CN115122633A - TiO with gradient structure 2 -Ti 3 C 2 T x 3D printing preparation method of/rGO electromagnetic shielding composite material - Google Patents
TiO with gradient structure 2 -Ti 3 C 2 T x 3D printing preparation method of/rGO electromagnetic shielding composite material Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 238000010146 3D printing Methods 0.000 title claims description 12
- 238000007639 printing Methods 0.000 claims abstract description 23
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000002135 nanosheet Substances 0.000 claims abstract description 15
- 229910010413 TiO 2 Inorganic materials 0.000 claims abstract description 13
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 13
- 238000004108 freeze drying Methods 0.000 claims abstract description 12
- 230000003647 oxidation Effects 0.000 claims abstract description 8
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 8
- 238000010438 heat treatment Methods 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 9
- 239000006185 dispersion Substances 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- 238000005530 etching Methods 0.000 claims description 6
- 238000001125 extrusion Methods 0.000 claims description 6
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims description 6
- 238000009210 therapy by ultrasound Methods 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 238000000227 grinding Methods 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 229910002804 graphite Inorganic materials 0.000 claims description 3
- 239000010439 graphite Substances 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000004570 mortar (masonry) Substances 0.000 claims description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims 2
- 229910000838 Al alloy Inorganic materials 0.000 claims 1
- 229910052782 aluminium Inorganic materials 0.000 claims 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims 1
- 238000003801 milling Methods 0.000 claims 1
- 229910052757 nitrogen Inorganic materials 0.000 claims 1
- 238000005516 engineering process Methods 0.000 abstract description 8
- 239000002073 nanorod Substances 0.000 abstract description 4
- 239000012299 nitrogen atmosphere Substances 0.000 abstract description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract description 3
- 230000007547 defect Effects 0.000 abstract description 3
- 230000007246 mechanism Effects 0.000 abstract description 3
- 230000002195 synergetic effect Effects 0.000 abstract description 3
- 241000446313 Lamella Species 0.000 abstract description 2
- 238000011065 in-situ storage Methods 0.000 abstract description 2
- 230000010287 polarization Effects 0.000 abstract description 2
- 239000010936 titanium Substances 0.000 description 34
- 239000000976 ink Substances 0.000 description 20
- 239000011148 porous material Substances 0.000 description 16
- 239000000463 material Substances 0.000 description 14
- 238000004626 scanning electron microscopy Methods 0.000 description 3
- 238000013461 design Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 239000002064 nanoplatelet Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- UQZIWOQVLUASCR-UHFFFAOYSA-N alumane;titanium Chemical compound [AlH3].[Ti] UQZIWOQVLUASCR-UHFFFAOYSA-N 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- MTPVUVINMAGMJL-UHFFFAOYSA-N trimethyl(1,1,2,2,2-pentafluoroethyl)silane Chemical compound C[Si](C)(C)C(F)(F)C(F)(F)F MTPVUVINMAGMJL-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- 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
- B29C64/20—Apparatus for additive manufacturing; Details thereof or accessories therefor
- B29C64/205—Means for applying layers
- B29C64/209—Heads; Nozzles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- 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
- B29C64/10—Processes of additive manufacturing
- B29C64/106—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material
- B29C64/124—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material using layers of liquid which are selectively solidified
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- 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
- B29C64/30—Auxiliary operations or equipment
-
- 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
- B33Y10/00—Processes of 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
- B33Y30/00—Apparatus for additive manufacturing; Details thereof or accessories therefor
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Mechanical Engineering (AREA)
- Optics & Photonics (AREA)
- Shielding Devices Or Components To Electric Or Magnetic Fields (AREA)
Abstract
The invention belongs to the technical field of electromagnetic shielding composite materials, and particularly relates to TiO with a gradient structure 2 ‑Ti 3 C 2 T x A3D printing preparation method of a/rGO electromagnetic shielding composite material. By introducing the graphene oxide, the problem of pure Ti is solved 3 C 2 T x The defect of printability of the nanosheet ink is overcome, and the conductivity loss and the reflection loss of the composite material are increased by utilizing the high conductivity and the two-dimensional lamella of the nanosheet ink; using the prepared ink to pass through 3D, constructing a composite material with a gradient structure by using a printing technology, and showing excellent impedance matching and multiple reflection loss of an internal structure after freeze drying; by performing controlled oxidation treatment on the printed frame in nitrogen atmosphere, Ti can be used 3 C 2 T x In-situ generation of anatase phase TiO on nano-sheet 2 Nanorods, TiO 2 ‑Ti 3 C 2 T x The heterostructure enhances the dipole polarization between the composite material and the incident electromagnetic wave, thereby obtaining the electromagnetic shielding composite material with the synergistic effect of multiple loss mechanisms, and having wide market prospect.
Description
Technical Field
The invention belongs to the technical field of electromagnetic shielding composite materials, and particularly relates to TiO with a gradient structure 2 -Ti 3 C 2 T x A3D printing preparation method of a/rGO electromagnetic shielding composite material.
Background
With the great progress made in electronic devices and technologies, they have been applied to various fields of radar systems, aerospace, 5G networks, computers, and the like. Although the rapid development of wireless communication and microwave equipment brings great convenience to the life of people, the problems of electromagnetic wave radiation and electromagnetic interference radiation are increasingly prominent, which not only affects the working precision of high-sensitivity equipment, but also jeopardizes human health. The development of high-performance electromagnetic shielding materials has become a great hotspot in the field of electromagnetic shielding nowadays.
Etching to strip titanium aluminum carbide (Ti) 3 AlC 2 ) Prepared two-dimensional titanium carbide (Ti) 3 C 2 T x ) The nano-sheet has excellent conductivity, abundant surface functional groups, unique layered structure and large specific surface area, and is widely applied to electromagnetic interference shielding materials. But as an electromagnetic shielding material Ti 3 C 2 T x There are still some drawbacks in itself: (1) ti 3 C 2 T x As a highly conductive two-dimensional lamellar structure, the high-conductivity two-dimensional lamellar structure can achieve the advantage of conductivity loss to a great extent, but simultaneously, the secondary reflection of electromagnetic waves is increased due to the imbalance of impedance matching, and the secondary reflection of the electromagnetic waves is increasedThe environment is again contaminated. (2) Ti 3 C 2 T x When the ink is configured as 3D printing ink, it is difficult to provide characteristics for forming printing ink. Electromagnetic shielding materials with 3D microstructures are considered to be more promising candidates due to their low density, high flexibility, and conductive network interconnections, etc., compared to 1D or 2D materials. Meanwhile, the 3D printing technology is an additive manufacturing technology different from the traditional processing mode, the principle is layered manufacturing and layer-by-layer superposition, and the method has the advantages of being long in forming time period, high in forming precision, small in material consumption and the like. The configured ink is deposited according to a preset path, so that a product at a printing position can be consistent with a preset structure, and the designability is extremely strong.
Disclosure of Invention
The invention designs a three-dimensional electromagnetic shielding composite material with special gradient aperture. By introducing graphene oxide and combining 3D printing technology, not only Ti is overcome 3 C 2 T x The printability of (b) also improves the impedance matching of the composite material. Simultaneous anatase phase TiO 2 The nanorods can be formed by controlled oxidation at an annealing temperature of 500 ℃, TiO 2 -Ti 3 C 2 T x Heterostructures can produce dielectric dipole synergy at multiple interfaces. The three-dimensional conductive structure with the gradient pores can not only enhance the conductivity loss, but also increase the multiple reflection of electromagnetic waves between pores. More noteworthy, the successful design of the gradient aperture structure improves the impedance matching of the material, and is an effective way to improve the electromagnetic shielding performance. From the existing materials to ideal components, the breakthrough successfully overcomes the inherent defect that the traditional processing technology cannot be customized, so that the electromagnetic shielding material can be developed to freely construct diversified frameworks, thereby realizing the multifunctional electromagnetic shielding material with different sizes and multiple loss mechanisms and synergistic effect.
In order to achieve the above object, the present invention provides the following technical solutions:
selective etching of Ti with 12M hydrochloric acid and lithium fluoride 3 AlC 2 The metal Al layer in the alloy is subjected to ultrasonic treatment to generate Ti with few sheets 3 C 2 T x . ColdFormation of Ti after lyophilization 3 C 2 T x Nanosheets;
stripping graphite into few-layer graphene oxide by adopting an improved Hummer method, and freeze-drying to form graphene oxide nanosheets;
freeze-drying Ti 3 C 2 T x Dispersing graphene oxide nano sheets into water according to a certain proportion to form a dispersion liquid, carrying out ultrasonic treatment for 15min, transferring the dispersion liquid into an agate mortar for grinding, and preparing printing ink;
directly extruding and printing the prepared printing ink by a 3D printer to obtain Ti with a three-dimensional gradient structure 3 C 2 T x a/GO electromagnetic shielding composite;
the three-dimensional frame is subjected to controlled oxidation in nitrogen atmosphere to obtain high-performance TiO 2 -Ti 3 C 2 T x the/rGO electromagnetic shielding composite material.
Preferably, the water bath heating temperature of the etching reaction is 45 ℃, the heating and stirring time is 48h, the ultrasonic power is 600W, and the ultrasonic time is 30 min.
Preferably, the water bath heating temperature of the stripping conditions is 50 ℃, and the heating stirring time is 24 h.
Preferably, the concentration of the dispersion liquid needs to reach 60mg/mL, the ultrasonic power is 600W, and the grinding time is 20 min.
Preferably, the printing parameters are set as the following table, the printing temperature is-10 ℃, the extrusion pressure is 70Pa, the diameter of the needle is 0.34mm, the receiving speed is 8-12mm/s, and the receiving speed of 1mm/s is increased for each two layers from bottom to top; .
Preferably, the carbonization treatment conditions are as follows: the heating rate is 3 ℃/min, and the temperature is kept for 4h at 500 ℃.
The invention provides TiO with a gradient structure prepared by the preparation method in the scheme 2 -Ti 3 C 2 T x the/rGO electromagnetic shielding composite material and the 3D printing preparation method thereof comprise utilizing Ti 3 C 2 T x And graphene oxide nanoplatelet configuration hasA printable 3D printing ink, and a printing method having a gradient three-dimensional structure formed using different pore sizes generated by a difference in receiving speed.
The invention adopts 3D printing technology to prepare TiO 2 -Ti 3 C 2 T x The method for introducing the graphene oxide solves the problem of pure Ti by adopting the rGO electromagnetic shielding composite material 3 C 2 T x The defect of printability of the nanosheet ink is overcome, and the conductivity loss and the reflection loss of the composite material are increased by utilizing the high conductivity and the two-dimensional lamella of the nanosheet ink; a three-dimensional frame with a gradient structure is constructed by using the prepared ink through a 3D printing technology, and excellent impedance matching and multiple reflection loss of an internal structure are shown after freeze drying; by performing controlled oxidation treatment on the printed frame in nitrogen atmosphere, Ti can be used 3 C 2 T x In-situ generation of anatase phase TiO on nano-sheet 2 Nano-rod, TiO 2 -Ti 3 C 2 T x The heterostructure enhances the dipole polarization between the composite material and the incident electromagnetic wave, thereby obtaining the electromagnetic shielding composite material with the synergistic effect of multiple loss mechanisms.
Drawings
FIG. 1 is Ti 3 C 2 T x And viscosity as a function of shear rate for GO formulated inks.
FIG. 2 is Ti 3 C 2 T x And storage and loss moduli of GO configured inks as a function of shear force.
FIG. 3 is TiO 2 -Ti 3 C 2 T x Scanning electron microscopy of top view of/rGO three-dimensional framework.
FIG. 4 is TiO 2 -Ti 3 C 2 T x Scanning electron microscope images of/rGO three-dimensional framework cross-sections.
FIG. 5 is TiO 2 -Ti 3 C 2 T x Scanning electron microscope images of/rGO three-dimensional framework monofilaments.
FIG. 6 is TiO 2 -Ti 3 C 2 T x rGO three-dimensional frame TiO 2 Scanning electron microscopy of nanorods.
FIG. 7 is a graph comparing electromagnetic shielding effectiveness of uniform pore and gradient pore structures
FIG. 8 is a graph of electromagnetic shielding effectiveness of simulated gradient pore structure
FIG. 9 is a graph of electromagnetic shielding effectiveness for simulating a uniform pore structure
Detailed Description
The following embodiments are provided to illustrate a TiO with a gradient structure 2 -Ti 3 C 2 T x the/rGO electromagnetic shielding composite material and the 3D printing preparation method thereof are explained in detail.
Example 1:
TiO with gradient structure 2 -Ti 3 C 2 T x The specific process of the/rGO electromagnetic shielding composite material and the 3D printing preparation method thereof comprises the following steps:
2gTi was selectively etched using 12M hydrochloric acid and 3.2g lithium fluoride 3 AlC 2 The water bath heating temperature of the etching reaction of the medium metal Al layer is 45 ℃, the heating and stirring time is 48h, and the low-sheet-layer Ti is generated 30min after 600W ultrasonic treatment 3 C 2 T x Formation of Ti after freeze drying 3 C 2 T x Nanosheets;
stripping graphite into few-layer graphene oxide by adopting an improved Hummer method, and freeze-drying to form graphene oxide nanosheets;
freeze-drying Ti 3 C 2 T x And graphene oxide nanoplatelets are prepared according to a molar ratio of 1: 1 into water to form a 60mg/mL dispersion, carrying out ultrasonic treatment for 15min, transferring the dispersion into an agate mortar, and grinding to prepare printing ink;
directly extruding and printing the prepared printing ink by a 3D printer to obtain TiO with a three-dimensional gradient structure 2 -Ti 3 C 2 T x The electromagnetic shielding composite material has the printing temperature of-10 ℃, the extrusion pressure of 70Pa, the needle diameter of 0.34mm, the receiving speed of 8-12mm/s and the receiving speed of 1mm/s increased for each two layers from bottom to top；
Heating the three-dimensional frame at a heating rate of 3 ℃/min in a nitrogen atmosphere, and keeping the temperature at 500 ℃ for 4h for controlled oxidation to obtain high-performance TiO 2 -Ti 3 C 2 T x the/rGO electromagnetic shielding composite material.
Comparative example 1:
the contrast sample is a three-dimensional structure with uniform aperture, and the specific printing parameters are as follows: the printing temperature is-10 ℃, the extrusion pressure is 70Pa, the diameter of the needle head is 0.34mm, and the receiving speed is 10 mm/s;
the sample was characterized by scanning electron microscopy and it can be seen from figure 1 that the ink showed shear thinning behavior of the non-newtonian fluid, that is, the viscosity decreased with increasing shear rate, which is a necessary condition for continuous flow of the printable ink. Also, FIG. 2 shows that G 'is an order of magnitude larger than G'. The difference between G' and G ", which stabilizes the flow of the ink during extrusion. When the ink is extruded through the nozzle, G 'is dominant, and G' is reduced more under high shear stress, which is beneficial to the smooth extrusion of the ink. More importantly, the recovery of a high G' will help preserve the complex 3D architecture of printing as ink leaves the nozzles. As can be seen from fig. 3, the three-dimensional frame maintains its predetermined shape and structure while maintaining a good linear combination. Fig. 4 shows a cross-sectional view of a three-dimensional structure, which can further illustrate the successful construction of a three-dimensional conductive framework with graded pore size variation. Figure 5 shows that the frame lines appear as a series of micro-porous shapes after freeze-drying. FIG. 6 demonstrates the formation of TiO by high temperature controlled oxidation 2 -Ti 3 C 2 T x A heterostructure. Comparing the electromagnetic shielding performance graphs, it can be seen that the maximum shielding efficiency of the gradient pore (T) structure can reach 59dB, which is 24.5% higher than the maximum shielding efficiency (44.5dB) of the composite material with the uniform pore structure (S). The excellent electromagnetic interference shielding properties of the gradient structure composite material are mainly a result of the synergy between the conductive layer and the three-dimensional structure. The gradient pore structure composite material has excellent performance mainly because the impedance matching can be adjusted to reduce the reflection of electromagnetic waves and promote multiple reflections inside the structure, therebyThe performance of electromagnetic interference shielding performance is enhanced. The pore diameter structure is gradually increased from bottom to top, the contact area between the uppermost layer and the air is the largest, the impedance matching electromagnetic waves of the surface of the gradient porous structure and the air are improved to be incident into the composite material, and more electromagnetic waves can enter the material along with relatively weak reflection. However, after the electromagnetic waves enter the material, some of the electromagnetic waves again contact the conductive layer inside the structure, which is reflected and refracted multiple times inside the material, thereby increasing the reflection loss inside the material. Fig. 8 and 9 represent electromagnetic interference shielding effectiveness graphs of a gradient pore structure and a uniform pore structure, respectively, simulated by CST simulation, and although the electromagnetic interference shielding effectiveness graphs do not completely overlap with the experimental structure, a trend almost identical to the experimental result can be obtained, and the electromagnetic shielding performance of the composite material with the gradient pore structure is superior to that of the uniform pore structure.
Claims (6)
1. TiO with gradient structure 2 -Ti 3 C 2 T x The 3D printing preparation method of the/rGO electromagnetic shielding composite material is characterized by comprising the following steps:
(1) selective etching of Ti with 12M hydrochloric acid and lithium fluoride 3 AlC 2 The metal aluminum layer in the aluminum alloy is subjected to ultrasonic treatment to generate few-layer Ti 3 C 2 T x . Formation of Ti after lyophilization 3 C 2 T x Nanosheets;
(2) stripping graphite into few-layer graphene oxide by adopting an improved Hummer method, and freeze-drying to form graphene oxide nanosheets;
(3) freeze-drying Ti 3 C 2 T x Dispersing graphene oxide nano sheets into water according to a certain proportion to form a dispersion liquid, carrying out ultrasonic treatment for 15min, transferring the dispersion liquid into an agate mortar for grinding, and preparing printing ink;
(4) directly extruding and printing the prepared printing ink by a 3D printer to obtain Ti with a three-dimensional gradient structure 3 C 2 T x a/GO electromagnetic shielding composite;
(5) subjecting the three-dimensional frame to a nitrogen atmosphereThe controlled oxidation is carried out to obtain high-performance TiO 2 -Ti 3 C 2 T x the/rGO electromagnetic shielding composite material.
2. The preparation method of claim 1, wherein the water bath heating temperature of the etching reaction in the step (1) is 45 ℃, the heating and stirring time is 48h, the ultrasonic power is 600W, and the ultrasonic time is 30 min.
3. The method according to claim 1, wherein the peeling conditions in the step (2) are carried out at a bath heating temperature of 50 ℃ and a heating stirring time of 24 hours.
4. The method according to claim 1, wherein the dispersion in the step (3) is prepared at a concentration of 60mg/mL, the ultrasonic power is 600W, and the milling time is 20 min.
5. The manufacturing method according to claim 1, wherein the printing parameters in the step (4) are set as follows, the printing temperature is-10 ℃, the extrusion pressure is 70Pa, the needle diameter is 0.34mm, the receiving speed is 8-12mm/s, and the receiving speed is increased by 1mm/s for every two layers from bottom to top; .
6. The production method as set forth in claim 1, characterized in that the step (5) controls the oxidation conditions: the heating rate is 3 ℃/min, and the temperature is kept for 4h at 500 ℃.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109608841A (en) * | 2018-12-12 | 2019-04-12 | 广安长明高端产业技术研究院 | A kind of preparation method and product of MXene enhancing polylactic acid 3D printing material |
| US20200317957A1 (en) * | 2017-11-21 | 2020-10-08 | The Texas A&M University System | Radio frequency heating for rapid curing of nanocomposite adhesives |
| CN113059870A (en) * | 2021-04-13 | 2021-07-02 | 西北工业大学 | High-thermal-conductivity Ti3C2 Tx/graphene microchip/polylactic acid electromagnetic shielding composite material and 3D printing preparation method thereof |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20200317957A1 (en) * | 2017-11-21 | 2020-10-08 | The Texas A&M University System | Radio frequency heating for rapid curing of nanocomposite adhesives |
| CN109608841A (en) * | 2018-12-12 | 2019-04-12 | 广安长明高端产业技术研究院 | A kind of preparation method and product of MXene enhancing polylactic acid 3D printing material |
| CN113059870A (en) * | 2021-04-13 | 2021-07-02 | 西北工业大学 | High-thermal-conductivity Ti3C2 Tx/graphene microchip/polylactic acid electromagnetic shielding composite material and 3D printing preparation method thereof |
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Application publication date: 20220930 |