CN116514113B - Carbon nano tube-graphene composite material with latticed shell structure and preparation method thereof - Google Patents
Carbon nano tube-graphene composite material with latticed shell structure and preparation method thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 240
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- 239000002131 composite material Substances 0.000 title claims abstract description 43
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- 238000002360 preparation method Methods 0.000 title claims abstract description 14
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- 238000000034 method Methods 0.000 claims abstract description 24
- 239000006185 dispersion Substances 0.000 claims abstract description 17
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- 239000002994 raw material Substances 0.000 claims abstract description 10
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- 238000003756 stirring Methods 0.000 claims description 5
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 239000002048 multi walled nanotube Substances 0.000 claims description 4
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- 238000009954 braiding Methods 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- ZIWRUEGECALFST-UHFFFAOYSA-M sodium 4-(4-dodecoxysulfonylphenoxy)benzenesulfonate Chemical compound [Na+].CCCCCCCCCCCCOS(=O)(=O)c1ccc(Oc2ccc(cc2)S([O-])(=O)=O)cc1 ZIWRUEGECALFST-UHFFFAOYSA-M 0.000 claims description 3
- KVCGISUBCHHTDD-UHFFFAOYSA-M sodium;4-methylbenzenesulfonate Chemical compound [Na+].CC1=CC=C(S([O-])(=O)=O)C=C1 KVCGISUBCHHTDD-UHFFFAOYSA-M 0.000 claims description 3
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 claims description 2
- IMCAQSSWXZDVKX-UHFFFAOYSA-N C(C1=CC=CC=C1)S(=O)(=O)OCCCCCCCCCCCCCCCCCC.[Na] Chemical compound C(C1=CC=CC=C1)S(=O)(=O)OCCCCCCCCCCCCCCCCCC.[Na] IMCAQSSWXZDVKX-UHFFFAOYSA-N 0.000 claims description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- 230000003213 activating effect Effects 0.000 claims description 2
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- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 2
- 239000011156 metal matrix composite Substances 0.000 abstract description 16
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- 239000003575 carbonaceous material Substances 0.000 abstract description 2
- 229910021392 nanocarbon Inorganic materials 0.000 abstract description 2
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- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910003481 amorphous carbon Inorganic materials 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000002135 nanosheet Substances 0.000 description 2
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- IYEOKWZWTANOOM-UHFFFAOYSA-N CC1=CC=C(C=C1)S(=O)(=O)OCCCCCCCCCCCCCCCCCC.[Na] Chemical compound CC1=CC=C(C=C1)S(=O)(=O)OCCCCCCCCCCCCCCCCCC.[Na] IYEOKWZWTANOOM-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
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- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
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- 238000012360 testing method Methods 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/194—After-treatment
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/158—Carbon nanotubes
- C01B32/168—After-treatment
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2202/00—Structure or properties of carbon nanotubes
- C01B2202/20—Nanotubes characterized by their properties
- C01B2202/36—Diameter
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/04—Specific amount of layers or specific thickness
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/20—Graphene characterized by its properties
- C01B2204/32—Size or surface area
Abstract
A carbon nano tube-graphene composite material with a latticed shell structure and a preparation method thereof belong to the composite material technology. Grinding the multi-layer graphene at a high speed for a long time to obtain graphene fragments adhered on the surface of the grinding ball and activated on the surface; then grinding at a low speed for a short time to clean graphene fragments on the surface of the grinding ball into dispersion liquid; grinding at a high speed and in a short time, obliquely inserting and linking raw material thick-diameter carbon nanotubes into a graphene chip lamellar structure, and constructing a thick-diameter carbon nanotube supporting rod system structure; finally, adding the small-diameter carbon nano tube for low-speed long-time grinding, and weaving a space reticulated shell structure formed by taking the large-diameter carbon nano tube as a rod tie beam and taking the small-diameter carbon nano tube as a curved surface grid by utilizing the self-winding characteristic of the carbon nano tube. The invention solves the problems that the nano carbon material is used as a reinforcing phase, the structure is unstable, the rigidity is low, the deformation and the peeling are easy in the wearing process, the plasticity of the metal matrix composite material can not be effectively improved, and the reinforcing effect on the comprehensive performance of the metal matrix composite material is obvious.
Description
Technical Field
The invention belongs to the technical field of composite materials, and particularly relates to a carbon nano tube-graphene composite material with a latticed shell structure and a preparation method thereof.
Background
Carbon Nanotubes (CNTs) or Graphene (GN) are often used in the preparation of metal-based composites with their excellent properties as reinforcement. But due to their one-or two-dimensional nature, their performance in metal matrix composites appears anisotropic. Secondly, in the pressing and bearing processes of the metal matrix composite material prepared by the powder metallurgy method, the C-C tubular and GN C-C lamellar structures of CNTs are easily damaged, amorphous carbon is formed, and the reinforcing effect of the amorphous carbon is reduced. Because CNTs and GN have large specific surface areas and are easy to tangle and agglomerate, the structure is unstable and the rigidity is insufficient when the CNTs and GN are carried in the metal matrix composite, and the load cannot be effectively transmitted, so that the tensile strength is reduced; in addition, in the abrasion process of the metal matrix composite, the reinforced phase CNTs or GN are easy to peel from the metal matrix due to the damage of the carbon layer structure, so that the abrasion rate is increased and the like. Generally, when a carbon nanotube or graphene reinforced metal matrix composite is used alone, the elongation is reduced while the hardness and tensile strength are improved.
The carbon nano tube-graphene composite material can improve the material performance due to the synergistic effect of graphene and carbon nano tubes. In recent years, although many reports about preparation and application of carbon nanotube-graphene composite materials are provided, the application of the product is mainly focused on the fields of photoelectric devices, energy storage batteries, electrochemical sensors and the like. For example, the chinese patent document with application number 2018111569851 discloses a preparation method of a high-stability graphene/carbon nanotube composite conductive paste, which is to grind graphene and carbon nanotubes at high speed respectively, and then simply mix the graphene and carbon nanotubes after adding a binder, so as to obtain a mixed paste of carbon nanotubes and graphene. The Chinese patent document with application number 2017114778623 discloses a graphene/carbon nanotube composite material, a preparation method and application thereof, wherein carbon nanotubes are added in the oxidation reaction process of graphite to obtain a mixture of the carbon nanotubes and graphene, and the mixture is used as a conductive agent in a lithium battery. Some methods utilize carbon sources to vapor deposit on carbon nanotubes on the basis of graphene or to prepare graphene in the structural gaps of carbon nanotubes. For example, chinese patent document No. 2019111777632 discloses a three-dimensional porous graphene skeleton-single-walled carbon nanotube flexible composite material and a preparation method thereof, wherein copper powder-based single-walled carbon nanotubes are mixed by ball milling, and graphene sheets are prepared in the space of the single-walled carbon nanotubes by chemical vapor deposition for flexible electronic materials. Although the Chinese patent document with the application number of 2018107795385 discloses a three-dimensional graphene-carbon nanotube network structure and a preparation method thereof, a benzene ring is used as a carbon source, a carbon nanotube cavernous body is deposited in a chemical vapor phase, and then graphene is prepared in the cavernous body through an amination-carbonization process; because the graphene is randomly distributed in the pores of the carbon nanotube sponge body, the carbon nanotube sponge body cannot be well supported, and therefore, if the product is used as a reinforcing phase, the problem of reducing the structural damage of the carbon nanotube and the graphene in the friction process cannot be solved. For the reinforcing phase of the metal matrix composite, in particular, the reinforcing phase of the metal matrix composite prepared by a powder metallurgy method, further development of the carbon nanotube-graphene composite with a new structure is required.
Disclosure of Invention
The invention aims to provide a carbon nano tube-graphene composite material with a latticed shell structure and a preparation method thereof, and the obtained material is particularly suitable for being used as a reinforcing phase of a metal matrix composite material.
To achieve the object of the invention, the applicant has developed a carbon nanotube-graphene composite material for preparing a reticulated shell structure with reference to the reticulated shell structure in architecture. The characteristic of self-winding of the carbon nano tube is utilized to lead the thick-diameter and thin-diameter carbon nano tube to be woven to prepare curved surface grid links and wrap the curved surface grid links outside the graphene nano sheet so as to solve the problems of carbon nano tube winding and graphene agglomeration; because the net shell woven by the carbon nano tube mainly transmits force point by point in multiple directions through the carbon nano tube woven by the net shell, the thick-diameter carbon nano tube mainly plays a role of a beam, and the load can be transmitted along the net woven by the thin-diameter carbon nano tube to multiple directions, so that the carbon nano tube net shell is uniform in stress, high in space rigidity and higher in stability, the hardness and tensile strength of the metal matrix composite material can be improved, and the problem of stripping and falling of a carbon nano tube or graphene reinforcing phase in the abrasion process of the metal matrix composite material is solved.
The invention relates to a carbon nano tube-graphene composite material with a latticed shell structure, which is characterized in that: the graphene surface is obliquely inserted into a thick-diameter carbon nanotube, then the thick-diameter carbon nanotube is used as a support and a rod system linking basis, a curved surface space grid shell structure is obtained on the graphene surface by weaving the thin-diameter carbon nanotube, and the curved surface space grid shell structure is linked and coated on the graphene surface by a net shell of a thick-diameter and thin-diameter carbon nanotube framework.
The invention relates to a method for preparing a carbon nano tube-graphene composite material with a latticed shell structure, which is characterized by comprising the following steps of:
(1) Mechanically activating the graphene surface: adding a multilayer graphene raw material into a horizontal stirring high-energy ball mill, adding a ceramic grinding ball, and grinding at high speed for a long time to ensure that graphene is sufficiently ground, graphene fragments are adhered to the surface of the ceramic grinding ball, carbon rings on the surfaces of the crushed graphene fragments are destroyed, gaps and incomplete surface coordination occur, the surface energy of the graphene is increased, and an activation site is provided for oblique insertion and embedding of carbon nanotubes;
(2) Preparing graphene dispersion liquid: pouring out the grinding balls and the materials after ball milling in the step (1), screening the grinding balls with graphene fragments adhered to the surfaces, taking out the grinding balls, adding a 0# dispersion solution, and carrying out ultrasonic treatment; adding the ultrasonic-treated grinding balls and the solution into a ball milling bin, grinding at low speed for a short time, and cleaning graphene fragments adhered to the surfaces of the grinding balls in the grinding process into a dispersion liquid to obtain a graphene fragment suspension A;
(3) Building a thick-diameter carbon nano tube support rod system: adding the large-diameter carbon nanotubes into the graphene fragment suspension A prepared in the step 2, and then grinding at a high speed for a short time. And (2) utilizing the kinetic energy of high-speed collision to enable the large-diameter carbon nano tube to form a structure of obliquely inserting and embedding graphene sheets at the gaps and defects on the surface of the graphene fragments mechanically activated in the step (1). The thick-diameter carbon nano tube is obliquely inserted into graphene fragments to provide a rod system supporting and linking effect for the woven carbon nano tube net shell;
(4) Braided carbon nanotube-graphene reticulated shell structure: adding small-diameter carbon nanotubes into the suspension of the large-diameter carbon nanotubes and graphene fragments prepared in the step 3, grinding at low speed for a long time until the small-diameter carbon nanotubes and the large-diameter carbon nanotubes are self-wound, braiding the small-diameter carbon nanotubes and the large-diameter carbon nanotubes on the outer layer of the graphene fragments to form a space reticulated shell structure formed by taking the large-diameter carbon nanotubes as a rod tie beam and taking the small-diameter carbon nanotubes as a curved surface grid, and then discharging, cleaning, suction filtering and drying to obtain the carbon nanotube-graphene composite material with the reticulated shell structure;
the number of the layers of the multilayer graphene raw material in the step (1) is 3-10, and the sheet diameter is 3-15 mu m; the ceramic grinding ball is ZrO2 grinding ball, the diameter of the grinding ball is 2-5mm, the volume ratio of the grinding ball to the graphene is 1:1-1.5, and the volume filling rate of the grinding ball and the graphene in the ball milling bin is 40% -60%; the high-speed long-time grinding is carried out at the collision speed of the grinding balls of 9-15 m/s for 3-6 hours;
the 0# dispersing solution in the step (2) consists of a 1# surfactant, a 2# dispersing agent and water, wherein the 2# dispersing agent is one or two of sodium dodecyl diphenyl ether disulfonate, dodecylbenzene sulfonic acid, sodium octadecyltoluene sulfonate, sodium p-toluene sulfonate, N-dimethyl pyrrolidone, sodium petroleum sulfonate and polyethylene glycol; the concentration of the surfactant 1 in the dispersing solution 0# is 1-3g/L, and the concentration of the dispersing agent 2 is 1-4g/L;
and (3) adding the grinding balls with the graphene fragments adhered to the surfaces in the step (2) into a 0# dispersion solution, wherein the volume ratio of the 0# dispersion solution to the grinding balls is 1.3-1:1. Adding the grinding balls and the solution into a ball milling bin after ultrasonic treatment, and grinding at a low speed and in a short time, wherein the collision speed of the grinding balls is as follows: 2-5 m/s, grinding time: 10-30 minutes.
The added thick-diameter carbon nanotubes in the step (3) are multi-wall carbon nanotubes, and the outer diameter is 90-120nm; the mass ratio of the thick-diameter carbon nano tube to the graphene fragments in the graphene fragment suspension A is 0.2-0.5:1; the grinding is carried out at high speed for a short time, the collision speed of the grinding balls is 9-15 m/s, and the grinding time is 10-30 minutes;
the added small-diameter carbon nano tube in the step (4) is a single-wall or multi-wall carbon nano tube, and the outer diameter is 20-50nm; the mass ratio of the small-diameter carbon nano tube to the graphene fragments in the graphene fragment suspension A is 0.8-1.5:1; the grinding is carried out at a low speed for a long time to reach a collision speed of the grinding balls of 2-5 m/s, and the grinding time is 3-6 hours.
The invention has the beneficial effects that: the self-winding property of the carbon nano tube is utilized to weave the carbon nano tube net shell, so that the structure is stable, the carbon nano tube net shell is completely wrapped and linked outside the graphene nano sheet, the net shell structure is uniformly stressed and has high space rigidity, the stress is in a main stress mode by taking the internal force of the net shell, and the stress can be transmitted point by point along the radial direction through the carbon nano tube on the net shell in the metal matrix composite. The elongation is reduced while the hardness and the tensile strength of the carbon nano tube or graphene reinforced metal matrix composite are improved, but the elongation is also improved while the tensile strength, the hardness and the wear resistance of the metal matrix composite are obviously improved by using the carbon nano tube-graphene reinforced metal matrix composite with the latticed shell structure. In addition, the preparation of the carbon nano tube-graphene latticed shell structure is simple, the requirements on raw materials of the carbon nano tube and graphene are low, and the cost is low.
Drawings
Fig. 1 is a graph showing tensile stress-strain curve comparison of the reinforced Al-based composite materials prepared in example 1, example 2, comparative example 1 and comparative example 2.
Fig. 2 is a morphology diagram of the carbon nanotube-graphene composite material with the reticulated shell structure obtained in example 2.
Fig. 3 is a morphology diagram of a carbon nanotube-graphene composite material with a reticulated shell structure obtained in example 2.
Detailed description of the preferred embodiments
The raw materials and equipment used in the following examples are commercially available.
Example 1
The carbon nano tube-graphene composite material with the latticed shell structure is prepared by the following steps:
(1) 500ml of multilayer graphene raw material with the number of layers of 3-6 and the sheet diameter of 5-8 mu m is added into a horizontal stirring high-energy ball mill, and ZrO with the diameter of 500ml and 3mm is added 2 And (3) grinding the ceramic grinding ball at a high speed for a long time, wherein the collision speed of the grinding ball is 14m/s, grinding for 3.5 hours, discharging the grinding ball by a ball mill, screening out the grinding ball with graphene fragments adhered to the surface, weighing, and subtracting the mass of the originally added grinding ball to obtain 2.13g of graphene fragments.
(2) Preparing a 0# dispersion solution: 1g of a No. 1 surfactant, 0.5g of sodium stearyl tosylate, 0.5g of polyethylene glycol and 1L of water are taken and fully stirred to obtain a No. 0 dispersion solution for standby.
(3) Adding 500ml of 0# dispersion solution into grinding balls with graphene fragments adhered to the surfaces, carrying out ultrasonic treatment for 10 minutes, adding the grinding balls and the solution into a ball milling bin body together, and carrying out low-speed and short-time grinding, wherein the collision speed of the grinding balls is that: 5 m/s, grinding for 10 minutes to obtain graphene fragment suspension A.
(4) To the graphene chip suspension A in the ball mill bin, 0.8g of a thick-diameter carbon nanotube with an outer diameter of 100nm was added, and the mixture was subjected to high-speed short-time grinding at a ball collision speed of 14m/s for 10 minutes.
(5) Adding 3.0g of small-diameter carbon nano tubes with the outer diameter of 20nm into graphene fragment suspension A+ large-diameter carbon nano tubes in a ball milling bin, and carrying out low-speed and long-time grinding, wherein the collision speed of grinding balls is 5 m/s, and the grinding time is as follows: 3 hours. And finally, discharging, washing, filtering and drying to obtain the carbon nano tube-graphene composite material with the reticulated shell structure.
The carbon nano tube-graphene composite material with the net shell structure is used as a novel reinforcing phase, a powder metallurgy method, a ball milling and vacuum hot pressing method is adopted to prepare 1wt.% CNTs-GN reinforced Al-based composite material, and the hardness, the tensile strength, the elongation and the wear rate of the reinforced Al-based composite material are detected.
Example 2
The carbon nano tube-graphene composite material with the latticed shell structure is prepared by the following steps:
(1) 600ml of multilayer graphene raw material with the layer number of 5-9 layers and the sheet diameter of 6-10 mu m is added into a horizontal stirring high-energy ball mill, and 600ml of ZrO with the diameter of 5mm is added 2 And (3) grinding the ceramic grinding ball at a high speed for a long time, wherein the collision speed of the grinding ball is 9.6m/s, grinding for 6 hours, discharging by a ball mill, screening out the grinding ball with graphene fragments adhered to the surface, weighing, and subtracting the mass of the originally added grinding ball to obtain 2.7g of graphene fragments.
(2) Preparing a 0# dispersion solution: taking 3g of a No. 1 surfactant, 2g of sodium dodecyl diphenyl ether disulfonate, 2g of sodium paratoluenesulfonate and 1L of water, and fully stirring to obtain a No. 0 dispersion solution for later use.
(3) 700ml of 0# dispersion solution is added into grinding balls with graphene fragments adhered to the surfaces, ultrasonic treatment is carried out for 10 minutes, the grinding balls and the solution are added into a ball milling bin body together, low-speed and short-time grinding is carried out, and the collision speed of the grinding balls is increased: 2.5 m/s, grinding for 30 minutes to obtain graphene fragment suspension A.
(4) To the graphene chip suspension A in the ball mill bin, 1.3g of a large-diameter carbon nanotube with an outer diameter of 120nm was added, and high-speed short-time grinding was performed, with a ball collision speed of 10 m/s, for 25 minutes.
(5) 2.16g of small-diameter carbon nano tubes with the outer diameter of 40nm are added into graphene fragment suspension A+ large-diameter carbon nano tubes in a ball milling bin, low-speed and long-time grinding is carried out, the collision speed of grinding balls is 2.5 m/s, and the grinding time is as follows: and 6 hours. And finally, discharging, washing, filtering and drying to obtain the carbon nano tube-graphene composite material with the reticulated shell structure.
The carbon nano tube-graphene composite material with the net shell structure is used as a novel reinforcing phase, a powder metallurgy method, a ball milling and vacuum hot pressing method is adopted to prepare 1wt.% CNTs-GN reinforced Al-based composite material, and the hardness, the tensile strength, the elongation and the wear rate of the reinforced Al-based composite material are detected.
Comparative example 1
The same powder metallurgy method, ball milling and vacuum hot pressing method were used as in example 1 and example 2 to prepare 1wt.% GN reinforced Al-based composite materials, and the hardness, tensile strength, elongation and wear rate were measured.
Comparative example 2
The same powder metallurgy method, ball milling and vacuum hot pressing method were used as in example 1 and example 2 to prepare 1wt.% CNTs reinforced Al-based composite material, and the hardness, tensile strength, elongation and wear rate were measured.
The net shell structure woven by the large-diameter and small-diameter carbon nanotubes can be seen in fig. 2, and the net shell structure is uniformly and completely wrapped on the outer layer of the graphene fragments. As can be seen from fig. 3, the thick-diameter carbon nanotubes are supported and connected in the graphene sheets by the rod system, the thin-diameter carbon nanotubes are wound and woven in the thin-diameter carbon nanotubes, and the carbon nanotube net shell structure is uniformly connected and wrapped outside the graphene sheets, so that the novel three-dimensional carbon nanotube-graphene with the net shell structure is formed.
The magnification of fig. 3 is higher than that of fig. 2.
Table 1 shows the test data of the tensile strength, elongation, hardness, and wear rate of example 1, example 2, comparative example 1, and comparative example 2. The carbon nano tube-graphene with the special reticulated shell structure has a rigid and stable structure, when bearing load, the load can be transmitted along a plurality of directions through the braiding nodes of the carbon nano tube in the reticulated shell, and the structural space of the reticulated shell has high rigidity, so that when the carbon nano tube-graphene is used as a metal base reinforcing phase, stable antifriction components with high hardness are formed in the friction and wear process, and the wear rate of the aluminum-based composite material can be obviously reduced in the embodiment 1 and the embodiment 2. As can be seen from table 1, the maximum tensile strength of the carbon nanotube-graphene composite material in the example 1 and the example 2 is significantly higher than that of the comparative examples 1 and 2, and the elongation is also significantly improved while the tensile strength is improved, which indicates that the carbon nanotube-graphene composite material in the reticulated shell structure is used as a novel reinforcing phase, and the strength and the plasticity of the aluminum-based composite material can be significantly improved, which is not found in the conventional reinforcing effect of the nano carbon material.
TABLE 1
The above examples are merely illustrative of the present invention for further illustration, but the scope of the present invention is not limited by the illustrated examples.
Claims (4)
1. The preparation method of the carbon nano tube-graphene composite material with the latticed shell structure is characterized by comprising the following steps of:
(1) Mechanically activating the graphene surface: adding a multilayer graphene raw material into a horizontal stirring high-energy ball mill, adding a ceramic grinding ball, and grinding at high speed for a long time to ensure that graphene is sufficiently ground, graphene fragments are adhered to the surface of the ceramic grinding ball, carbon rings on the surfaces of the crushed graphene fragments are destroyed, gaps and incomplete surface coordination occur, the surface energy of the graphene is increased, and an activation site is provided for oblique insertion and embedding of carbon nanotubes;
(2) Preparing graphene dispersion liquid: pouring out the grinding balls and the materials after ball milling in the step (1), screening the grinding balls with graphene fragments adhered to the surfaces, taking out the grinding balls, adding a 0# dispersion solution, and carrying out ultrasonic treatment; adding the ultrasonic-treated grinding balls and the solution into a ball milling bin, grinding at low speed for a short time, and cleaning graphene fragments adhered to the surfaces of the grinding balls in the grinding process into a dispersion liquid to obtain a graphene fragment suspension A;
(3) Building a thick-diameter carbon nano tube support rod system: adding a thick-diameter carbon nanotube into the graphene fragment suspension A prepared in the step (2), grinding at a high speed for a short time, and utilizing the kinetic energy of high-speed collision to enable the thick-diameter carbon nanotube to form a structure of obliquely inserting and embedding graphene fragments at the gaps and defects of the surface of the graphene fragments mechanically activated in the step (1), wherein the thick-diameter carbon nanotube is obliquely inserted and embedded into the graphene fragments, so as to provide rod system supporting and linking effects for the woven carbon nanotube network shell;
(4) Braided carbon nanotube-graphene reticulated shell structure: adding small-diameter carbon nanotubes into the suspension of the large-diameter carbon nanotubes and graphene fragments prepared in the step (3), grinding at low speed for a long time until the small-diameter carbon nanotubes and the large-diameter carbon nanotubes are self-wound, braiding the outer layer of the graphene fragments to form a space reticulated shell structure consisting of a rod system beam of the large-diameter carbon nanotubes and a curved grid of the small-diameter carbon nanotubes, and then discharging, cleaning, suction filtering and drying to obtain the carbon nanotube-graphene composite material with the reticulated shell structure;
the number of the layers of the multilayer graphene raw material in the step (1) is 3-10, and the sheet diameter is 3-15 mu m; the diameter of the ceramic grinding ball is 2-5mm, the volume ratio of the grinding ball to the graphene is 1:1-1.5, and the volume filling rate of the grinding ball to the graphene in the ball milling bin is 40% -60%; the high-speed long-time grinding is carried out at the collision speed of the grinding balls of 9-15 m/s for 3-6 hours;
the 0# dispersing solution in the step (2) consists of a 1# surfactant, a 2# dispersing agent and water, wherein the 2# dispersing agent is one or two of sodium dodecyl diphenyl ether disulfonate, dodecylbenzene sulfonic acid, sodium octadecyltoluene sulfonate, sodium p-toluene sulfonate, N-dimethyl pyrrolidone, sodium petroleum sulfonate and polyethylene glycol; the concentration of the surfactant 1 in the dispersing solution 0# is 1-3g/L, and the concentration of the dispersing agent 2 is 1-4g/L;
adding the grinding balls with the graphene fragments adhered to the surfaces in the step (2) into a 0# dispersion solution, wherein the volume ratio of the 0# dispersion solution to the grinding balls is 1.3-1:1, adding the grinding balls and the solution into a ball milling bin after ultrasonic treatment, and grinding at a low speed for a short time, wherein the collision speed of the grinding balls is as follows: 2-5 m/s, grinding time: 10-30 minutes;
the added thick-diameter carbon nanotubes in the step (3) are multi-wall carbon nanotubes, and the outer diameter is 90-120nm; the mass ratio of the thick-diameter carbon nano tube to the graphene fragments in the graphene fragment suspension A is 0.2-0.5:1; the grinding is carried out at high speed for a short time, the collision speed of the grinding balls is 9-15 m/s, and the grinding time is 10-30 minutes;
the added small-diameter carbon nano tube in the step (4) is a single-wall or multi-wall carbon nano tube, and the outer diameter is 20-50nm; the mass ratio of the small-diameter carbon nano tube to the graphene fragments in the graphene fragment suspension A is 0.8-1.5:1; the grinding is carried out at a low speed for a long time to reach a collision speed of the grinding balls of 2-5 m/s, and the grinding time is 3-6 hours.
2. The method for preparing the carbon nanotube-graphene composite material with the latticed shell structure according to claim 1, wherein the raw material of the multi-layer graphene in the step (1) is 3-6 layers or 5-9 layers.
3. The method for preparing a carbon nanotube-graphene composite material with a reticulated shell structure according to claim 1, wherein the ceramic grinding balls in the step (1) are ZrO2 grinding balls.
4. The carbon nanotube-graphene composite material with the reticulated shell structure, which is prepared by the preparation method of the carbon nanotube-graphene composite material with the reticulated shell structure, is characterized in that: the graphene surface is obliquely inserted into the thick-diameter carbon nano tube, the thick-diameter carbon nano tube is used as a support and link rod system foundation, the thin-diameter carbon nano tube is woven into a curved surface space grid shell structure on the graphene surface, and the net shell of the thick-diameter and thin-diameter carbon nano tube framework is linked and coated on the graphene surface.
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| WO2010038784A1 (en) * | 2008-09-30 | 2010-04-08 | 保土谷化学工業株式会社 | Composite material containing carbon fiber |
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