CN109970450A - A kind of light sensitive ceramics liquid and its ceramic member for 3D printing - Google Patents
A kind of light sensitive ceramics liquid and its ceramic member for 3D printing Download PDFInfo
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- CN109970450A CN109970450A CN201910242364.3A CN201910242364A CN109970450A CN 109970450 A CN109970450 A CN 109970450A CN 201910242364 A CN201910242364 A CN 201910242364A CN 109970450 A CN109970450 A CN 109970450A
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- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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- B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
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- B29C64/106—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material
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- 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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- C04B35/565—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides based on silicon carbide
- C04B35/571—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides based on silicon carbide obtained from Si-containing polymer precursors or organosilicon monomers
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Abstract
The invention discloses a kind of light sensitive ceramics liquid for photocuring 3D printing, it include: the photoinitiator of the photosensitive silicone oil of 74.3%-89.3%, the silicone oil additive of 8.7%-22.3%, the metallic catalyst of 0.9%-2.6%, the coloring agent of 0-0.02%, 0.9%-2.0%, wherein, the photosensitive silicone oil is made of the acrylic acid of the liquid silicone and 13.8%-24.9% containing epoxy group of 74.6%-83.2%.The present invention can obtain the ceramic member product of well-formed through oversintering.
Description
Technical field
The invention belongs to ceramic fields, and in particular to a kind of light sensitive ceramics liquid for photocuring 3D printing and with the ceramics
Liquid is the ceramic member of raw material preparation.
Background technique
Traditional ceramics preparation process such as sizing material forming method and dry pressing are difficult to form near-net-shape labyrinth, and mechanical
Processing again can damage green body micro-structure, and time-consuming and laborious.3D printing adds up molding manufacturing theory, it is made to have complexity
Structure rapid shaping, the technical advantage efficiently produced, are highly suitable as the preparation method of special-shaped ceramics.
The main application method of the 3D printing of ceramic material is stereo lithography (SLA), digital optical processing technique (DLP),
Selective laser sintering technology (SLS), layer separated growth technology (LOM), inkjet printing technology (IJP), fused glass pellet skill
Art (FDM).Wherein, using photocuring technology as the 3D printing technique of principle, such as stereolithography, digital light processing, the accuracy of manufacture
It is the excellent means for producing accurate advanced ceramics structural material up to micron level.
There are two types of photocuring 3D printing useful raw materials: one is photosensitive resin macromolecules and powder mixing slurry, and one is preceding
Body polymer is driven, wherein the former is the raw material mainly used in current photocuring 3D printing technique, mainly for the manufacture of oxide
Ceramics, such as zirconium oxide, aluminium oxide, hydroxyapatite, calcium phosphate, silica.For reduce sintering process in green body shrinking percentage,
Photosensitive resin need to uniformly carry ceramic powder as much as possible；In addition to this, powder and liquid resin optical parameter such as refractive index
Need matched well.Such as Publication No. CN108191410A, CN109227877A, CN108249930A earlier patent application,
Although the ceramics of ceramic slurry preparation show the low advantage of shrinking percentage, in order to keep low glutinous while more multiple-bearer powder
It spends, keeps good light-cured performance and resolution ratio, solves the particulate matters such as powder because leading to print resolution to light scattering
It is low, prevent sintering densification process generate defect and crackle etc., need during the preparation process using plurality of reagents handle powder, and
A variety of auxiliary agents are added in the slurry, and preparation process complex is not environmentally protective.
Relative to drawbacks described above, the problem of two-phase matches then is not present in precursor polymer, and prepared by precursor ceramic
Method design of material scale can be as small as molecular level, have can liquid phase molding, can low-temp ceramics, even green body it is good etc. a variety of excellent
Gesture is the raw material of 3D printing ceramic technology most application prospect.But the current research of such raw material is less, and stops at substantially
As high molecular application is formed after printing, it cannot pass through sintering and be converted into ceramics.This is because solvent contains in its preparation process
Measure that more, silicon content is few, viscosity is low, heating is difficult to be crosslinked as close network structure after being sintered, and photocuring green body can not be through sintering into
For ceramic member, it is easy acutely contraction, cracking, is crushed and intensity is extremely low.
Summary of the invention
In view of this, the present invention is directed to propose a kind of light sensitive ceramics liquid and its ceramic member for 3D printing, on solving
State technical problem.
The present invention uses a kind of raw material of precursor polymer as photocuring 3D printing, with the silicone oil being in a liquid state under room temperature
For the ceramic source Si, and photosensitive modification is carried out to silicone oil first, promotes being effectively formed for photocured cross-linked network, can be avoided solvent
Use, while being aided with small molecule silicone oil as liquid phase flexibility additive, improve the consistency of ceramic member, formed through 3D printing
Green body can obtain the ceramic member product of well-formed through oversintering.
A kind of light sensitive ceramics liquid for photocuring 3D printing of the present invention, comprising: the photosensitive silicone oil of 74.3%-89.3%,
The silicone oil additive of 8.7%-22.3%, the metallic catalyst of 0.9%-2.6%, 0-0.02% coloring agent, 0.9%-2.0%
Photoinitiator, wherein the photosensitive silicone oil by 74.6%-83.2% the liquid silicone and 13.8%- containing epoxy group
24.9% acrylic acid is made.
Wherein, at least containing there are two the epoxies being connected with silane in each molecule of the liquid silicone containing epoxy group
Group, epoxy group content 2-10%, viscosity 50-200mPas.
Acrylate with photosensitive property introduces liquid silicone by way of epoxy ring-opening, so that obtain
Photosensitive silicone oil has a considerable amount of secondary hydroxyls, can make photosensitive silicone oil effective activation, reactivity worth enhancing, while ring-opening reaction
Increase the photosensitive silicone oil branch of product, segment hardness is improved, and the cured Quick cross-linking of subsequent optical and crosslinking are conducive to
The quick release of stress in the process reduces the shrinkage cracking risk of sintering.
Wherein, the silicone oil additive is dimethicone or hydroxy silicon oil；The metallic catalyst is tin dilaurate two
Butyl tin or butyl titanate；The coloring agent is lipid coloring agent, preferably oil red, S Ⅳ；Photoinitiator is stated as freely
Base photoinitiator, preferably 2,4,6- trimethylbenzoyl phenyl phosphinic acid ethyl esters (TPO-L), 2,4,6- trimethylbenzoyl phosphines
Acetoacetic ester (TPO).The silicone oil additive can improve the brittleness of ceramic body, and can be in pyrolytic process in dense body structure
Further alleviate green body internal stress in favor of the smooth exclusion of gas molecule, prevent green body from opening in the middle channel for forming gas release
It splits, to improve the consistency of ceramic member.
A kind of preparation method of the ceramic member of photocuring 3D printing, includes the following steps:
(1) by the photosensitive silicone oil of 74.3%-89.3%, the silicone oil additive of 8.7%-22.3%, 0.9%-2.6% gold
Metal catalyst, the coloring agent of 0-0.02%, 0.9%-2.0% photoinitiator obtain light sensitive ceramics liquid after mixing；
(2) green body is obtained to light sensitive ceramics liquid printing shaping using photocuring 3D printer；
(3) green body is sintered, obtains ceramic member.
Wherein, the photosensitive silicone oil is made by following step: by the poly- silicon oxygen of the liquid containing epoxy group of 74.6%-83.2%
Alkane, the acrylic acid of 13.8%-24.9%, 0.04%-0.07% modified catalyst mixing after at 90-120 DEG C heat 3-8 it is small
When；Wherein, the modified catalyst is amines catalyst, preferably N, N- dimethyl cyclohexyl amine, N, N- dimethyl benzylamine, triethylamine
In any one.
Wherein, the 3D printing parameter of the step (2) are as follows: 50 μm of single layer, single layer time for exposure 5-10s, unit area exposes
Light energy 1.5-6mJ/cm2。
Wherein, the sintering schedule of the step (3) are as follows: with 2 DEG C/min heating rate from room temperature to 1000 DEG C, and in
1000 DEG C of heat preservation 1h.
Compared with prior art, the invention has the benefit that
Light sensitive ceramics liquid provided by the present invention for 3D printing is single-phase neat liquid, is free of solvent, without such as ceramic powder
The addition of the solid matters such as body, filler can increase substantially print resolution as printing raw material, and Si content is high, in advance through photosensitive
The modified light-cured performance obtained is good, and when single layer print thickness is set as 50 μm, which exposes 5-10s
Solidification, print resolution is high, and printing green body has higher mechanical strength, and green body details is clear, structural integrity, and silicone oil is soft or hard suitable
In, be conducive to cross moulding and discharge stress, cracking caused by a large amount of decomposed substance evolutions etc. is also avoided in sintering process and is burnt
Knot property difference problem, sintering densification degree is high, can obtain the ceramic member that complete densification has considerable mechanical strength.
Detailed description of the invention
The attached drawing for constituting a part of the invention is used to provide further understanding of the present invention, schematic reality of the invention
It applies example and its explanation is used to explain the present invention, do not constitute improper limitations of the present invention.In the accompanying drawings:
Preset model photo in Digital Light Processing apparatus used in Fig. 1 present invention.
The super depth of field three-dimensional microscope for the ceramic body that Fig. 2 present invention gained light sensitive ceramics liquid is obtained through photocuring 3D printing
Photo.
The super depth of field three-dimensional microscope photo of the made ceramic member of Fig. 3 present invention.
Fig. 4 is not add the light sensitive ceramics liquid of hydroxy silicon oil or dimethicone as the super scape of ceramic member made from raw material
Deep three-dimensional microscope photo.
The photo for other ceramic bodies that Fig. 5 present invention gained light sensitive ceramics liquid is obtained through photocuring 3D printing.
Specific embodiment
In order to better understand the present invention, below with reference to specific attached drawing, the present invention will be described in detail.
Embodiment 1:
It is a kind of for the light sensitive ceramics liquid of photocuring 3D printing and the preparation of ceramic member, comprising the following steps:
(1) 79.2% epoxy silicon oil, 19.8% acrylic acid, 1% triethylamine are heated in 105 DEG C after mixing
6 hours, photosensitive silicone oil was obtained after cooling；
(2) dimethicone that photosensitive silicone oil quality 10% is added in photosensitive silicone oil is obtained in step (1), the two of 1%
Dibutyl tin laurate, 1% TPO-L, 0.02% oil red are uniformly mixed, obtain light sensitive ceramics liquid；
(3) light sensitive ceramics liquid obtained in step (2) is put into digital light processing 3D printing equipment, print parameters is set
It is 50 μm of single layer, single layer time for exposure 5s, unit area exposure energy 6mJ/cm2, printed, made pottery according to preset model
Porcelain billet body；
(4) ceramic body obtained in step (3) is put into sintering in high temperature argon tube furnace and obtains silicon-oxygen-carbon ceramic part, makes pottery
Porcelain piece is 35% with respect to green body shrinking percentage, compressive strength 18MPa.
Embodiment 2:
It is a kind of for the light sensitive ceramics liquid of photocuring 3D printing and the preparation of ceramic member, comprising the following steps:
(1) by 81.7% epoxy silicon oil, 16.3% acrylic acid, 2% N, N- dimethyl cyclohexyl amine is after mixing
It is heated 5 hours in 95 DEG C, obtains photosensitive silicone oil after cooling；
(2) hydroxy silicon oil that photosensitive silicone oil quality 20% is added in photosensitive silicone oil, 2.5% titanium are obtained in step (1)
Sour four butyl esters, 1% TPO, 0.02% S Ⅳ are uniformly mixed, obtain light sensitive ceramics liquid；
(3) light sensitive ceramics liquid obtained in step (2) is put into digital light processing 3D printing equipment, print parameters is set
It is 50 μm of single layer, single layer time for exposure 7s, unit area exposure energy 3mJ/cm2, printed, made pottery according to preset model
Porcelain billet body；
(4) ceramic body obtained in step (3) is put into sintering in high temperature argon tube furnace and obtains silicon-oxygen-carbon ceramic part, makes pottery
Porcelain piece is 38% with respect to green body shrinking percentage, compressive strength 20MPa.
Embodiment 3:
It is a kind of for the light sensitive ceramics liquid of photocuring 3D printing and the preparation of ceramic member, comprising the following steps:
(1) 8.32% epoxy silicon oil, 13.8% acrylic acid, 3% triethylamine are heated 3 in 90 DEG C after mixing
Hour, photosensitive silicone oil is obtained after cooling；
(2) hydroxy silicon oil that photosensitive silicone oil quality 30% is added in photosensitive silicone oil, 3% metatitanic acid are obtained in step (1)
Four butyl esters, 2% TPO-L, 0.01% oil red are uniformly mixed, obtain light sensitive ceramics liquid；
(3) light sensitive ceramics liquid obtained in step (2) is put into digital light processing 3D printing equipment, print parameters is set
It is 50 μm of single layer, single layer time for exposure 10s, unit area exposure energy 2.8mJ/cm2, printed, obtained according to preset model
To ceramic body；
(4) ceramic body obtained in step (3) is put into sintering in high temperature argon tube furnace and obtains silicon-oxygen-carbon ceramic part, makes pottery
Porcelain piece is 40% with respect to green body shrinking percentage, compressive strength 20MPa.
Embodiment 4:
It is a kind of for the light sensitive ceramics liquid of photocuring 3D printing and the preparation of ceramic member, comprising the following steps:
(1) by 74.6% epoxy silicon oil, 24.9% acrylic acid, 0.5% N, N- dimethyl benzylamine is after mixing
It is heated 8 hours in 120 DEG C, obtains photosensitive silicone oil after cooling；
(2) dimethicone that photosensitive silicone oil quality 15% is added in photosensitive silicone oil is obtained in step (1), 1.5%
Dibutyl tin dilaurate, 2.5% TPO, does not add coloring agent, is uniformly mixed, obtains light sensitive ceramics liquid；
(3) light sensitive ceramics liquid obtained in step (2) is put into digital light processing 3D printing equipment, print parameters is set
It is 50 μm of single layer, single layer time for exposure 6s, unit area exposure energy 5mJ/cm2, printed, made pottery according to preset model
Porcelain billet body；
(4) ceramic body obtained in step (3) is put into sintering in high temperature argon tube furnace and obtains silicon-oxygen-carbon ceramic part, makes pottery
Porcelain piece is 38% with respect to green body shrinking percentage, compressive strength 18MPa.
Preset model used in embodiment 1-4 step (3) is shown in attached drawing 1.Model is the cylindrical body of diameter 2cm, and inside is
Engraved structure.Molding green body is shown in attached drawing 2, and a diameter of 2cm ± 0.1cm is consistent with model structure.Ceramic body warp
Obtain silicon-oxygen-carbon ceramic part after the sintering of high temperature argon tube furnace, sintering schedule be with 2 DEG C/min heating rate from room temperature to
1000 DEG C, and in 1000 DEG C of heat preservation 1h, it is taken out after furnace cooling.Ceramic member is as shown in Fig. 3, and structure is consistent with model, compared with
The defects of green body size is shunk, and surface topography and quality are good, no local deformation, flawless and stomata.Attached drawing 3 and attached drawing
4 comparisons are it is found that light sensitive ceramics liquid structure of the present invention is more relative to the light sensitive ceramics liquid for not adding dimethicone or hydroxy silicon oil
To be regular, structure is more fine and close.The light sensitive ceramics liquid that embodiment 1-4 is prepared also can print other labyrinth green bodies, such as
Shown in attached drawing 5.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Within mind and principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.
Claims (10)
1. a kind of light sensitive ceramics liquid for photocuring 3D printing, comprising: photosensitive silicone oil, the 8.7%- of 74.3%-89.3%
22.3% silicone oil additive, the metallic catalyst of 0.9%-2.6%, the coloring agent of 0-0.02%, 0.9%-2.0% light draw
Send out agent, wherein the photosensitive silicone oil by 74.6%-83.2% the liquid silicone and 13.8%-24.9% containing epoxy group
Acrylic acid be made.
2. the light sensitive ceramics liquid according to claim 1 for photocuring 3D printing, which is characterized in that described to contain epoxy group
The each molecule of liquid silicone at least containing there are two the epoxy group that is connected with silane, epoxy group content 2-10%,
Viscosity is 50-200mPas.
3. the light sensitive ceramics liquid according to claim 1 for photocuring 3D printing, which is characterized in that the silicone oil addition
Agent is dimethicone or hydroxy silicon oil；The metallic catalyst is dibutyl tin dilaurate or butyl titanate；The dye
Toner is lipid coloring agent；The photoinitiator is free radical photo-initiation.
4. the light sensitive ceramics liquid according to claim 1 for photocuring 3D printing, which is characterized in that the coloring agent is
Oil red or S Ⅳ；The photoinitiator is 2,4,6- trimethylbenzoyl phenyl phosphinic acid ethyl ester (TPO-L) or 2,4,6-
Trimethylbenzoyl phosphinic acid ethyl ester (TPO).
5. a kind of preparation method of the ceramic member of photocuring 3D printing, includes the following steps:
(1) metal of the photosensitive silicone oil of 74.3%-89.3%, the silicone oil additive of 8.7%-22.3%, 0.9%-2.6% are urged
Agent, the coloring agent of 0-0.02%, 0.9%-2.0% photoinitiator obtain light sensitive ceramics liquid after mixing；
(2) green body is obtained to light sensitive ceramics liquid printing shaping using photocuring 3D printer；
(3) green body is sintered, obtains ceramic member.
6. the preparation method of the ceramic member of photocuring 3D printing according to claim 5, which is characterized in that the photosensitive silicon
Oil is made by following step: by the liquid silicone containing epoxy group of 74.6%-83.2%, the propylene of 13.8%-24.9%
It is heated 3-8 hours at 90-120 DEG C after sour, 0.04%-0.07% modified catalyst mixing.
7. the preparation method of the ceramic member of photocuring 3D printing according to claim 5, which is characterized in that the modification is urged
Agent is amines catalyst.
8. the preparation method of the ceramic member of photocuring 3D printing according to claim 5, which is characterized in that the modification is urged
Agent is N, N- dimethyl cyclohexyl amine, N, any one in N- dimethyl benzylamine, triethylamine.
9. the preparation method of the ceramic member of photocuring 3D printing according to claim 5, which is characterized in that the step
(2) 3D printing parameter are as follows: 50 μm of single layer, single layer time for exposure 5-10s, unit area exposure energy 1.5-6mJ/cm2。
10. the preparation method of the ceramic member of photocuring 3D printing according to claim 5, which is characterized in that the step
(3) sintering schedule are as follows: with 2 DEG C/min heating rate from room temperature to 1000 DEG C, and in 1000 DEG C of heat preservation 1h.
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| CN201910242364.3A CN109970450B (en) | 2019-03-28 | 2019-03-28 | Photosensitive ceramic liquid for 3D printing and ceramic part thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110903089A (en) * | 2019-11-27 | 2020-03-24 | 辽宁大学 | SiOC ceramic prepared by 3D printing and preparation method thereof |
| CN114042424A (en) * | 2021-10-26 | 2022-02-15 | 上海簇睿低碳能源技术有限公司 | Metal-based autocatalytic reactor based on 3D printing and preparation method and application thereof |
| CN115010877A (en) * | 2022-05-27 | 2022-09-06 | 深圳大学 | Carbon-oxygen-silicon ceramic precursor, thick and compact ceramic part and 3D printing preparation method thereof |
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| CN115010877B (en) * | 2022-05-27 | 2023-11-24 | 深圳大学 | Carbon-oxygen-silicon ceramic precursor, thick compact ceramic piece and 3D printing preparation method thereof |
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