformation, loosely organized situation.
A kind of two-component ceramics 3D printing method, includes the following steps：
（1）Build the threedimensional model of target part；
（2）Ceramic slurry is delivered to slurry nozzle by feed system, while being delivered to additive using another set of system The feeding simultaneously of additive nozzle, the slurry nozzle and the additive nozzle, carries out layering printing；
（3）After green body is stood 10 ~ 60min, it is placed in baking oven in 40 ~ 80 DEG C of dry 10 ~ 60min；
（4）Green body after drying is sintered, the sintering temperature is 1200 ~ 1400 DEG C, and sintering time is 30 ~ 36h.
For the present invention using the scheme of slurry nozzle and the feeding simultaneously of additive nozzle, avoiding will slurry in conventional printing methods Slurry caused by being printed after material and adhesive mixing is cured in delivery pipe to be occurred so as to cause the case where line clogging, In addition slurry and additive convey be layered printing and can improve simultaneously coheres efficiency, it is therefore prevented that additive dispersion is uneven and leads The green body of cause deforms upon, and the loose situation of casting structure occurs.
The beneficial effects of the present invention are：The present invention has solidified forming quick, ceramic hardness and the high advantage of intensity.
Specific implementation mode
The present invention is further expalined with reference to specific implementation case：
Embodiment 1
A kind of two-component ceramics 3D printing material, including ceramic slurry and additive, the ceramic slurry include following weight The component of part：
75 parts of ceramic microsphere, 0.1 part of anion surfactant assist 1 part of adhesive, 6 ~ 8 parts of citric acid；
The additive includes the component of following parts by weight：3 parts of silicon carbide powder, 5 parts of p-aminobenzene sulfonic acid, 5 parts of triethylamine.
Wherein, the ceramic microsphere includes the component of following parts by weight：
30 parts of the wooden Mount Tai china clay, 10 parts of kaolin, 16 parts of aluminium oxide, 10 parts of zirconium oxide, 3 parts of carragheen, 7 parts of polyvinyl alcohol.
Wherein, the auxiliary adhesive uses waterborne organic silicon resin.
Wherein, the metal-powder uses aluminium powder.
Wherein, the metal-powder grain size crosses 4000 mesh sieve.
Wherein, the ceramic microsphere is titanium nitride ceramic, aluminium oxide ceramics, silicon carbide ceramics, boron carbide ceramics, oxidation The grain size of one or more of silicon ceramics, the ceramic microsphere crosses 80 mesh sieve.
Wherein, the anion surfactant uses neopelex.
A kind of two-component ceramics 3D printing method, includes the following steps：
（1）Build the threedimensional model of target part；
（2）Ceramic slurry is delivered to slurry nozzle by feed system, while being delivered to additive using another set of system The feeding simultaneously of additive nozzle, the slurry nozzle and the additive nozzle, carries out layering printing；
（3）After green body is stood 10 ~ 60min, it is placed in baking oven in 40 DEG C of dry 10min；
（4）Green body after drying is sintered, the sintering temperature is 1200 DEG C, sintering time 30h.
Embodiment 2
A kind of two-component ceramics 3D printing material, including ceramic slurry and additive, the ceramic slurry include following weight The component of part：
75 parts of ceramic microsphere, 0.13 part of anion surfactant assist 1 part of adhesive, 6 parts of citric acid；
The additive includes the component of following parts by weight：3 parts of silicon carbide powder, 5 parts of p-aminobenzene sulfonic acid, 5 parts of triethylamine.
Wherein, the ceramic microsphere includes the component of following parts by weight：
40 parts of the wooden Mount Tai china clay, 15 parts of kaolin, 23 parts of aluminium oxide, 10 parts of zirconium oxide, 3 ~ 6 parts of carragheen, 15 parts of polyvinyl alcohol.
Wherein, the auxiliary adhesive uses waterborne organic silicon resin.
Wherein, the metal-powder uses aluminium powder.
Wherein, the metal-powder grain size crosses 5000 mesh sieve.
Wherein, the ceramic microsphere is titanium nitride ceramic, aluminium oxide ceramics, silicon carbide ceramics, boron carbide ceramics, oxidation The grain size of one or more of silicon ceramics, the ceramic microsphere sieves with 100 mesh sieve.
Wherein, the anion surfactant uses neopelex.
A kind of two-component ceramics 3D printing method, includes the following steps：
（1）Build the threedimensional model of target part；
（2）Ceramic slurry is delivered to slurry nozzle by feed system, while being delivered to additive using another set of system The feeding simultaneously of additive nozzle, the slurry nozzle and the additive nozzle, carries out layering printing；
（3）After green body is stood 10 ~ 60min, it is placed in baking oven in 40 ~ 80 DEG C of dry 60min；
（4）Green body after drying is sintered, the sintering temperature is 1400 DEG C, sintering time 36h.
Embodiment 3
A kind of two-component ceramics 3D printing material, including ceramic slurry and additive, the ceramic slurry include following weight The component of part：
80 parts of ceramic microsphere, 0.3 part of anion surfactant assist 2 parts of adhesive, 8 parts of citric acid；
The additive includes the component of following parts by weight：4 parts of silicon carbide powder, 7 parts of p-aminobenzene sulfonic acid, 6 parts of triethylamine.
Wherein, the ceramic microsphere includes the component of following parts by weight：
40 parts of the wooden Mount Tai china clay, 15 parts of kaolin, 23 parts of aluminium oxide, 18 parts of zirconium oxide, 6 parts of carragheen, 15 parts of polyvinyl alcohol.
Wherein, the auxiliary adhesive uses waterborne organic silicon resin.
Wherein, the metal-powder uses aluminium powder.
Wherein, the metal-powder grain size crosses 5000 mesh sieve.
Wherein, the ceramic microsphere is titanium nitride ceramic, aluminium oxide ceramics, silicon carbide ceramics, boron carbide ceramics, oxidation The grain size of one or more of silicon ceramics, the ceramic microsphere sieves with 100 mesh sieve.
Wherein, the anion surfactant uses neopelex.
A kind of two-component ceramics 3D printing method, includes the following steps：
（1）Build the threedimensional model of target part；
（2）Ceramic slurry is delivered to slurry nozzle by feed system, while being delivered to additive using another set of system The feeding simultaneously of additive nozzle, the slurry nozzle and the additive nozzle, carries out layering printing；
（3）After green body is stood 60min, it is placed in baking oven in 80 DEG C of dry 60min；
（4）Green body after drying is sintered, the sintering temperature is 1400 DEG C, sintering time 36h.
Embodiment 4
A kind of two-component ceramics 3D printing material, including ceramic slurry and additive, the ceramic slurry include following weight The component of part：
77 parts of ceramic microsphere, 0.2 part of anion surfactant assist 1.5 parts of adhesive, 7 parts of citric acid；
The additive includes the component of following parts by weight：4 parts of silicon carbide powder, 6 parts of p-aminobenzene sulfonic acid, 5 parts of triethylamine.
Wherein, the ceramic microsphere includes the component of following parts by weight：
35 parts of the wooden Mount Tai china clay, 12 parts of kaolin, 20 parts of aluminium oxide, 15 parts of zirconium oxide, 5 parts of carragheen, 10 parts of polyvinyl alcohol.
Wherein, the auxiliary adhesive uses waterborne organic silicon resin.
Wherein, the metal-powder uses aluminium powder.
Wherein, the metal-powder grain size crosses 4500 mesh sieve.
Wherein, the ceramic microsphere is titanium nitride ceramic, aluminium oxide ceramics, silicon carbide ceramics, boron carbide ceramics, oxidation The grain size of one or more of silicon ceramics, the ceramic microsphere crosses 90 mesh sieve.
Wherein, the anion surfactant uses neopelex.
A kind of two-component ceramics 3D printing method, includes the following steps：
（1）Build the threedimensional model of target part；
（2）Ceramic slurry is delivered to slurry nozzle by feed system, while being delivered to additive using another set of system The feeding simultaneously of additive nozzle, the slurry nozzle and the additive nozzle, carries out layering printing；
（3）After green body is stood 30min, it is placed in baking oven in 50 DEG C of dry 30min；
（4）Green body after drying is sintered, the sintering temperature is 1300 DEG C, sintering time 32h.
Embodiment 5
A kind of two-component ceramics 3D printing material, including ceramic slurry and additive, the ceramic slurry include following weight The component of part：
78 parts of ceramic microsphere, 0.2 part of anion surfactant assist 1.6 parts of adhesive, 7.5 parts of citric acid；
The additive includes the component of following parts by weight：3.5 parts of silicon carbide powder, 6 parts of p-aminobenzene sulfonic acid, triethylamine 5.5 part.
Wherein, the ceramic microsphere includes the component of following parts by weight：
35 parts of the wooden Mount Tai china clay, 12 parts of kaolin, 18 parts of aluminium oxide, 14 parts of zirconium oxide, 5 parts of carragheen, 10 parts of polyvinyl alcohol.
Wherein, the auxiliary adhesive uses waterborne organic silicon resin.
Wherein, the metal-powder uses aluminium powder.
Wherein, the metal-powder grain size crosses 4500 mesh sieve.
Wherein, the ceramic microsphere is titanium nitride ceramic, aluminium oxide ceramics, silicon carbide ceramics, boron carbide ceramics, oxidation The grain size of one or more of silicon ceramics, the ceramic microsphere crosses 90 mesh sieve.
Wherein, the anion surfactant uses neopelex.
A kind of two-component ceramics 3D printing method, includes the following steps：
（1）Build the threedimensional model of target part；
（2）Ceramic slurry is delivered to slurry nozzle by feed system, while being delivered to additive using another set of system The feeding simultaneously of additive nozzle, the slurry nozzle and the additive nozzle, carries out layering printing；
（3）After green body is stood 30min, it is placed in baking oven in 45 DEG C of dry 40min；
（4）Green body after drying is sintered, the sintering temperature is 1300 DEG C, sintering time 32h.

Claims (9)

1. a kind of two-component ceramics 3D printing material, which is characterized in that including ceramic slurry and additive, the ceramic slurry Material includes the component of following parts by weight：
75 ~ 80 parts of ceramic microsphere, 0.1 ~ 0.3 part of anion surfactant assist 1 ~ 2 part of adhesive, 6 ~ 8 parts of citric acid；
The additive includes the component of following parts by weight：3 ~ 4 parts of silicon carbide powder, 5 ~ 7 parts of p-aminobenzene sulfonic acid, triethylamine 5 ~ 6 parts.
2. a kind of two-component ceramics 3D printing material according to claim 1, which is characterized in that the ceramic microsphere packet Include the component of following parts by weight：
30 ~ 40 parts of the wooden Mount Tai china clay, 10 ~ 15 parts of kaolin, 16 ~ 23 parts of aluminium oxide, 10 ~ 18 parts of zirconium oxide, 3 ~ 6 parts of carragheen gather 7 ~ 15 parts of vinyl alcohol.
3. a kind of two-component ceramics 3D printing material according to claim 1, it is characterised in that：The auxiliary adhesive Using waterborne organic silicon resin.
4. a kind of two-component ceramics 3D printing material according to claim 1, it is characterised in that：The metal-powder is adopted Use aluminium powder.
5. a kind of two-component ceramics 3D printing material according to claim 1, it is characterised in that：The metal-powder grain Diameter crosses 4000 ~ 5000 mesh sieve.
6. a kind of two-component ceramics 3D printing material according to claim 1, it is characterised in that：The ceramic microsphere is One or more of titanium nitride ceramic, aluminium oxide ceramics, silicon carbide ceramics, boron carbide ceramics, silicon oxide ceramics, the pottery The grain size of porcelain microballoon crosses 80 ~ 100 mesh sieve.
7. according to a kind of two-component ceramics 3D printing material described in claim 1, it is characterised in that：The ceramic microsphere is nitrogen Change titanium ceramics.
8. a kind of two-component ceramics 3D printing material according to claim 1, it is characterised in that：The anionic surface Activating agent uses neopelex.
9. a kind of two-component ceramics 3D printing method according to one of claim 1-8, which is characterized in that including following step Suddenly：
（1）Build the threedimensional model of target part；
（2）Ceramic slurry is delivered to slurry nozzle by feed system, while being delivered to initiator using another set of system The feeding simultaneously of additive nozzle, the slurry nozzle and the additive nozzle, carries out layering printing；
（3）After green body is stood 10 ~ 60min, it is placed in baking oven in 40 ~ 80 DEG C of dry 10 ~ 60min；
（4）Green body after drying is sintered, the sintering temperature is 1200 ~ 1400 DEG C, and sintering time is 30 ~ 36h.
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