CN105128127A - Method for printing graphene aerogel material through 3D printing technology - Google Patents
Method for printing graphene aerogel material through 3D printing technology Download PDFInfo
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- CN105128127A CN105128127A CN201510375733.8A CN201510375733A CN105128127A CN 105128127 A CN105128127 A CN 105128127A CN 201510375733 A CN201510375733 A CN 201510375733A CN 105128127 A CN105128127 A CN 105128127A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B28—WORKING CEMENT, CLAY, OR STONE
- B28B—SHAPING CLAY OR OTHER CERAMIC COMPOSITIONS; SHAPING SLAG; SHAPING MIXTURES CONTAINING CEMENTITIOUS MATERIAL, e.g. PLASTER
- B28B1/00—Producing shaped prefabricated articles from the material
- B28B1/001—Rapid manufacturing of 3D objects by additive depositing, agglomerating or laminating of material
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B26/00—Compositions of mortars, concrete or artificial stone, containing only organic binders, e.g. polymer or resin concrete
- C04B26/02—Macromolecular compounds
- C04B26/026—Proteins or derivatives thereof
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Abstract
Provided is a method for printing a graphene aerogel material through a 3D printing technology. After a phenol, melamine, methanol and furfural mixed system is added, the possibility of defects is reduced greatly; meanwhile, as collagen is added, the forming performance is improved, the deformation phenomenon is reduced, and binding force between layers is increased; preparation of graphene aerogel products is achieved by better utilizing the existing advanced 3D printing technology.
Description
Technical field
The present invention relates to a kind of method that 3D printing technique prints aerogel material, particularly utilize 3D printing technique to print the method for graphene aerogel.
Background technology
Aerogel material is a kind of ultralight synthetic material of porous, and the liquid component of aerogel material gel is replaced by gas usually.Aeroge is the porous amorphous solid material be made up of nanoscale colloidal particle or high-polymer molecular, is also condensed state material the lightest in current synthetic material.The nanometer porous structure of opening of its uniqueness and continuous print three-dimensional network, make it to have extremely low density, high-ratio surface sum high porosity, show the characteristics such as strong adsoption catalysis ability, lower thermal conductivity, low acoustic impedance and low-refraction, therefore aeroge has become good catalyst and carrier, adsorbent and gas filtering material, and is successfully applied to Cherenkov detector, acoustic impedance coupling material, high efficiency heat insulation material etc.The fractal structure of its uniqueness, dynamic characteristic and low temperature thermal property also make it to become desirable theoretical research material, especially new technology as the catching of cosmic dust, muonic atom research and
3he-
4the application of the aspects such as He phase in version research.In prior art before this, attempt in the industry to manufacture in the process of large-scale graphene aerogel, can produce a kind of larger random pore structure, this structure, in the special applications such as sorting, fluid cell and pressure sensor, has the ability of the mechanical attributes such as the transport of adjustment material.
But current pore structure is all random, graphene aerogel as in controlled and easily extensible mode for special applications provides the structure of making to measure still cannot realize.Cannot for the demand of the application-specific such as picture separation, flow battery and pressure sensor, on material, design transmission or other mechanical properties limit the function of graphene aerogel and further expandable applications to a certain extent specially.
3D printing technique appears at the mid-90 in 20th century, is actually the up-to-date rapid molding device of technology such as utilizing photocuring and ply of paper to fold.It is substantially identical with common print operation principle, and printer, built with liquid or powder etc. " printed material ", after being connected, is stacked up " printed material " by conputer controlled from level to level with computer, finally the blueprint on computer is become in kind.
Have researcher's view to utilize 3D printing technique to print aerogel material, but current aerogel material does not conform in 3D printing, there will be crackle, distortion etc., in the product of the reality that cannot apply when 3D prints.Therefore, aerogel material and the technique of printing is not also suitable at present.
Summary of the invention
The present invention is according to prior art Problems existing, is applied in the generative process of graphene aerogel by 3D printing technique, and it can design the pore space structure of gas-gel, thus can control a large amount of manufacture and transmission, and optimization physical characteristics, such as rigidity.This development is expected to apply into the innovation of gas-gel and creativity to open more design spaces.By Method and process of the present invention, Graphene gas-gel is made to have high surface, excellent electric conductivity, lightweight and represent the feature such as mechanical stiffness and supercompressibility (compression stress up to 90%).In addition, the Graphene gas-gel that 3D prints also shows than the further performance boost of large-scale grapheme material, and more effective a large amount of transmission.
The present invention is directed to the feature of 3D printing technique, first have developed specially the graphene aerogel material being suitable for 3D printing technique, there is certain toughness, make the material prepared be suitable for layering shaping, reduce the distortion in forming process, maintain higher compressive strength and heat endurance simultaneously; Secondly, being studied by printing technique for the 3D of graphene aerogel material, more ensure that the final performance of material.
The concrete 3D Method of printing of graphene aerogel comprises:
1) 3D printed material is configured: by the dispersion of the mixture of Graphene, graphene oxide in aqueous, then in above-mentioned solution, adding phenol-carbamide-furfural mixed system and KHSO gradually
4, wherein phenol-carbamide-furfural mixed system and KHSO
4mol ratio be respectively 0.8: 1: 06: 0.9: 0.7, utilize ultrasonic vibration, form uniform solution; And formation uniform solution after, then when ultrasonic vibration collagen, the mass ratio of collagen and Graphene is 1: 5 ~ 1: 30, then at the temperature of 50-60 DEG C, heats 70-90 minute, obtains hydrogel;
2) AutoCAD Software for Design is used to go out the part model of desired structure shape, mainly for the part model having enclosed cavity, complicated inner cavity, part model is carried out hierarchy slicing process, and synusia thickness is 0.02mm ~ 0.20mm, obtains the three-dimensional modeling data of part;
3) three-dimensional modeling data of the part after section is imported in the memory of 3D printing device, then by step 1) in the hydrogel that obtains be injected in 3D printing device, the hydrogel material of mixing is successively printed according to three-dimensional data model by the nozzle of 3D printing device, the thickness of every layer is no more than 0.20mm, preferably every layer prints with identical thickness, the organic monomer that layering prints in disposed slurry forms three-dimensional network polymer gel by chemical crosslinking, thus rapid solidification, successively accumulation forms base substrate:
4) bad body formed after, put into vacuum and carry out drying process, and bad body is processed when 200-300 DEG C, obtain the product of needs.
Compared with prior art, the invention has the advantages that:
(1) the present invention utilizes now more advanced 3D printing technique to achieve the preparation of graphene aerogel product, reaches the object of saving material, facilitating the control of product;
(2) the present invention is specially for the shaping characteristic of 3D printing technique---and layering is shaping has carried out material development, the layer shaping due to layering is thinner, if use the material of prior art, the every one deck generation warpage in the process that layering is shaping can be made, also can deform and ftracture after multi-layer forming, the present invention is after adding phenol-carbamide-furfural mixed system gradually, considerably reduce the appearance of above-mentioned defect, and owing to adding collagen simultaneously, improve processability, reduce metaboly, improve adhesion between layers.
Detailed description of the invention
Embodiment 1
The concrete 3D Method of printing of graphene aerogel comprises:
1) 3D printed material is configured: by the dispersion of the mixture of Graphene, graphene oxide in aqueous, then in above-mentioned solution, adding phenol-carbamide-furfural mixed system and KHSO gradually
4, wherein phenol-carbamide-furfural mixed system and KHSO
4mol ratio be respectively 0.8: 1: 06: 0.9: 0.7, utilize ultrasonic vibration, form uniform solution; And formation uniform solution after, then when ultrasonic vibration collagen, the mass ratio of collagen and Graphene is 1: 15, then at the temperature of 50-60 DEG C, heats 70-90 minute, obtains hydrogel;
2) use AutoCAD Software for Design to go out the part model of desired structure shape, mainly for the part model having enclosed cavity, complicated inner cavity, part model is carried out hierarchy slicing process, synusia thickness is 0.02mm, obtains the three-dimensional modeling data of part;
3) three-dimensional modeling data of the part after section is imported in the memory of 3D printing device, then by step 1) in the hydrogel that obtains be injected in 3D printing device, the hydrogel material of mixing is successively printed according to three-dimensional data model by the nozzle of 3D printing device, the thickness of every layer is no more than 0.20mm, preferably every layer prints with identical thickness, the organic monomer that layering prints in disposed slurry forms three-dimensional network polymer gel by chemical crosslinking, thus rapid solidification, successively accumulation forms base substrate:
4) bad body formed after, put into vacuum and carry out drying process, and bad body is processed when 250 DEG C, obtain the product of needs.
Embodiment 2
The concrete 3D Method of printing of graphene aerogel comprises:
1) 3D printed material is configured: by the dispersion of the mixture of Graphene, graphene oxide in aqueous, then in above-mentioned solution, adding phenol-carbamide-furfural mixed system and KHSO gradually
4, wherein phenol-carbamide-furfural mixed system and KHSO
4mol ratio be respectively 0.8: 1: 06: 0.9: 0.7, utilize ultrasonic vibration, form uniform solution; And formation uniform solution after, then when ultrasonic vibration collagen, the mass ratio of collagen and Graphene is 1: 30, then at the temperature of 50-60 DEG C, heats 70-90 minute, obtains hydrogel;
2) use AutoCAD Software for Design to go out the part model of desired structure shape, mainly for the part model having enclosed cavity, complicated inner cavity, part model is carried out hierarchy slicing process, synusia thickness is 0.10mm, obtains the three-dimensional modeling data of part;
3) three-dimensional modeling data of the part after section is imported in the memory of 3D printing device, then by step 1) in the hydrogel that obtains be injected in 3D printing device, the hydrogel material of mixing is successively printed according to three-dimensional data model by the nozzle of 3D printing device, the thickness of every layer is no more than 0.20mm, preferably every layer prints with identical thickness, the organic monomer that layering prints in disposed slurry forms three-dimensional network polymer gel by chemical crosslinking, thus rapid solidification, successively accumulation forms base substrate:
4) bad body formed after, put into vacuum and carry out drying process, and bad body is processed when 200 DEG C, obtain the product of needs.
Claims (4)
1. utilize 3D printing technique to print a method for graphene aerogel material, it is characterized in that the method comprises:
1) 3D printed material is configured: by the dispersion of the mixture of Graphene, graphene oxide in aqueous, then in above-mentioned solution, adding phenol-carbamide-furfural mixed system and KHSO gradually
4, wherein phenol-carbamide-furfural mixed system and KHSO
4mol ratio be respectively 0.8: 1: 06: 0.9: 0.7, utilize ultrasonic vibration, form uniform solution; And formation uniform solution after, then when ultrasonic vibration collagen, the mass ratio of collagen and Graphene is 1: 5 ~ 1: 30, then at the temperature of 50-60 DEG C, heats 70-90 minute, obtains hydrogel;
2) AutoCAD Software for Design is used to go out the part model of desired structure shape, mainly for the part model having enclosed cavity, complicated inner cavity, part model is carried out hierarchy slicing process, and synusia thickness is 0.02mm ~ 0.20mm, obtains the three-dimensional modeling data of part;
3) three-dimensional modeling data of the part after section is imported in the memory of 3D printing device, then by step 1) in the hydrogel that obtains be injected in 3D printing device, the hydrogel material of mixing is successively printed according to three-dimensional data model by the nozzle of 3D printing device, the thickness of every layer is no more than 0.20mm, preferably every layer prints with identical thickness, the organic monomer that layering prints in disposed slurry forms three-dimensional network polymer gel by chemical crosslinking, thus rapid solidification, successively accumulation forms base substrate;
4) bad body formed after, put into vacuum and carry out drying process, and bad body is processed when 200-300 DEG C, obtain the product of needs.
2. a kind of method utilizing 3D printing technique to print graphene aerogel material according to claim 2, it is characterized in that, the mass ratio of collagen and Graphene is 1: 15.
3. a kind of method utilizing 3D printing technique to print graphene aerogel material according to claim 1 and 2, is characterized in that, is processed when 250 DEG C by bad body, obtains the product needed.
4. a kind of method utilizing 3D printing technique to print graphene aerogel material according to Claims 2 or 3, it is characterized in that, part model is carried out hierarchy slicing process, synusia thickness is 0.10mm.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105837214A (en) * | 2016-03-22 | 2016-08-10 | 西安铂力特激光成形技术有限公司 | Preparation method of graphene product |
| WO2017029495A1 (en) * | 2015-08-17 | 2017-02-23 | Imperial Innovations Limited | Ink composition comprising thermo-responsive polymer |
| CN106543687A (en) * | 2016-11-01 | 2017-03-29 | 宁夏共享化工有限公司 | A kind of modified 3D printing resin of graphene oxide and its production method |
| CN107555422A (en) * | 2017-08-18 | 2018-01-09 | 复旦大学 | A kind of 3D printing aeroge based on graphene oxide composite material and preparation method thereof |
| CN112430094A (en) * | 2020-11-25 | 2021-03-02 | 中国科学院上海硅酸盐研究所 | Macrostructure ordered graphene aerogel and preparation method thereof |
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| WO2013191654A1 (en) * | 2012-06-18 | 2013-12-27 | National University Of Singapore | Porous graphene oxide materials |
| CN104408214A (en) * | 2014-05-31 | 2015-03-11 | 福州大学 | 3D manufacturing method for an electrode of an in-planeswitching blue phase liquid crystal display device |
| CN104552947A (en) * | 2014-12-30 | 2015-04-29 | 张辉开 | Graphene fused deposition 3D printing method and application thereof |
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Patent Citations (5)
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| CN102774824A (en) * | 2012-06-11 | 2012-11-14 | 北京化工大学 | Method for preparing graphene crosslinked type organic aerogel and carbon aerogel by normal-pressure drying |
| WO2013191654A1 (en) * | 2012-06-18 | 2013-12-27 | National University Of Singapore | Porous graphene oxide materials |
| CN102938321A (en) * | 2012-12-03 | 2013-02-20 | 济南航医纳科技有限公司 | Manufacturing method of high-power super energy storage power supply |
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Cited By (5)
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|---|---|---|---|---|
| WO2017029495A1 (en) * | 2015-08-17 | 2017-02-23 | Imperial Innovations Limited | Ink composition comprising thermo-responsive polymer |
| CN105837214A (en) * | 2016-03-22 | 2016-08-10 | 西安铂力特激光成形技术有限公司 | Preparation method of graphene product |
| CN106543687A (en) * | 2016-11-01 | 2017-03-29 | 宁夏共享化工有限公司 | A kind of modified 3D printing resin of graphene oxide and its production method |
| CN107555422A (en) * | 2017-08-18 | 2018-01-09 | 复旦大学 | A kind of 3D printing aeroge based on graphene oxide composite material and preparation method thereof |
| CN112430094A (en) * | 2020-11-25 | 2021-03-02 | 中国科学院上海硅酸盐研究所 | Macrostructure ordered graphene aerogel and preparation method thereof |
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Inventor after: Yang Shuling Inventor after: Zhou Yu Inventor after: Zhu Hong Inventor after: Shi Lei Inventor before: Zhu Hong Inventor before: Shi Lei |
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Effective date of registration: 20160518 Address after: 277000 No. 40, Wenhua East Road, Shizhong District, Shandong, Zaozhuang Applicant after: Zhu Hong Address before: 277000 No. 40, Wenhua East Road, Shizhong District, Shandong, Zaozhuang Applicant before: Zhu Hong Applicant before: Shi Lei |
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