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Paper ball-shaped graphene modified photocuring fibroin three-dimensional printing material and preparation method thereof

A graphene modification and silk protein technology, applied in the field of textile materials, can solve problems such as the influence of material stability, increase in dosage, and increase in material cost

Inactive Publication Date: 2018-05-29
DONGGUAN LIANZHOU INTPROP OPERATION MANAGEMENT CO LTD
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

3D printing technology includes powder bonded 3D printing, photocurable material 3D printing and molten material 3D printing, but most of these technologies are currently monopolized by foreign countries, so there is an urgent need to improve 3D printing materials and their supporting technologies
It can be seen from the above prior art that carbon materials such as graphene can be added to polymer 3D materials as reinforcing agents at present, but carbon materials such as graphene are easy to agglomerate and difficult to disperse has always been a problem, which not only affects the stability of the material, but also Will increase the amount and increase the cost of materials
Paper-like graphene is a microscopic paper-like three-dimensional graphene material, which not only has better specific surface area, mechanical properties and good electrical conductivity, but also can reduce the agglomeration of graphene sheets. Little research has been done on enhancing 3D materials

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0027] (1) Put 0.2wt% graphene oxide solution on the spray dryer, the fluid flow rate is 300mL / h, the inlet temperature is 230°C, and the gas flow rate is 0.7m 3 Under the condition of / h, carry out spray-drying, high-temperature reduction 1h at 1000 ℃, obtain paper ball shape graphene microsphere.

[0028] (2) Add the degummed silk fibers into a calcium chloride-ethanol-water ternary solution with a molar ratio of 1:2:8, heat and stir at 60°C until completely dissolved, filter, and dialyze to obtain a concentration of 1 wt%. silk protein solution.

[0029] (3) According to the mass ratio of paper ball-shaped graphene microspheres and silk protein of 0.2:5, paper ball-shaped graphene microspheres are added to the silk protein solution, mixed to form a mixed solution, evaporated and concentrated to a solid content of 10wt%, After microwave treatment at 300W for 10min, a silk protein composite hydrogel containing paper-like graphene microspheres was obtained.

[0030] (4) by w...

Embodiment 2

[0032] (1) Put 2wt% graphene oxide solution on the spray dryer, the fluid flow rate is 320mL / h, the inlet temperature is 260°C, and the gas flow rate is 0.8m 3 Under the condition of / h, carry out spray-drying, high-temperature reduction 2h at 1100 ℃, obtain paper ball-like graphene microspheres.

[0033](2) Add the degummed silk fibers into a calcium chloride-ethanol-water ternary solution with a molar ratio of 1:2:8, heat and stir at 70°C until completely dissolved, filter, and dialyze to obtain a concentration of 3wt%. silk protein solution.

[0034] (3) According to the mass ratio of paper ball-shaped graphene microspheres and silk protein 0.5:10, paper ball-shaped graphene microspheres are added to the silk protein solution, mixed to form a mixed solution, evaporated and concentrated to a solid content of 20wt%, After microwave treatment at 400W for 60min, a silk protein composite hydrogel containing paper-like graphene microspheres was obtained.

[0035] (4) in parts b...

Embodiment 3

[0037] (1) Put 0.5wt% graphene oxide solution on the spray dryer, the fluid flow rate is 310mL / h, the inlet temperature is 250°C, and the gas flow rate is 0.75m 3 Under the condition of / h, carry out spray-drying, high-temperature reduction 1.5h at 1050 ℃, obtain paper ball shape graphene microsphere.

[0038] (2) Add the degummed silk fibers into a calcium chloride-ethanol-water ternary solution with a molar ratio of 1:2:8, heat and stir at 65°C until completely dissolved, filter, and dialyze to obtain a concentration of 1.5wt % silk protein solution.

[0039] (3) According to the mass ratio of paper ball-shaped graphene microspheres and silk protein of 0.4:6, paper ball-shaped graphene microspheres are added to the silk protein solution, mixed to form a mixed solution, evaporated and concentrated to a solid content of 15wt%, After microwave treatment at 350W for 30min, a silk protein composite hydrogel containing paper-like graphene microspheres was obtained.

[0040] (4) ...

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Abstract

The invention provides a paper ball-shaped graphene modified photocuring fibroin three-dimensional printing material and a preparation method thereof. The material comprises paper ball-shaped graphene, fibroin hydrogel, a photoinitiator and an auxiliary agent. The specific preparation method includes the steps that a graphene oxide solution is spray-dried on a spray dryer and then subjected to high-temperature reduction to obtain paper ball-shaped graphene microspheres; the paper ball-shaped graphene microspheres are added to a fibroin solution with low concentration for mixing, evaporating, concentrating and microwave treatment to obtain fibroin composite hydrogel containing the paper ball-shaped graphene microspheres; the photoinitiator and the auxiliary agent are added to the fibroin composite hydrogel containing the paper ball-shaped graphene microspheres, and the mixture above is transferred to a three-dimensional printing device for printing layer by layer under irradiation of ultraviolet light to obtain the paper ball-shaped graphene modified fibroin composite material. The fibroin composite material prepared by the method is in a fiber shape or an irregular non-woven fabricshape or a regular cross-woven fabric shape, and has excellent skin-friendly performance, mechanical properties, biocompatibility and conductive properties.

Description

technical field [0001] The invention belongs to the technical field of textile materials, and in particular relates to a light-cured silk protein three-dimensional printing material modified by paper-like graphene and a preparation method thereof. Background technique [0002] Three-dimensional printing technology is a three-dimensional rapid prototyping technology. It is a technology that uses CAD computer-aided technology design data to make printed materials into objects in a stacked manner through forming equipment. Three-dimensional printing technology has the specific characteristics of fast and accurate preparation of parts and molds. , to effectively shorten the product development cycle, improve product quality, and reduce production costs. 3D printing technology includes powder bonded 3D printing, photocurable material 3D printing and molten material 3D printing, but most of these technologies are currently monopolized by foreign countries, so there is an urgent ne...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): D01F4/02D01F1/09D01F1/10C08L89/00C08L29/04C08K7/00C08K3/04B33Y70/00
CPCD01F4/02B33Y70/00C08L89/00C08L2203/12D01F1/09D01F1/10D01F1/103C08L29/04C08K7/00C08K3/04
Inventor 陈东进
Owner DONGGUAN LIANZHOU INTPROP OPERATION MANAGEMENT CO LTD
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