3D-Printing photo-curable slurry and preparation method thereof

A 3D printing and light-curing technology, applied in the field of 3D printing, can solve the problems of black light-curing system, such as hard curing and curing thickness, and achieve the effect of improving the ability of curing reaction

Active Publication Date: 2018-12-25

SHENZHEN SUNSHINE LASER & ELECTRONICS TECH CO LTD

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AI-Extracted Technical Summary

Problems solved by technology

[0005] In order to solve the problem that the black photocuring system is difficult to cure or the curing thic...

Method used

Solvent selects ethanol for use, and ethanol is easy to volatilize, has no residue after being convenient to dry, and economical and environmental protection.

[0028] By first carrying out a pretreatment of an initiator ...

Abstract

The invention discloses 3D-printing photo-curable slurry and a preparation method thereof. The preparation method includes S1, preparing materials, to be specific, fully mixing a black material, a photoinitiator, a dispersant and a solvent, and drying to obtain a pretreated material; S2, preparing a premixed liquid, to be specific, mixing photosensitive resin mixture, a photoinitiator and a dispersant to obtain the premixed liquid; S3, preparing slurry, to be specific, fully mixing the premixed liquid and the pretreated material to obtain the slurry. The black material is mixed with the photoinitiator, the dispersant the solvent to be pretreated before the slurry is prepared; the ability of the slurry to cure in ultraviolet irradiation can be greatly improved, the curing thickness of a single layer may reach 180 mu m and above, and printing forming is achieved.

Application Domain

Additive manufacturing apparatus

Technology Topic

SolventPhotoinitiator +5

Image

Examples

Experimental program(4)
Comparison scheme(1)

Example Embodiment

[0020] The preparation method of the 3D printing photocurable paste provided in this embodiment, the process flow chart is as figure 1 Shown, including:

[0021] S1. Material pretreatment: the black material, photoinitiator, dispersant, and solvent are thoroughly mixed and then dried to obtain the pretreatment material.

[0022] The black material in this embodiment mainly uses lithium iron phosphate powder used to form the electrode material, preferably the particle size of the lithium iron phosphate powder is 10-15 μm, and the specific surface area (BET) is 8-15 m 2 /g, purity> 99%.

[0023] The photoinitiator is selected from commercial photoinitiator 389 (2-dimethylamino-2-benzyl-1-(4-piperidinphenyl)-1-butanone), photoinitiator 184 (1-hydroxycyclohexylbenzene) Ketone), photoinitiator EMK (4,4-bis(diethoxy)benzophenone), photoinitiator TPO (2,4,6-trimethylbenzoyl-diphenylphosphine oxide) , Photoinitiator 819 (phenyl bis(2,4,6-trimethylbenzoyl) phosphine oxide), photoinitiator 907 (2-methyl-2(4-morpholinyl)-1-[4 -(Methylthio)phenyl]-1-acetone), photoinitiator ITX (2-isopropylthioxanthone) and other ultraviolet photoinitiators.

[0024] Commercial oil-soluble dispersants such as BYK111 and BYK163 from BYK of Germany and RQT-FS from Richite Chemical are used as dispersants.

[0025] Ethanol is used as the solvent. Ethanol is volatile, easy to dry, without residue, and economical and environmentally friendly.

[0026] Among them, the weight percentage of black material: photoinitiator: dispersant is preferably 1:1%-4%:0.5%-2%.

[0027] In the pretreatment process, one of the keys is to fully mix the black material with the initiator and the dispersant. Therefore, the black material, initiator, dispersant and solvent are put into the corundum ball mill tank together by ball milling, and the temperature is 150r The rotation speed of /min-250r/min is dispersed for 3-5h. After being thoroughly mixed, it is filtered and dried to obtain the pretreated material.

[0028] The black material is pretreated by an initiator and a dispersant. It not only improves the dispersion performance of the black material, but also allows the photoinitiator to participate in the subsequent photocuring reaction more effectively.

[0029] S2. Preparation of premix: the photosensitive resin mixture, photoinitiator and dispersant are mixed to obtain a premix.

[0030] The photosensitive resin mixture includes: a difunctional monomer and a trifunctional monomer are mixed according to a mass ratio of 2-6:1. Difunctional monomers include: HDDA (1,6-hexanediol diacrylate), DEGDMA (diethylene glycol dimethacrylate), HDDMA (1,6-hexanediol dimethacrylate), TEGDMA (Triethylene glycol dimethacrylate), TPGDA (tripropylene glycol diacrylate), etc. It has two reactive functional groups, viscosity <50cps. Trifunctional monomers are: PET3A (pentaerythritol triacrylate), TMPTA (trimethylolpropane triacrylate), TMP3EOTA (ethoxylated trimethylolpropane triacrylate), etc. One of them, which has three reactions Reactive functional groups, which can increase the reaction speed and improve the crosslinkability of the product.

[0031] The photoinitiator and dispersant are the same as the photoinitiator and dispersant in step S1.

[0032] Among them, the weight percentage of the photosensitive resin mixture, photoinitiator, and dispersant is preferably 1:1%-4%:1%-2.5%. The photoinitiator and the dispersant are added to the photosensitive resin mixture, and the mixture is stirred and ultrasonic for 10-30 minutes to obtain a premix.

[0033] S3. Slurry preparation: fully mix the premixed liquid and the pretreatment material to obtain a slurry.

[0034] Specifically, the premixed liquid and the pretreatment materials are poured into a corundum ball mill tank, and ball milled at a speed of 150-200 r/min for 15-25 hours to collect the slurry.

[0035] Taking into account the fluidity of the slurry (related to printing performance) and the effectiveness of the print (generally it is required that the higher the content of the powder in the print, the better), so in step S3, the pretreatment material accounts for black 15%-60% of the total weight of the slurry.

[0036] The slurry obtained in the above steps is used for three-dimensional printing and molding with SLA equipment based on the principle of light curing.

Example Embodiment

[0037] Example 1

[0038] Weigh 120g of lithium iron phosphate powder into a 1L corundum ball mill tank, pour about 120g of absolute ethanol, and add 3.6g of photoinitiator TPO and 1.2g of dispersant RQT-FS. Then start ball milling, the speed is set to 170r/min, ball milling for 3h. After completion, filter and dry the pretreated lithium iron phosphate powder to be used.

[0039] Pour 120 g of HDDA and 36 g of TMPTA into the beaker, and ultrasonically stir for 20 minutes to obtain a photosensitive resin mixture, which is set aside.

[0040] Add 120 g of the photosensitive resin mixture, 2.4 g of the photoinitiator TPO and 2.4 g of the dispersant RQT-FS into the beaker, ultrasonicate for 30 minutes, and transfer to a 1L corundum ball mill tank after a uniform and stable solution is formed. Then weigh 120g of the pretreated lithium iron phosphate powder and add it to it, ball mill 170r/min for 20h. After completion, the black slurry was collected. The black paste is directly used in the SLA equipment of the light curing principle for 3D printing and the single layer curing thickness is 200μm. The final printed product is figure 2 Shown.

Example Embodiment

[0041] Example 2

[0042] Weigh 120g of lithium iron phosphate powder into a 1L corundum ball mill tank, pour about 120g of absolute ethanol, and then add 1.2g of photoinitiator 389 and 3g of dispersant BYK111. Then start ball milling, the speed is set to 250r/min, ball milling 4h. After completion, filter and dry the pretreated lithium iron phosphate powder to be used.

[0043] Pour 120 g of DEGDMA and 60 g of PET3A into a beaker, and ultrasonically stir for 20 minutes to obtain a photosensitive resin mixture, which is set aside.

[0044] Add 120 g of the photosensitive resin mixture, 1.2 g of photoinitiator 389 and 1.2 g of dispersant BYK111 into the beaker, ultrasonicate for 20 minutes, and transfer to a 1L corundum ball mill tank after a uniform and stable solution is formed. Then weigh 21.6g of pretreated lithium iron phosphate powder and add it to it, and ball mill 150r/min for 25h. After completion, the black slurry was collected. The black paste is directly used in the SLA equipment of the light curing principle for 3D printing and the single layer curing thickness is 230μm. The final printed product is the same figure 2.

PUM

Property	Measurement	Unit
Particle size	10.0 ~ 15.0	µm
Specific surface area	8.0 ~ 15.0	m²/g

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