CN108047495B - In-situ preparation method of carbon nano tube and carbon black super-strong composite filler - Google Patents
In-situ preparation method of carbon nano tube and carbon black super-strong composite filler Download PDFInfo
- Publication number
- CN108047495B CN108047495B CN201711279620.3A CN201711279620A CN108047495B CN 108047495 B CN108047495 B CN 108047495B CN 201711279620 A CN201711279620 A CN 201711279620A CN 108047495 B CN108047495 B CN 108047495B
- Authority
- CN
- China
- Prior art keywords
- carbon black
- carbon
- composite filler
- carbon nanotube
- super
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/001—Conductive additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Abstract
The invention belongs to the technical field of composite filler preparation, and particularly relates to an in-situ preparation method of a carbon nano tube and carbon black super-strong composite filler. The carbon nano tubes are added into a liquid raw material for preparing the carbon black in advance, the super-strong composite filler of the carbon nano tubes and the carbon black is synthesized in situ, and a perfect grape string-like structure which takes the pre-mixed carbon nano tubes as a main line and the generated carbon black particles as a string bead form is prepared. The super-strong composite filler formed in situ can freely control the composition proportion of the carbon nano tube and the carbon black, has good conductive and reinforcing effects, and can completely replace imported superconducting carbon black. The invention has simple and stable process and convenient operation, and does not need to change the prior carbon black production device and equipment.
Description
Technical Field
The invention belongs to the technical field of composite filler preparation, and particularly relates to an in-situ preparation method of a carbon nano tube and carbon black super-strong composite filler.
Background
Carbon nanotubes, which are one-dimensional nanomaterials having excellent physical and mechanical properties, are mainly coaxial circular tubes having several to tens of layers of carbon atoms arranged in a hexagonal pattern. It has a very large aspect ratio, typically between 1-100nm in diameter and several microns to hundreds of microns in length. Due to the large length-diameter ratio, the carbon nano tube has excellent mechanical, electrical, electric conduction and heat conduction performances. Because of the excellent performance, the carbon nano tube has wide and potential application prospect in various fields such as catalyst carriers, rubber plastic composite materials, electrochemical materials, photoelectric sensing and the like.
After the carbon nano tube and the carbon black are compounded, a conductive structure similar to a grape string shape can be formed microscopically, a three-dimensional conductive network is formed by the organic combination of the points and the lines, the conductive capability is greatly improved, and the reinforcing effect is also greatly improved. With the development of technology and the reduction of cost, the compound filler of the carbon nano tube and the carbon black can be more widely applied to plastic and rubber products.
Patent CN201410693341.1 discloses a multi-element structure composite conductive filler. The invention plates a layer of wave-absorbing magnetic material (such as Ni, Fe, Co, Ni-P, Co-P, Ni-Co-P, Co-W-P, barium ferrite, ferroferric oxide, carbonyl iron and the like) on the surface of light inorganic powder (such as hollow glass micro-beads, mica, carbon fiber, flake graphite and the like), and plates a layer of conductive material (such as silver, nickel, copper and other metals or doped tin oxide, doped indium oxide, doped zinc oxide, titanium dioxide and other inorganic oxides) to prepare the novel multi-element structure composite conductive filler-inorganic powder core/magnetic material coating/conductive material coating. The composite conductive filler can further improve the electromagnetic shielding performance by utilizing the absorption performance of the wave-absorbing material to electromagnetic waves and the reflection performance of the conductive material to the electromagnetic waves, has the advantages of light weight, low cost, wide shielding frequency band, good shielding performance and the like, and has great application value in the field of electromagnetic shielding composite materials. But the operation is complex, the process is complicated and is not easy to control, and the method is not beneficial to direct popularization and industrialization enlargement.
Patent CN201610469431.1 discloses a preparation method of a sulfur-based byproduct carbon black composite conductive filler, belonging to the technical field of conductive filler preparation. The preparation method comprises the steps of primarily hydrolyzing peach gum by using microwave irradiation under an alkaline condition to prepare peach gum slurry for later use, treating petrochemical byproduct carbon black by using acidic methane tank supernatant, dissolving ash in the petrochemical byproduct carbon black to purify the carbon black, mixing the purified peach gum slurry with the prepared peach gum slurry, adding yeast for fermentation to enable the mixture to have a porous structure, extruding by using a screw to improve the uniformity of the filler, adding sublimed sulfur for compounding, carbonizing the peach gum adhesive by calcining, using the remaining carbon as a framework, and fixing the sulfur and the carbon black in the filler to prepare the composite conductive filler. The preparation process steps are still complicated, the requirement on equipment is high, and the cost is high.
Patent CN201610898391.2 discloses a preparation method of aqueous environment-friendly conductive carbon paste based on graphene-carbon black composite filler, which is characterized by comprising the following components in percentage by mass: adhesive: 5-20%, mixed solvent: 65-85%, graphene: 0.1-5%, carbon black: 1-15%, dispersant: 0.05-1%, defoamer: 0.1-1%, crosslinking agent: 0.1-1%, thickener: 0.1 to 1 percent. The invention still needs the external force compounding of the carbon black product with graphene, dispersant and the like at the later stage to meet the corresponding requirements.
Although the preparation process and the preparation method of the conductive filler are improved, the problems that the in-situ preparation cannot be carried out, the carbon black needs to be compounded with other conductive agents at the later stage, the preparation steps are complex and tedious, the process control is difficult, the large-scale amplification is not easy to realize and the like still exist, and therefore, an in-situ preparation method of the carbon nano tube and carbon black super-strong composite filler is urgently needed.
Disclosure of Invention
The invention aims to provide an in-situ preparation method of a carbon nano tube and carbon black super-strong composite filler, aiming at solving the problems of high cost, complex and fussy process steps, no in-situ preparation method of the carbon nano tube and carbon black super-strong composite filler and the like of the existing preparation process of the conductive filler. The invention can realize the free control (realized by calculating the quantity of the generated carbon black in advance so as to calculate the quantity of the carbon nano tubes needing to be added in advance according to the final proportion) of the composition ratio of the carbon nano tubes and the carbon black, and has the advantages of simple production process, easy operation of the process, low cost and easy large-scale popularization.
The technical scheme of the invention is as follows:
an in-situ preparation method of carbon nano tube and carbon black super-strong composite filler is characterized by that the carbon nano tube is mixed with liquid raw material for preparing carbon black, then the carbon nano tube and carbon black super-strong composite filler are prepared by means of high-temp. in-situ treatment, and when the carbon black raw material is undergone the process of high-temp. production of carbon black, the pre-mixed carbon nano tube is used as main line, and the produced carbon black particles are used as perfect grape string-like structure with string-bead form.
An in-situ preparation method of a carbon nano tube and carbon black super-strong composite filler comprises the following specific steps:
(1) mixing carbon nanotubes into a liquid raw material for preparing carbon black, wherein the weight ratio of the carbon nanotubes to the liquid raw material is carbon nanotubes: liquid feedstock =0.1:100 and 500: 100;
(2) heating the mixture of the carbon nano tube and the liquid raw material to 50-110 ℃ for dehydration;
(3) preheating the mixture of the carbon nano tube and the liquid raw material to 600-650 ℃, and atomizing and spraying the mixture into the reaction furnace;
(4) after being heated in stages, the superstrong composite filler of the carbon nano tube and the carbon black is prepared in situ at the temperature of 1000-2300 ℃;
(5) the quenching section sprays water to cool to 800-860 ℃, and the water is cooled to 230-240 ℃ in three stages;
(6) separating, collecting and drying at 70-120 ℃.
The invention is also characterized in that:
the weight ratio of the carbon nano tube to the liquid raw material is carbon nano tube: liquid feedstock =10:100-50:100, the preferred interval being more likely to form an effective grape bunch conducting structure.
The liquid raw material for preparing the carbon black is one or a mixture of more of coal tar, asphalt, clarified oil and ethylene tar, wherein the clarified oil is catalytic slurry oil which is simply treated during catalytic cracking reaction, the clarified oil has high density and low hydrogen content, and the content of saturated hydrocarbon and aromatic hydrocarbon accounts for 50-60%.
The carbon nano tube is one or a mixture of a plurality of single-wall carbon nano tubes, double-wall carbon nano tubes and multi-wall carbon nano tubes, the particle size range of the carbon nano tube is 50nm-500 mu m, preferably 100nm-50 mu m, more preferably 1 mu m-20 mu m, and the proper particle size of the carbon nano tube can provide a more proper space for matching and combining with the formed carbon black.
The mixture of the carbon nano tube and the liquid raw material is heated to a dehydration temperature of 80-90 ℃, and the efficiency is improved in the drying process and high-hardness agglomeration is not easy to form in a proper temperature range.
The step (4) of heating in three stages (three-stage heating, temperature gradually rising and carbon deposition caused by sudden temperature rising) is adopted; the in-situ preparation temperature is 1400-1700 ℃, the proportion of the amorphous carbon formed at too low temperature is increased, the forming speed is too high at too high temperature, and the formation of the grape string-shaped structure is insufficient, which have adverse effects on the electric conduction and reinforcement performance of the composite material.
The carbon nano tube and carbon black super-strong composite filler obtained by the in-situ preparation method of the carbon nano tube and carbon black super-strong composite filler has a perfect grape string-like structure which takes the pre-mixed carbon nano tube as a main line and the generated carbon black particles as a bead string form.
The obtained carbon nano tube and carbon black super-strong composite filler is used for electric conduction, heat conduction and reinforcement of plastic and rubber products.
The invention has the beneficial effects that: the invention adopts a certain proportion of carbon nano tubes to be doped into the liquid raw material for preparing the carbon black in advance; when preparing the carbon black, the superstrong composite conductive material of the carbon nano tube and the carbon black is synthesized in situ; the ideal grape string-shaped conductive filler is obtained by controlling the adding proportion of the carbon nano tubes; compared with the traditional process, the method greatly improves the conductivity of the original carbon black product and improves the market competitiveness of the product. The seamless cut-in of the existing carbon black preparation equipment can be realized, the change is not needed, the cost is low, and the large-scale production is easy to realize.
In a word, the super-strong composite filler formed in situ can freely control the composition ratio of the carbon nano tube and the carbon black, has good conductive and reinforcing effects, and can completely replace imported superconducting carbon black; and the process is simple and stable, the operation is convenient, and the existing carbon black production device and equipment do not need to be changed.
Drawings
FIG. 1 is an SEM picture of a carbon nanotube and carbon black beaded composite filler prepared in situ.
FIG. 2 SEM picture of carbon nanotube and carbon black beaded composite filler prepared in situ.
Detailed Description
The technical solution of the present invention will be more clearly and completely explained in the following with reference to the contents of the embodiments of the present invention. It is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all experimental cases. Based on the embodiment of the invention. Other embodiments available to others skilled in the art are within the scope of the invention.
Example 1:
(1) mixing carbon nanotubes with a liquid raw material for preparing carbon black, wherein the crushed particle size of the carbon nanotubes is 5-15 mu m, and the weight of the carbon nanotubes is 110 g; the weight of the liquid raw material is 1000 g;
(2) heating the mixture of the carbon nano tube and the liquid raw material to 90 ℃ for dehydration;
(3) preheating the mixture of the carbon nano tube and the liquid raw material to 650 ℃, and atomizing and spraying the mixture into a reaction furnace;
(4) after graded heating, preparing the super-strong composite filler of the carbon nano tube and the carbon black in situ at 1700 ℃;
(5) spraying water to the quenching section to cool to 850 ℃, and cooling to 240 ℃ in three stages (specifically arranged);
(6) separating, collecting, and drying at 110 deg.C;
(7) weighing the sample, wherein the weight is 525 g; sample SEM is fig. 1.
Example 2:
(1) mixing carbon nanotubes with a liquid raw material for preparing carbon black, wherein the crushed particle size of the carbon nanotubes is 15-20 mu m, and the weight of the carbon nanotubes is 90 g; the weight of the liquid raw material is 900 g;
(2) heating the mixture of the carbon nano tube and the liquid raw material to 85 ℃ for dehydration;
(3) preheating the mixture of the carbon nano tube and the liquid raw material to 640 ℃, and atomizing and spraying the mixture into a reaction furnace;
(4) after graded heating, preparing the super-strong composite filler of the carbon nano tube and the carbon black in situ at 1650 ℃;
(5) cooling the quenching section by water spraying to 840 ℃ in three stages (specifically set) to 230 ℃;
(6) separating, collecting, and drying at 120 deg.C;
(7) weighing a sample, wherein the weight is 457 g; sample SEM is fig. 2.
Test example 1 the same rubber formulation, mixed rubber with different fillers added, and the properties were compared.
In this comparative example, a conventional natural rubber formulation was used, and the reinforcing fillers were compared as follows: a carbon nanotube and carbon black composite filler prepared in situ by the invention (adopting the product of example 2); b conventional carbon black without carbon nanotube treatment (Cabot N220 carbon black), the specific formulation is shown in Table 1.
TABLE 1 mixing formula of natural rubber
The specific operation is as follows: the two natural rubber compound formulas are plasticated on an open mill, banburied by an internal mixer, mixed by the open mill, placed, and vulcanized on a flat vulcanizing machine at 150 ℃ and 10MPa for 15 minutes after the final rubber compound is discharged by the same equipment and process, and then the respective mixed vulcanized rubber can be obtained.
The vulcanized rubbers obtained from A and B were subjected to physical property tests, and the test results obtained are shown in Table 2.
TABLE 2 vulcanizate physical Properties test results
As can be seen from Table 2, under the same formulation conditions, the physical properties such as tensile strength, tear strength, elongation at break and the like of the rubber compound A are obviously improved compared with those of the rubber compound B; the Mooney viscosity of the rubber compound A is obviously reduced compared with that of the rubber compound B; the above shows that the dispersion degree of the filler of the A rubber compound in the rubber is greatly improved; the vulcanization process of the rubber compound A is obviously shortened, the vulcanization efficiency is improved, and a large amount of energy consumption can be saved; the tan delta of the A compound vulcanized rubber at the temperature of 25 ℃ is obviously reduced, which shows that the A compound vulcanized rubber has lower hysteresis loss and can be used for manufacturing a tread to have lower rolling resistance.
Test example 2
In this comparative example, a plastic PE formulation was used, and the conductive filler comparisons were: c, preparing the carbon nano tube and carbon black composite filler in situ; d the traditional carbon black without carbon nanotube treatment (N220 carbon black of Cabot corporation), E the conductive filler imported from Czech carbon black (Czech highly conductive carbon black CHEZACARB type B), the specific formulation is shown in Table 3.
TABLE 3 PE Plastic formulation
The specific operation is as follows: C. d and E, under the condition of the same equipment and process, uniformly mixing the materials, adding the mixture into a double-screw extruder, controlling the temperature of a machine head to be 180-220 ℃, and extruding the plastic adhesive tape.
C. The conductivity tests were carried out on the plastic specimens obtained in D and E, and the test results are shown in Table 4. TABLE 4 Performance data
As can be seen from Table 4, under the same formulation conditions, the physical properties such as volume resistance, surface resistance, elongation at break and the like of the C plastic sample strip are obviously improved compared with those of the D plastic sample strip, and particularly, the resistance is different by about 4 to 5 orders of magnitude; the composite filler has extremely obvious advantages and stability, and can completely replace foreign imported products E from data.
In summary, according to the above technical solution of the present invention, by blending a certain amount of carbon nanotubes into a liquid raw material and then performing an in-situ preparation method, while carbon black is generated from the carbon black raw material at a high temperature, a perfect grape-string-like structure is prepared, in which the carbon nanotubes pre-mixed are used as main lines and the generated carbon black particles are used as beads, and the grape-string-like structure has good conductive and reinforcing effects and can completely replace imported superconducting carbon black.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (8)
1. A carbon nanotube and carbon black superstrong compound filler in situ preparation method, mix carbon nanotube into prepare carbon black liquid raw materials after mixing, prepare carbon nanotube and carbon black superstrong compound filler in situ through the high temperature, while the carbon black raw materials produce the carbon black through the high temperature, prepare and use carbon nanotube that mix in advance as the thread, use the perfect grape bunch structure of the beaded form of carbon black particle produced; the method comprises the following specific steps:
(1) mixing carbon nanotubes into a liquid raw material for preparing carbon black, wherein the weight ratio of the carbon nanotubes to the liquid raw material is carbon nanotubes: the liquid raw material is 10:100-50: 100;
(2) heating the mixture of the carbon nano tube and the liquid raw material to 50-110 ℃ for dehydration;
(3) preheating the mixture of the carbon nano tube and the liquid raw material to 600-650 ℃, and atomizing and spraying the mixture into the reaction furnace;
(4) after the graded heating, the three-stage heating is carried out; preparing the super-strong composite filler of the carbon nano tube and the carbon black in situ at the temperature of 1400-1700 ℃;
(5) the quenching section sprays water to cool to 800-860 ℃, and the water is cooled to 230-240 ℃ in three stages;
(6) separating, collecting and drying at 70-120 ℃;
the particle diameter range of the carbon nano tube is 50nm-500 mu m.
2. The in-situ preparation method of the carbon nanotube and carbon black super-strong composite filler according to claim 1, characterized in that the liquid raw material for preparing the carbon black is one or a mixture of coal tar, pitch, decant oil and ethylene tar, wherein the decant oil is a simply treated catalytic oil slurry during catalytic cracking reaction, the decant oil has high density and low hydrogen content, and the content of saturated hydrocarbon and aromatic hydrocarbon is 50% -60%.
3. The in-situ preparation method of the carbon nanotube and carbon black super-strong composite filler according to claim 1, wherein the carbon nanotube is one or a mixture of a single-walled carbon nanotube, a double-walled carbon nanotube and a multi-walled carbon nanotube.
4. The in-situ preparation method of the carbon nanotube and carbon black super-strong composite filler according to claim 1, wherein the particle size of the carbon nanotube ranges from 100nm to 50 μm.
5. The in-situ preparation method of the carbon nanotube and carbon black super-strong composite filler according to claim 4, wherein the particle size of the carbon nanotube ranges from 1 μm to 20 μm.
6. The in-situ preparation method of the carbon nanotube and carbon black super-strong composite filler according to claim 1, wherein the temperature of the mixture of the carbon nanotube and the liquid raw material is increased to 80-90 ℃.
7. The carbon nanotube and carbon black super composite filler obtained by the in-situ preparation method of carbon nanotube and carbon black super composite filler according to any one of claims 1 to 6 has a perfect grape-string-like structure with pre-mixed carbon nanotubes as main lines and the generated carbon black particles in the form of beads.
8. The carbon nanotube and carbon black super composite filler obtained by the in-situ preparation method of the carbon nanotube and carbon black super composite filler according to any one of claims 1 to 6 is used for electric conduction, heat conduction and reinforcement of plastic and rubber products.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711279620.3A CN108047495B (en) | 2017-12-06 | 2017-12-06 | In-situ preparation method of carbon nano tube and carbon black super-strong composite filler |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711279620.3A CN108047495B (en) | 2017-12-06 | 2017-12-06 | In-situ preparation method of carbon nano tube and carbon black super-strong composite filler |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108047495A CN108047495A (en) | 2018-05-18 |
| CN108047495B true CN108047495B (en) | 2020-03-10 |
Family
ID=62122451
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711279620.3A Active CN108047495B (en) | 2017-12-06 | 2017-12-06 | In-situ preparation method of carbon nano tube and carbon black super-strong composite filler |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108047495B (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110721699B (en) * | 2018-07-16 | 2023-01-13 | 中国石油化工股份有限公司 | Gasoline hydrodesulfurization catalyst and preparation method and application thereof |
| CN110721692B (en) * | 2018-07-16 | 2023-01-13 | 中国石油化工股份有限公司 | Gasoline adsorption desulfurization catalyst and preparation method and application thereof |
| CN109467783A (en) * | 2018-11-08 | 2019-03-15 | 上海应用技术大学 | A kind of polyethylene/carbon nanotube conducting material and preparation method thereof |
| CN109651700A (en) * | 2018-11-28 | 2019-04-19 | 江苏松上科技有限公司 | A kind of permanent conductive plastics particle and preparation method thereof |
| CN110330794A (en) * | 2019-04-08 | 2019-10-15 | 绍兴文理学院元培学院 | A kind of pressure sensitive composite material and preparation method thereof in flexible sensor |
| CN111795764B (en) * | 2019-04-09 | 2021-11-09 | 绍兴文理学院元培学院 | Sandwich type large-area high-density flexible array sensor and preparation method thereof |
| CN110684375B (en) * | 2019-11-01 | 2020-11-17 | 青岛科技大学 | Pyrolytic carbon black modification method for loading carbon nano tube on surface of pyrolytic carbon black |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104868125A (en) * | 2015-04-21 | 2015-08-26 | 深圳市三顺中科新材料有限公司 | Carbon nano tube and carbon black composite dispersing liquid and preparation method thereof |
| CN105419096A (en) * | 2015-12-21 | 2016-03-23 | 赵社涛 | Method for producing carbon black composite powder material |
| CN106170880A (en) * | 2014-04-14 | 2016-11-30 | 英默里斯石墨及活性炭瑞士有限公司 | Amorphous carbon coating from the carbonaceous particle of the dispersion including amphiphilic organic cpd |
| WO2017068147A1 (en) * | 2015-10-21 | 2017-04-27 | Imerys Graphite & Carbon Switzerland Ltd. | Carbonaceous composite materials with snowball-like morphology |
| CN107383419A (en) * | 2017-08-28 | 2017-11-24 | 中创奕龙科技股份有限公司 | A kind of CNT and cracking black carbon composite material and preparation method thereof |
-
2017
- 2017-12-06 CN CN201711279620.3A patent/CN108047495B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106170880A (en) * | 2014-04-14 | 2016-11-30 | 英默里斯石墨及活性炭瑞士有限公司 | Amorphous carbon coating from the carbonaceous particle of the dispersion including amphiphilic organic cpd |
| CN104868125A (en) * | 2015-04-21 | 2015-08-26 | 深圳市三顺中科新材料有限公司 | Carbon nano tube and carbon black composite dispersing liquid and preparation method thereof |
| WO2017068147A1 (en) * | 2015-10-21 | 2017-04-27 | Imerys Graphite & Carbon Switzerland Ltd. | Carbonaceous composite materials with snowball-like morphology |
| CN105419096A (en) * | 2015-12-21 | 2016-03-23 | 赵社涛 | Method for producing carbon black composite powder material |
| CN107383419A (en) * | 2017-08-28 | 2017-11-24 | 中创奕龙科技股份有限公司 | A kind of CNT and cracking black carbon composite material and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108047495A (en) | 2018-05-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108047495B (en) | In-situ preparation method of carbon nano tube and carbon black super-strong composite filler | |
| Wang et al. | Electromagnetic interference shielding MWCNT-Fe3O4@ Ag/epoxy nanocomposites with satisfactory thermal conductivity and high thermal stability | |
| Mittal et al. | Chemical vapor deposition-based grafting of CNTs onto basalt fabric and their reinforcement in epoxy-based composites | |
| KR101682007B1 (en) | Preparation method of graphene | |
| Al-Saleh et al. | A review of vapor grown carbon nanofiber/polymer conductive composites | |
| KR101135672B1 (en) | Conductive thermosets by extrusion | |
| Uddin et al. | Enhanced microwave absorption from the magnetic-dielectric interface: a hybrid rGO@ Ni-doped-MoS2 | |
| CN102321379B (en) | Electroconductive graphene/polymer composite material | |
| Zhang et al. | Exfoliation and defect control of graphene oxide for waterborne electromagnetic interference shielding coatings | |
| CN108864773B (en) | Modified spiral carbon nanofiber, preparation method and application thereof, and rubber composite material | |
| US20150340117A1 (en) | Method for producing conductive film | |
| CN105255113A (en) | Polymer composite material with double-network structure and preparation method thereof | |
| Khan et al. | Reinforcement effect of acid modified nanodiamond in epoxy matrix for enhanced mechanical and electromagnetic properties | |
| WO2020025025A1 (en) | Conductive liquid silicone rubber and preparation method and use thereof | |
| CN105384962A (en) | Carbon black composite material | |
| CN111170309A (en) | Preparation method of ultra-long few-wall carbon nanotube array | |
| CN103937265A (en) | Graphene-silicone rubber composite material and preparation method thereof | |
| CN112210130A (en) | Semi-steel base rubber material using carbon nanotube composite masterbatch and preparation method thereof | |
| Bai et al. | Controllable synthesis of leaflet-like poly (3, 4-ethylenedioxythiophene)/single-walled carbon nanotube composites with microwave absorbing property | |
| CN105602066B (en) | A kind of polyethylene/nylon composite and preparation method thereof | |
| Chen et al. | Growth of single-crystal α-MnO2 nanorods on multi-walled carbon nanotubes | |
| Zhang et al. | Electromagnetic interference shielding property of polybenzoxazine/graphene/nickel composites | |
| KR101135055B1 (en) | Fabrication method of polymer/carbon nanotube composite with good electromagnetic interference shielding efficiency and polymer/carbon nanotube composite using the same | |
| CN102690528B (en) | Method for preparing polymer-base conductive composite material by melt blending | |
| CN112080106B (en) | Graphene-carbon nanotube/epoxy resin nonlinear conductive composite material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |